Lithium-ion Batteries

Materials and Applications

Edited by

Inamuddin1,2,3, Rajender Boddula4, Mohammad Faraz Ahmer5 and

Abdullah M. Asiri1,2

1
Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia
2
Centre of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah 21589,
Saudi Arabia
3
Department of Applied Chemistry, Faculty of Engineering and Technology, Aligarh Muslim University,
Aligarh-202 002, India
4
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and
Technology, Beijing 100190, PR China
5
Department of Electrical Engineering, Mewat College of Engineering and Technology, Mewat-122103,
India
Copyright © 2020 by the authors

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Materials Research Foundations
Volume 80 (2020)
ISSN 2471-8890 (Print)
ISSN 2471-8904 (Online)

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10 9 8 7 6 5 4 3 2 1
 Table of Contents
Preface

Fabrication of TiO2 Materials for Lithium-ion Batteries

Chang-Seop Lee, Hasan Jamal.......................................................................................... 1

A Brief History of Conducting Polymers Applied in

Lithium-ion Batteries
Suzhe Liang, Yonggao Xia, Peter Müller-Buschbaum, Ya-Jun Cheng.......................... 28

2D Transition Metal Dichalcogenides for Lithium-ion Batteries

S.V. Prabhakar Vattikuti ................................................................................................. 63

Metal Sulphides for Lithium-ion Batteries

Udaya Bhat K., Sunil Meti, C. Prabukumar, Suma Bhat ................................................ 91

Magnetic Nanomaterials for Lithium-ion Batteries

Mine Kurtay, Haydar Göksu, Husnu Gerengi, Hakan Burhan,
Mohd Imran Ahamed, Fatih Şen ................................................................................... 123

Recent Advances in Nanomaterials for Li-ion Batteries

K. Chandra Babu Naidu, N. Suresh Kumar, Rajender Boddula, S. Ramesh,
Ramyakrishna Pothu, Prasun Banerjee, M.S.S.R.K.N. Sarma, H. Manjunatha,
B. Kishore ..................................................................................................................... 148

Silicon Materials for Lithium-ion Battery Applications

Sarigamala Karthik Kiran, Martha Ramesh, Shobha Shukla and Sumit Saxena .......... 161

Keyword Index
About the Editors
 Preface
Lithium-ion batteries (LIBs) are one of the most important energy storage systems to
cope with the energy cricis challenges faced in electronics and automobile industries.
Lithium-ion batteries exhibit high voltage window, high energy density, low-rate
discharge, and long life span. Lithium-ion batteries are preferred to use in consumer
applications such as phone batteries, laptops, and hybrid electric vehicles, etc.
However, the development of lithium-ion batteries with high power density is
challenging. Therefore, research efforts devoted to designing high-performance
electrode materials and electrolytes for lithium-ion battery applications. The research in
the area of lithium-ion batteries has been in progress towards the development of
practically viable technologies. The lithium-ion batteries have an incredible future, but
still more research and development studies are needed to commercialize them at a
large performance scale.
The book on “Lithium-ion Batteries: Materials and Applications” provides a
comprehensive overview of lithium-ion batteries and their applications in consumer
and industrial sectors, including safety and reliability features. This book introduces
systematic and broad coverage of the properties, theoretical insights, and experimental
pieces of evidence from laboratory scale to commercial scale applications of lithium-
ion batteries. The book chapters summarize the mechanisms, principles, analytical
insights, fundamental concepts and recent advances of anodes, cathodes, electrolytes,
separators, binders, fabrication of device assemblies, electrochemical performance, etc.
This book delivers information on basic research, case studies, and lithium-ion batteries
applications. It is a well structured and essential resource for scientists, undergraduate
and postgraduate students, faculty members, R&D professionals, energy chemists, and
industrial experts.

Inamuddin1,2,3, Rajender Boddula4, Mohammad Faraz Ahmer5

and Abdullah M. Asiri1,2
1
Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia
2
Centre of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah 21589, Saudi Arabia
3
Department of Applied Chemistry, Faculty of Engineering and Technology, Aligarh Muslim University, Aligarh-
202 002, India
4
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and
Technology, Beijing 100190, PR China
5
Department of Electrical Engineering, Mewat College of Engineering and Technology, Mewat-122103, India
Lithium-ion Batteries - Materials and Applications Materials Research Forum LLC
Materials Research Foundations 80 (2020) 1-27 https://doi.org/10.21741/9781644900918-1

Chapter 1

Fabrication of TiO2 Materials for

Lithium-ion Batteries

Chang-Seop Lee 1*, Hasan Jamal1

1
Department of Chemistry, Keimyung University, Daegu 42601, Korea
*[email protected]
Abstract
Among transition metal oxides, TiO2 based materials are quite promising and extensively
studied in lithium-ion batteries (LIBs) owing to their high safety, low cost, and low
volume expansion (< 4%). In the present study, nanocomposites of TiO2 (nanoparticles,
nanorods, nanofibers) with graphene (TiO2@rGO) were successfully synthesized by
hydrothermal and calcination treatment. Coaxial SnO2@TiO2 nanotube arrays
(SnO2@TNTs) were assembled through electrochemical fabrication technique using
pristine TiO2 nanotube arrays (TNTs) and metallic-Sn. All as-synthesized products were
applied as negative materials for LIBs. Their physicochemical properties were
investigated via scanning and transmission electron microscope (SEM/TEM), X-ray
diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy
and Brunauer–Emmett–Teller (BET). Electrochemical testing was performed with
galvanostatic charge/discharge system. TiO2 nanoparticles nanocomposites with rGO
exhibited rate capacity of 155 mAhg-1 at C-rate of 0.5 C. After applying a high C-rate of
20 C, its rate capability was 109 mAhg-1 at 0.5 C, showing capacity loss of 30 %.
Reversible capacity delivered by SnO2@TNTs was 113 µA h cm-2 at current density of
100 µA cm-2 after 50 cycles, higher than that by pristine TNTs (51.6 µA h cm-2).
Keywords
TiO2 Nanostructure, Graphene, Lithium-Ion Batteries, TiO2 Nanotube Arrays,
Hydrothermal, Electrochemical Fabrication

Contents

1. Introduction................................................................................................3

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2. Synthesis of TiO2 /graphene nanocomposites and metal oxides core-

shells SnO2@TiO2 nanotube hybrids..................................................................6
2.1 Preparation of TiO2 NRDS ..................................................................6
2.2 Synthesis of TiO2 NFBS ......................................................................6
2.3 Synthesis of TiO2 nanocomposites with graphene ..............................6
2.4 Synthesis of coaxial SnO2@TiO2 nanotube hybrids ...........................7
3. Fabrication of cell for electrochemical characterization .......................8
3.1 Electrochemical measurements for TiO2/graphene
nanocomposite .....................................................................................8
3.2 Electrochemical tests for coaxial SnO2@TiO2 nanotube
hybrids .................................................................................................8
4. Characterization of TiO2/graphene nanocomposites .............................8
4.1 TiO2 /graphene nanocomposites ..........................................................8
4.1.1 SEM .....................................................................................................8
4.1.2 TEM ...................................................................................................10
4.1.3 XRD ...................................................................................................12
4.1.4 Raman ................................................................................................13
4.1.5 BET ....................................................................................................14
4.1.6 EDX ...................................................................................................15
4.2 Electrochemical Testing ....................................................................15
5. Characterization of coaxial SnO2@TiO2 nanotube hybrids...............18
5.1 Coaxial SnO2@TiO2 nanotube hybrids .............................................18
5.1.1 SEM & TEM......................................................................................19
5.1.2 XRD ...................................................................................................21
5.1.4 Electrochemical testing ......................................................................21
Conclusion...........................................................................................................23
Acknowledgement ..............................................................................................24
References ...........................................................................................................24

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Prefix Symbol for Prefix

TiO2 nanoparticles TiO2 NPAS
TiO2 nanorods TiO2 NRDS
TiO2 nanofibers TiO2 NFBS
TiO2 nanoparticles/rGO TiO2 NPAS@rGO
TiO2 nanorods/rGO TiO2 NRDS@rGO
TiO2 nanofibers/rGO TiO2 NFBS@rGO

1. Introduction
With increasing development of portable electronics, solar energy, wind energy, and
hybrid/full electric vehicles (EVs), stationary energy storage devices are stringently
needed [1,2]. Rechargeable LIBs are more advanced energy storage systems than other
battery technologies due to their higher volumetric and gravimetric energy density.
Hybrid vehicles account for 3% of all cars today. However, it has been predicted that
their number will increase rapidly in the coming years [3]. Utilizing EVs instead of
traditional combustion engine can significantly reduce pollution. Thus, LIBs are
anticipated to have a very positive effect on sustainable-energy economy and the
environment [4,5].
The anode is the key part in LIBs. It performs a critical role in determining the capacity
of the device. According to previous studies [6,7], an ideal anode should meet the
following conditions: (i) exposed large surface area offering more channels for Li-
insertion, (ii) low volume expansion for lithiation and de-lithiation essential for stable
cycling, (iii) low intrinsic resistance which supports fast lithiation and de-lithiation, (iv)
large pore size and shorter path length that favor the fast diffusion of Li-ions which is
paramount for superior rate capability, (v) low lithium intercalation potential, (vi) cheap
price, and (vii) environmental benignity. Based on the mechanism of lithium storage,
negative material for LIBs can be classifieds into the succeeding classes: (i) carbon
related materials like graphite, graphene, amorphous carbon, and carbon nanotube; (ii)
alloy/dealloy materials such as Si, Al, Bi, Sn, and Ge; (iii) transition metal oxides (MxOy,
M = Ni, Co, Cu, Mn, Fe, etc.); and 4) metal nitrides, metal sulphides, and metal
phosphides [8–10]. Figure 1 shows the capacity of some potential anode materials and
corresponding potential versus Li/Li+. Overall, transition metal oxides have relatively
higher capacity and potential than other electrode materials.

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Figure 1. Comparison of some potential anode materials for lithium ion batteries [18].

Among transition metal oxides, TiO2 has been extensively investigated as negative
candidate for LIBs due to its environmental benignity, corrosion resistivity, abundant
availability, high safety, and non-toxic nature. TiO2 exhibits high discharge voltage
plateau (> 1.7 V vs. Li/Li+) and outstanding cycling reversibility [11,12]. In addition,
TiO2 undergoes very small volume expansion (< 4 %) at the time of lithium insertion and
extraction process, prompt to longer cyclibility and resilience [13]. These characteristics
make TiO2 a favorable negative material for high energy storage [14–16].
However, TiO2 has some limitations such as poor rate capability, low capacity, and low
electrical conductivity. Reversible lithiation-delithiation in TiO2 occurs according to the
following reaction [17].

𝑥𝐿𝐿 + + 𝑇𝑇𝑂2 + 𝑥𝑒 − ↔ 𝐿𝐿𝑥 𝑇𝑇𝑂2 (1)

Where, x ranges from 0 to 1 largely depending on the morphology, polymorph, and

particle size of TiO2. Hence, the discharge capacity of TiO2 largely relies on structural
parameters of TiO2. Table 1 outlines structural and lithiation quantity of various TiO2

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polymorphs [18]. Of these, TiO2 anatase, rutile, brookite, and bronze phases for LIBs
have been outlined. However, TiO2 has some major drawbacks such as low electrical
conductivity (10-12 - 10-7 s cm-1) and low lithium-ion diffusion coefficient (10-15 - 10-9 cm2
s-1), leading to poor rate capability and thus to the unavailability of open channels for Li-
ion insertion [19–21].

Table 1. Structural and electrochemical properties of various TiO2 polymorphs [13].

Structure Space group Density Lattice Lithiation quantity (mole)

(g cm-3) parameter
values Bulk Nano

Rutile Tetragonal 4.13 a = 4.59, 0.1

P42/mnm c = 2.96 0.85
Anatase Tetragonal 3.79 a = 3.79, 0.5
141/amd c = 9.51 1.0
a = 9.17,
Brookite Orthorhombic 3.99 b = 5.46, 0.1 1.0
Pbcv c = 5.14
a = 12.17,
TiO2–B Monoclinic 3.64 b = 3.74, 0.71 1.0
(bronze) C2/m c = 6.51,
ꞵ = 107.298
a = 4.52,
TiO2–II Orthorhombic 4.33 b = 5.5,
(Columbite) Pbcn c = 4.94
TiO2-H Tetragonal 3.46 a = 10.18,
(hollandite) 14/m c = 2.97
a = 4.64,
TiO2-III Monoclinic b = 4.76,
(baddeleyite) P21/c c = 4.81,
ꞵ = 99.28
a = 4.9,
TiO2-R Orthorhombic 3.87 b = 9.46,
(ramsdellite) Pbmn c = 2.96
TiO1-O I Orthorhombic

TiO2–O II Orthorhombic

Due to aforementioned shortcomings of TiO2 anodes, several techniques have been

evolved to address these issues. Four approaches have been suggested to improve the

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electrochemical performance of TiO2 electrode. The first approach is to crop electronic

and ion transport length by fabricating different types of TiO2 nanostructures. The second
approach is by reducing charge transfer resistance, compensating volume expansion, and
improving lithium-ion diffusion coefficient by coating or engulfing with carbonaceous
materials. The third approach is by restraining nearly zero volume change during the
insertion of Li+ ions by fabricating metal oxide core-shell nanocomposites with TiO2
materials. The fourth approach focuses improving the intrinsic nature and increasing the
internal surface area opens more reactive sites for Li-ion transport by doping with other
atom or ions.

2. Synthesis of TiO2 /graphene nanocomposites and metal oxides core-shells

SnO2@TiO2 nanotube hybrids

2.1 Preparation of TiO2 NRDS

Titanium sulfate (2.0 g) was first dispersed in 40 ml of deionized water (DI). Then 20 ml
ammonia solution was dissolved drop-wise for 1 h in the preceding solution. The
obtained mixture was transferred into autoclave, heated to 180 °C and then kept for 24 h.
Afterward, the obtained products were thoroughly washed with water and dried at 60 °C
for 24 h. After calcination [13], anatase phase of TiO2 NRDS were obtained.

2.2 Synthesis of TiO2 NFBS

Typically, 0.5 g of TiO2 anatase powder (particle size: 25 nm) was transferred into Teflon
reactor and suspended in 65 ml of 10 M sodium hydroxide solution. The Teflon reactor
was sealed and installed into a stainless steel autoclave for 22 h at 190 °C. PH 7 was
obtained after washing with DI water. The collected sample was dried at 60 °C for 12 h.
The obtained sample powder was supplemented with sodium ions by stirring in 0.1 M
hydrochloric acid and washed with DI water until pH 7 was obtained. After drying the
sample in vacuum at 60 °C, the anatase phase of TiO2 NFBS were achieved by annealing
in Ar flow at 800 °C for 1h.

2.3 Synthesis of TiO2 nanocomposites with graphene

First, an aqueous solution (200 ml, 2 mg/ml) of graphene oxide (GO) was dispersed with
1.2 g of anatase TiO2 NPAS (nanopowder with particle size of 25 nm, Sigma-Aldrich).
The obtained sample was refluxed at 90 °C for 2 h, then cooled at room temperature.
After cooling, sample was centrifuged and washed with H2O and C2H5OH. In obtained
products, 20 ml C2H5OH and 10 ml distilled H2O were stirred and autoclaved at 180 °C
for 24 h in 500 ml Teflon lined autoclave. To obtain highly crystalline composites,

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samples were calcinated in argon (Ar) flow at 400 °C for 4 h. Similar procedure was used
to obtain nanocomposites of other TiO2 nanostructures with graphene [15]. Schematic
representation for the fabrication of TiO2@rGO nanocomposites are displayed in Fig. 2.

Figure 2. Synthesis procedure of TiO2/graphene nanocomposites [13].

2.4 Synthesis of coaxial SnO2@TiO2 nanotube hybrids

TNTs were produced in electrolyte solution (ethylene glycol, 0.25 wt% NH4F, 2 vol%
H2O) for 15-30 min at 50 V. To obtain crystalline form of TiO2, sample was annealed at
450 °C for 1 h under air atmosphere. SnO2-core layers were grown using sequential
fabrication without compromising the pore structure.
For electrochemical deposition process, a conventional two-electrode system (Pt as
counter electrode, annealed TNTs as working electrode) PARSTAT 2273 was used. The
electrolyte consisted of 18 mM SnCl2.H2O buffered with 50 mM Na3C6H5O7.2H2O.
Metallic Sn deposition relied on regulated pulse signals in microsecond span. Firstly, for
short time current negative pulse was activated for the deposition of Sn. Secondly, to
discharge the barrier layer capacitance, an extended positive impulse was imposed.
Finally, for the conversion of metallic Sn to SnO2, previously prepared products were
annealed in air atmosphere for 90 min at 500 °C. Systematic illustration for the
fabrication of SnO2@TNTs hybrids can be found in Fig. 12.

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3. Fabrication of cell for electrochemical characterization

3.1 Electrochemical measurements for TiO2/graphene nanocomposite

For electrochemical evaluation, electrodes were prepared with active material powder (80
wt%), carbon black as conducting agent (10 wt%), and polyvinylidene fluoride (PVDF,
10 wt%) as a binder. They were dissolved in N-methylpyrrolidone (NMP) and stirred for
30 min. The prepared slurry was coated onto copper foil using “doctor blade” technique.
After evaporating the solvent at 80 °C under vacuum, coin cells (CR-2032) were
fabricated under Ar (O2 and H2O content < 1 ppm). The electrolyte was 1 M Lithium
hexafluorophosphate (LiPF6) containing in ethylene carbonate (EC) dimethyl carbonate
(DMC) 1:1 vol. ratio. Fabricated coin cells were charged and discharged
galvanostatically (Neware Co, Ltd, Shenzhen, China) at different C-rates between 1.0 and
3.0 V.

3.2 Electrochemical tests for coaxial SnO2@TiO2 nanotube hybrids

Electrochemical performance was investigated by fabricating coin cells in Ar filled glove
box (MBRAUN). Active material and Li-foil were used as a working and reference
electrode. A 1 M LiPF6 consists of (EC) and diethyl carbonate (DEC) with a volume
ration of 1:1, used as a electrolyte. Celgard 2300 was used as a separator. The assembled
cells were charged/discharged galvanostatically at various current rates. Impedance
spectra measurements were carried out at several frequencies by implementing 10 mV
AC voltage amplitude signals.

4. Characterization of TiO2/graphene nanocomposites

4.1 TiO2 /graphene nanocomposites

Based on morphology, different types of TiO2 were synthesized using titanium sulphate
and commercial TiO2 nanopowder as precursor. Nanocomposites of TiO2/graphene were
synthesized with morphologically different forms of TiO2 nanostructures (nanoparticles,
nanorods, and nanofibers) through hydrothermal and calcination approach. All
nanocomposites of TiO2 with graphene were reduced in Ar at 400 °C for 4 h.

4.1.1 SEM
SEM images of TiO2 before synthesis of TiO2 nanocomposites (nanoparticles, nanorods,
nanofibers) with graphene are shown in Figs. 3a-3e. All TiO2 nanostructures had distinct
morphology as shown in Figs. 3a-3e. SEM images of TiO2@rGO nanocomposites after
calcination at 400 °C for 4 h under Ar are presented in Figs. 4a-4f. After calcination

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under Ar atmosphere, morphologies of all nanocomposites were preserved with little

agglomeration (Figs. 4a-4f).

Figure 3. FE-SEM images of anatase TiO2 before synthesis of nanocomposite with

graphene. (a) TiO2 NPAS, (b, c) TiO2 NRDS, (d, e) TiO2 NFBS [13].

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Figure 4. FE-SEM images after fabricating nanocomposite of anatase TiO2 with

graphene (TiO2@rGO). (a, b) TiO2 NPAS@rGO, (c, d) TiO2 NRDS@rGO, (e, f) TiO2
NFBS@rGO [13].

4.1.2 TEM
TEM images of TiO2 nanostructures before fabrication of nanocomposite with graphene
are depicted in Figs. 5a-5c. TiO2 NPAS and TiO2 NRDS had average diameters of ~30
nm and ~180 nm, respectively. Lengths of TiO2 NFBS were up to several hundred

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nanometers as seen in Figs. 5a-5c.TEM images of TiO2@rGO nanocomposites after

calcination at 400 °C for 4 h under Ar are illustrated in Figs. 6a-6f. High-resolution TEM
images of TiO2 nanocomposites with graphene are shown in Figs. 6b, 6d, and 6f
indicated that anatase TiO2 had a well-defined crystal structure. The d-spacing of 0.353
nm is in well agreement with (101) anatase plane of TiO2 and that of 0.35 nm is in
agreement with (002) plane of graphene. TiO2 nanostructures were dispersed successfully
among graphene sheets after hydrothermal and calcination treatment as shown in Figs.
6a-6f. The successful dispersion of TiO2 between graphene layers provided high surface
area, thus endowing more reaction sites for lithium insertion and de-insertion.

Figure 5. HR-TEM images of anatase TiO2 before synthesis of nanocomposite with

graphene. (a) TiO2 NPAS, (b) TiO2 NRDS, (c) TiO2 NFBS [13].

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Figure 6. HR-TEM images after fabrication of nanocomposite of anatase TiO2 with

graphene (TiO2@rGO). (a, b) TiO2 NPAS@rGO, (c, d) TiO2 NRDS@rGO, (e, f) TiO2
NFBS@rGO [13].

4.1.3 XRD
TiO2 NRDS and TiO2 NFBS were annealed in Ar atmosphere for 1 h at 500 °C and 800
°C, respectively. XRD patterns of all TiO2 nanostructures before fabrication of

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nanocomposites with graphnen are depicted in Fig. 7a. TiO2 NRDS and TiO2 NFBS
underwent phase change into anatase crystalline form after annealing. Diffraction peaks
of all nanostructures are ascribed to tetragonal anatase TiO2 (JCPDS No. 21-1272).
After fabrication of nanocomposites TiO2@rGO were calcinated in Ar at 400 °C for 4 h.
XRD patterns of all nanocomposites after calcination are illustrated in Fig. 7b. GO
sample unveiled one characteristic peak (001) interlayer spacing, reflecting oxidation of
natural graphite into GO [15]. Diffraction intensities of TiO2@rGO nanocomposites were
improved after hydrothermal and calcination treatment, demonstrating increment in
crystallinity of TiO2. Notably, reflections related to graphene oxide or graphene were not
observed, suggesting small percentage of carbon in these nanocomposites.

Figure 7. XRD patterns of TiO2 nanostructures. (a) Before fabrication of nanocomposites

with graphene, (b) After fabrication of nanocomposites with graphene [13].

4.1.4 Raman
To obtain further evidence about the structure of as-prepared samples, Raman spectra
were collected. Results are shown in Fig. 8. Three consecutive Raman scattering peaks
within 300–700 cm-1 corresponded to TiO2 anatase vibrational modes [22]. The peak at
around 1351 cm-1 corresponded to k-point phonons of A1g and the peak at 1595 cm-1 G
band originated from E2g phonon of sp2 in TiO2@rGO nanocomposites [23]. As shown in
Table 2, intensity ratios of (ID/IG) of all nanocomposites suggested that TiO2
nanostructures were dispersed between graphene sheets [24]. These intensity ratios
(ID/IG) of TiO2@rGO nanocomposites compared to ID/IG of GO (0.81) indicated reduction
of GO [25].

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Table 2. ID/IG ratio of all nanocomposites characterized by Raman spectra [13].

Samples ID/IG
TiO2 NPAS@rGO 1.06
TiO2 NRDS@rGO 1.05
TiO2 NFBS@rGO 1.02

Figure 8. Raman spectra of TiO2 nanostructures after fabrication of nanocomposites with

graphene TiO2@rGO. Inset: Raman spectra of TiO2 NPAS before fabrication of
nanocomposite with graphene [13].

4.1.5 BET
Table 3 indicates N2 adsorption-desorption isotherms and similarly pore size distribution
of all TiO2 nanostructures before and after fabrication of nanocomposites with graphene.
From adsorption isotherm curves, TiO2 NPAS showed the highest specific surface area of
69.0 m2g-1 along pore size distribution of 10.3 nm as illustrated in Table. 3. TiO2 NFBS
had the lowest surface area of 10.9 m2g-1 with Barrett-Joyner-Halenda (BJH) pore
diameter of 11.6 nm (Table 3). BET and BJH of all nanostructures of TiO2 after
fabricating nanocomposites with graphene are shown in Table 3. After fabricating
nanocomposites with graphene, all nanostructures of TiO2 improved its surface area
owing to the contribution of graphene. Among TiO2@rGO nanocomposites, TiO2

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NPAS@rGO hold the highest surface area of 97 m2g-1 due to contribution of graphene as
shown in Table 3. Diffusion of lithium-ions largely depends on the surface area and pore
size distribution as large pore size and surface area would provide more open channels
for the transport of lithium ions throughout the TiO2@rGO nanocomposites. This is
favorable for application in LIBs. Homogeneous dispersion of graphene layers among
TiO2 nanostructures can serve as a bridge which is favorable for fast insertion of lithium-
ions.

Table 3. BET & BJH for all TiO2 nanostructures and their nanocomposites with
graphene [13].
Samples BET surface BJH pore Cumulative pore
area (m2g-1) diameter (nm) volume (cm3g-1)
TiO2 NPAS 69.0 10.3 0.2113
TiO2 NRDS 22.76 43.47 0.3010
TiO2 NFBS 10.9 11.68 0.0215
TiO2 NPAS@rGO 97.709 3.761 0.307
TiO2 NRDS@rGO 69.385 3.739 0.350
TiO2 NFBS@rGO 19.358 3.695 0.086

4.1.6 EDX
Fig. 9 shows EDX spectra of TiO2 nanocomposites fabricated with graphene after
calcination in Ar flow at 400 °C for 4 h. EDX spectra results revealed that TiO2
nanocomposites fabricated with graphene contained elements Titanium, Carbon, and
Oxygen. Particularly, there was no significant amount of Na in resulting nanocomposites,
confirming purity of the sample. EDX spectra results of TiO2 nanocomposites fabricated
with graphene also indicated that actual percentages of graphene in these nanocomposites
were around ~13%.

4.2 Electrochemical Testing

Electrochemical performances of as-prepared samples were tested as negative materials
for LIBs using lithium metal as reference electrodes fabricated into CR2032 coin cells.
Electrochemical performances of TiO2@rGO nanocomposites were investigated within
potential between of 1.0 and 3.0 V vs Li/Li+. Results of specific capacity and rate
capability relays on many aspects, including size and morphology of TiO2, type of

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bonding among TiO2 and graphene, and surficial properties (such as surface area, pore
size, porosity) of TiO2 nanostructures. Fig. 10a-10c display initial four cycles of
charge/discharge plateaus of TiO2@rGO nanocomposites at a C-rate of 0.5 C. In Figs.
10a and 10b, plateaus at about ~1.7 V and 2.0 V vs Li/Li+ were horizontal typical lithium
insertion and viceversa. They could be ascribed to lithium insertion and extraction
between TiO2 and Li0.5TiO2 [26–28]. The small capacity decay in initial few cycles
owing to irreversible reactions and formation of byproducts [29]. However, the profile for
TiO2 NFBS@rGO in Fig. 10(c) for lithium ion storage was distinct. The slope profile was
likely due to uniform results with a small capacity fade. Additionally, TiO2 NFBS@rGO
with small surface area and pore volume prompted a capacitive behavior owing to
improved lithium ion storage due to lithiation mechanism.

Figure 9. EDX spectra of TiO2 nanocomposites with graphene TiO2@rGO after

calcination in Ar at 400 °C for 4 h. (a) TiO2 NPAS@rGO, (b) TiO2 NRDS@rGO, (c)
TiO2 NFBS@rGO [13].

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Rate capabilities at various C rates for nanocomposites of TiO2@rGO are shown in Fig.
10d. Rate capabilities of TiO2 NRDS@rGO at 10 C and 20 C were higher than those of
TiO2 NPAS@rGO because TiO2 NAPS@rGO underwent high resistive path at high C-
rate. However, TiO2 NRDS/rGO supplied a low resistive path compared to TiO2
NPAS@rGO because rate capabilities of TiO2 NRDS@rGO were higher at higher C-rate.
TiO2 NRDS@rGO and TiO2 NFBS@rGO had rate capabilities of 42 mAhg-1 and 24
mAhg-1, respectively, at 20 C. However, after applying a high C-rate of 20 C, TiO2
NFBS@rGO delivered a rate capability of 64 mAhg-1 at C-rate of 0.5 C. This might be
due to a high contact area that could lead to large electrode/electrolyte contact area. The
high rate capacity TiO2 NRDS@rGO, could be as a result of lower aggregation and well
mixing of TiO2 NRDS among graphene that might retain a high contact area to supply
more reactive channels as a result of specific C-rate. Interestingly, TiO2 NPAS@rGO
after application of a high C-rate, rate capability at C-rate of 0.5 C recovered to 109
mAhg-1, unveiling a low structural stability owing to phase change from anatase into
rutile [28,30].

Figure 10. Charge-discharge profiles at 0.5 C (1C = 168 mAhg-1). (a) TiO2 NPAS@rGO,
(b) TiO2 NRDS@rGO, (c) TiO2 NFBS@rGO, (d) Rate performance at different current
densities of TiO2 NPAS@rGO, TiO2 NRDS@rGO, and TiO2 NFBS@rGO [13].

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Cyclic performances of all TiO2@rGO nanocomposites for 100 cycles at C-rate of 10 C

were estimated. Results are shown in Fig. 11. In the first 20 cycles, TiO2 NPAS@rGO
underwent high capacity loss and exhibited a discharge capacity of 52 mAhg-1 for 100
cycles. Solid-electrolyte interface (SEI) layer formation could be a main reason of
capacity fade in initial cycles. TiO2 NRDS@rGO delivered a discharge capacity of 53
mAhg-1 at C-rate of 10 C for 100 cycles, demonstrating good retention capability. TiO2
NRDS offered low resistive path at high C-rate, demonstrating that TiO2 NRDS would be
quite reversible for lithiation-delithiation. TiO2 NFBS@rGO displayed an initial
discharge capacity of 26 mAhg-1. After 100 cycles, they delivered a capacity of 30 mAhg-
1
. Gradual increase in capacity of electrode over time was caused by the mechanism of
Li-insertion and extraction process which would gently increase its porosity, leading to
more open channels and more lithium storage.

Figure 11. Discharge capacities of all TiO2@rGO nanocomposites for 100 cycles at 10 C
[13].

5. Characterization of coaxial SnO2@TiO2 nanotube hybrids

5.1 Coaxial SnO2@TiO2 nanotube hybrids

To improve quantum efficiency, conductivity and discharged capacity of TiO2 nanotube
arrays (TNTs) were encapsulated uniformly through electrochemical fabrication with

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SnO2 including exterior-interior space. To investigate Li+ storage capacity, synthesized

hybrid material was applied as negative material for LIBs.

Figure 12. Schematic illustration of SnO2@TiO2 coaxial nanotube hybrids (SnO2@TNTs)

and its benefit as an electrode material for Li-ion storage [31].

5.1.1 SEM & TEM

Morphological analyses results of coaxial Sn@TiO2 nanotubes (Sn@TNTs) and
SnO2@TiO2 nanotubes (SnO2@TNTs) synthesized via electrochemical fabrication
method are illustrated in Figs. 13a-13e. These synthesized materials showed a
hierarchical structure, in which TNTs were encapsulated uniformly from inside-outside in
a similar fashion. It was noticed that some walls of SnO2 were not firmly attached with
TNTs. In spite of that, a definite double-shell core structure was evident could be seen in
Fig. 13(a). The inset of Fig. 13(a) confirms successful annealing at 500 °C for 90 min in
air atmosphere. After annealing, desired crystalline phase was achieved without
sacrificing the original morphology.
From TEM images shown in Fig. 13(b), the thickness of doubled-shelled core structure
can be evaluated. Fig. 13(b) revealed that the thickness of multilayer was around 40 nm
and average thicknesses of TNTs and SnO2 were in the range of 10 to 20 nm. Apparently,
there was an inner space between walls of TNTs and metallic Sn possibly caused by
hydrogen evolution (2𝐻+ + 2𝑒 − → 𝐻2 ) during the deposition of Sn at high negative
potential. Irrespective of reaction time, thickness and attachment of SnO2 layer depended
on the concentration of Sn+2 as shown in Fig. 13c. TEM images further confirmed the
uniform tin deposition on TNTs. As shown in insets of Figs. 13b and 13d, layer
distribution and thickness of SnO2 were uniform; revealing that Sn deposition in the inner
space of TNTs was initiated simultaneously. Besides, boundary walls between TNTs and
tin were not well distinguishable as shown in Fig. 13d. This might be because good
fusion between the interface of TNTs and Sn could be achieved after particular heat

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treatment. The spot and ring patterns in selected area electron diffraction (SAED) image
indicated the existence of both materials (anatase and cassiterite). In Fig. 13e, the lattice
fringes with a period of (d = 0.33 nm) corresponds to the (110) lattice planes of SnO2.

Figure 13. Characterization of coaxial bimodal SnO2@TNTs and Sn@TNTs synthesized

by sequential electrochemical fabrication. (a) Top look of Sn nanotubes encapsulated in
TNTs and after annealing the sample (inset), (b) TEM images of coaxial Sn@TNTs
bottom view, mouth view (inset), (c) SnO2@TNTs images with tightly encapsulated SnO2
monolayer, (d) Segmented TEM image of SnO2@TNTs, with inset SAED pattern
indicating that the sample is polycrystalline, (e) Upper region HR-TEM image of
SnO2@TNTs and Fast Fourier Transform (FFT) revealing the existence of single
crystalline SnO2. (f) Before and after annealing of similar coaxial nanotube XRD
patterns (Ⅰ) and EDX patterns observed from SnO2@TNTs (Ⅱ) [31].

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5.1.2 XRD
Fig. 13f(I) shows XRD patterns of samples before and after annealing at 500 °C for 90
min in air atmosphere. After deposition of Sn on TNTs, most of diffraction peaks could
be well indexed to the anatase phase of TiO2 (JCPDS no. 21-1272). However, the two
diffraction peaks at 30.6° and 32° corresponded to ꞵ-Sn. After annealing at 500 °C for 90
min in air atmosphere, the existence of two low diffraction peaks at 26.8° and 34.05° was
evident. Most of metallic Sn was transformed into cassiterite SnO2 (JCPDS no. 41-1445).
5.1.3 EDX
EDX spectra of individual SnO2@TNTs are shown in Fig. 13f(Ⅱ). Peaks in the range of
3.4 - 4.1 KeV indicated the existence of Sn element. The weight ratio of Sn : Ti was 3 :
17.

5.1.4 Electrochemical testing

Fig. 14 shows the 5th cycle charge/discharge curves of pristine TNTs, Sn@TNTs, and
SnO2@TNTs. The profile of SnO2@TNTs demonstrated low voltage difference among
charge and discharge profile compared to that of pristine TNTs owing to its low energy
barrier for the conversion reaction. Notably prominent plateaus at around 1.75 V and 2.0
V were assigned to the biphasic equilibrium of TiO2, reflecting the fusion of SnO2
nanotubes. The fusion of SnO2 nanotubes also participates to harvest the TiO2 capacity
and offers Li-ions to move through the SnO2 layer without much hindrance at the stated
current density.

Figure 14. Fifth cycle galvanostatic charge/discharge profile of pristine TNTs,

Sn@TNTs, and SnO2@TNTs [31].

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Fig. 15 depicts discharge capacity for 50 cycles of pristine TNTs, Sn@TNTs, and
SnO2@TNTs at current density of 100 µA cm-2 (film thickness: ca.1.8 µm). SnO2@TNTs
electeode exhibited the first step discharge capacity of 469.8 µA h cm-2. The irreversible
fade in capacity in the first few cycles owing to the formation of SEI layer as a result of
irreversible reaction between Li-ion and electrolyte solvent molecules. Nevertheless, in
subsequent cycles, coulombic efficiency of more than 94 % was obtained, showing
reversible capacity of ~113 µA h cm-2 after 50 cycles which was higher than that of
pristine TNTs (51.6 µA h cm-2). Furthermore, unlike Sn@TNTs, the significant increase
in capacity of annealed sample (SnO2@TNTs) also attributed to enhanced fusion between
two components. Additionally, the fade in capacity of composite electrode indicated that
pulverization of Sn material in the nano-hetrostructure form was greatly increased.

Figure 15. Cyclic performance and coulombic efficiency vs. cycle number/n for pristine
TNTs, Sn@TNTs, and SnO2@TNTs at current density of 100 µA cm-2 [31].

It is notable to consider the interfacial chemical reaction at high temperature between

oxygen from the titanium dioxide lattice and metallic Sn. In this case, Ti undergoes
partial reduction from Ti4+ to Ti+3 or Ti2+, which promotes an oxygen deficient
environment among TiO2 and metallic Sn interface layer. The electronic conductivity of
TNTs increases with the increase in defect sites, which results in favorable charge
transport. To further verify the improvement in conductivity of SnO2@TNTs impedance
measurements were performed, as depicted in Fig. 16. In Fig. 16, it is evident that the

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charge-transfer resistance (Rct) of SnO2@TNTs in a wide potential window is smaller

than pristine TiO2. Furthermore, during the discharge process the decline in Rct of
SnO2@TNTs should be attributed to the slow reduction of Ti4+ to Ti+3 or Ti2+,
accompanied by the lithiation among TNTs. Which in turn, reduces the mobility gap and
electrical resistance.

Figure 16. Electrochemical impedance data of coaxial SnO2@TNTs and pristine TNTs
[31].

Conclusion
In this chapter, nanocomposites of TiO2 (nanoparticles, nanorods, nanofibers) with
graphene (TiO2@rGO) were synthesized using hydrothermal and calcination treatment.
Coaxial SnO2@TNTs were successfully assembled through electrochemical fabrication
technique using pristine TNTs and metallic Sn. Physicochemical characteristics of as-
synthesized products TiO2@rGO and SnO2@TNTs were analyzed using SEM, HR-TEM,
XRD, RAMAN, BET, and EDX spectroscopy. Their electrochemical performances were
carried out as negative materials for LIBs by fabricating half-cell for as-synthesized

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products using lithium metal as a counter electrode. Based on our results, the following
conclusions were drawn.
I. As a consequence of hydrothermal and calcination treatment, well mixing and
uniform dispersion of TiO2 nanostructure between graphene layers were obtained.
II. TiO2 NPAS@rGO delivered a rate capability of 155 mAhg-1 at C-rate of 0.5 C.
After applying a high C-rate of 20 C, rate capability was 109 mAhg-1 at 0.5 C,
showing capacity loss of 30 %.
III. TiO2 NRDS@rGO exhibited cyclic reversibility of 53 mAhg-1 after 100 cycles at 10
C with almost ~100 reversibility, indicating strong bonding between TiO2 NRDS and
graphene.
IV. TiO2 NFBS@rGO unveiled cycling reversibility of 30 mAhg-1 after 100 cycles at 10
C with a remarkable retention capacity owing to its expandable porosity during
lithiation and delithiation.
V. Coaxial SnO2@TNTS monohybrid were fabricated successfully using
electrochemical fabrication methodology, resulting in uniform deposition of metallic-
Sn inside/outside of TNTs.
VI. Enhanced fusion was achieved between TNTs and metallic Sn by annealing at 500
°C for 90 min in air atmosphere.
VII. SnO2@TNTs displayed reversible capacity of 113 µA h cm-2 after 50 cycles at
current density of 100 µA cm-2 compared to pristine TNTs (51.6 µA h cm-2). The
enhanced capacity was attributed to the addition of high capacity component and
subsequent sample annealing.

Acknowledgement
We acknowledge financial support from BISA Research Grant of Keimyung University
in 2019.

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Chapter 2

A Brief History of Conducting Polymers Applied in

Lithium-ion Batteries

Suzhe Liang1,2, Yonggao Xia2,3*, Peter Müller-Buschbaum1,4*, Ya-Jun Cheng2,5*

1
Lehrstuhl für Funktionelle Materialien, Physik-Department, Technische Universität München,
James-Franck-Str. 1, 85748, Garching, Germany
2
Ningbo Institute of Materials Technology & Engineering, Chinese Academy of Sciences, 1219
Zhongguan West Rd, Zhenhai District, Ningbo, Zhejiang Province, 315201, PR China
3
Center of Materials Science and Optoelectronics Engineering，University of Chinese Academy
of Sciences, 19A Yuquan Rd, Shijingshan District, Beijing 100049, P. R. China
4
Heinz Maier-Leibnitz Zentrum (MLZ), Technische Universität München, Lichtenbergstr. 1,
85748, Garching, Germany
5
Department of Materials, University of Oxford, Parks Rd, OX1 3PH, Oxford, United Kingdom
*[email protected], [email protected], and [email protected]
Abstract
As the most important portable power source at present, lithium-ion batteries still suffer
from several problems due to lack of perfect electrode materials. Conducting polymers,
owning both good electrical and physical properties, not only can composite with
conventional electrode materials to improve their electrochemical performance but also
are able to separately used as electrodes. In this chapter, the related studies of conducting
polymer applied in electrodes will be reviewed by a chronological approach. With the
unique perspective, this chapter will shed light on the future trends of the studies on
applications of conducting polymers in lithium-ion batteries.
Keywords
Conducting Polymer, Brief History, Cathode, Anode, Lithium-Ion Battery

Contents

1. Introduction..............................................................................................29
2. Applications on cathode materials .........................................................31
2.1 Before 2000: Emergence stage ..........................................................31

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2.2 2000-2006: Preliminary stage ............................................................32

2.3 Since 2007: Fast development stage..................................................33
3. Applications on anode materials ............................................................39
3.1 Before 2010: Emergence stage ..........................................................39
3.2 Since 2010: Rising stage....................................................................39
Conclusions & Outlooks ....................................................................................44
Acknowledgment ................................................................................................46
References ...........................................................................................................46

1. Introduction
Since the successful commercialization in the 1990s, the lithium-ion battery (LIB) has
become one of the most important power storage media in contemporary era [1-4].
Because of high output voltage, high energy density, long cycle life, and good rate
capability, lithium-ion batteries have dominated the portable electronics market and are
expanding the electric vehicles market in an astonishing speed [5, 6]. However, the first-
generation lithium-ion batteries no longer meet the gradually increasing demands of
higher energy density and more diverse operation environments [6, 7]. Generally, a
lithium-ion battery consists of the copper current collector, anode, electrolyte, separator,
cathode, aluminum current collector, and packing materials. Among these, the kind and
form of electrode materials can directly determine the final electrochemical performance
and applicability of batteries. At present, lithium transition metal oxides or phosphates,
such as LiCO2, LiMnO4, LiFePO4, or Li(NiCoMn)O2, constitute the cathode materials of
commercialized LIBs, while graphite-based materials act as anodes [8]. The relative-low
theoretical capacities of these existing electrode materials limit the gravimetric energy
density of LIBs under 250 Wh kg-1. To pursue higher energy density, it is very urgent to
implement an update revolution for the global LIB market. Naturally, designing and
fabricating high-performance electrode materials is the key point of this revolution. For
the cathode materials, how to improve the capacity and Coulombic efficiency is the
hotpot in both academia and industry, because many kinds of cathode materials have not
yet fully realized their potentials [9-11]. In terms of anode materials, various high-
capacity materials have been developed in academia, such as silicon (Si), phosphorus (P),
germanium (Ge), tin (Sn) and antimony (Sb)-based materials [12-14]. However, these
alloy-type anode materials suffer from sever volumetric changes during charge/discharge
processes, which leads to fast electrode pulverization and capacity fading. This is the

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major obstacle against the practical applications of these anode materials. In addition, the
emergence of flexible and wearable electronic devices also needs the new-type power
sources [15-18]. In recent years, organic/inorganic hybrid electrode materials attract
much attention due to their unique advantages compared to the conventional inorganic
electrodes [19-21]. The existence of an organic component can provide several new
characteristics to the traditional electrodes. Firstly, some organic molecules have a higher
theoretical capacity than that of traditional inorganic cathode materials, which benefits to
achieve higher energy density [22]. Secondly, the flexible and plastic organic materials
not only act as a buffer matrix to alleviate the volume expansion of alloy-type anodes but
also endow the flexibility to the electrodes [23]. Moreover, the utilization of organic
materials can relieve the pressure of large-scale use of transition metal as electrode
materials, leading to more sustainable and environment-friend development [24]. Among
numerous organic materials, conducting polymers (CPs) are ideal materials for hybrid
electrodes of lithium-ion batteries, due to good electrical conductivity and basic
properties of organic materials [20].
Conducting polymers or intrinsically conductive polymers, as the name implies, are a
kind of polymers which present electric conductivity [25, 26]. Their conductive nature is
derived from altering single and double carbon-carbon bonds in polymer chains.
Conducting polymer belongs to conjugated polymer, in which the sp2pz configuration of
carbon orbitals (in π-bonding) and the overlap of successive carbon atoms’ orbitals along
the backbone, leading to electron delocalization along the backbone of the polymer [27].
The delocalized electrons can freely move along the backbone of the chain, resulting in
the conductivity of the polymer. In 1976, Alan MacDiarmid, Hideki Shirakawa and Alan
J. Heeger discovered conducting polymers and introduced electrochemical doping into
conducting polymers to control the conductivity which ranged from insulative to fully
conductive in 1980 [27-29]. Therefore, they were awarded the Noble Prize in Chemistry
in 2002 “for the discovery and development of conductive polymers”. After about 40-
years development, conducting polymers have been successfully applied in various fields,
including transistors, sensors, memories, actuators/artificial muscles, supercapacitors, and
lithium-ion batteries [30-35].
Combined flexibility of polymer and conductivity of the metal, conducting polymers
have played a significant role in constructing advanced LIB electrode materials and
gained great progress. On the one hand, CPs can be directly applied as electrodes of Li-
ion batteries, due to the conversion redox mechanism [36]. On the other hand, more
commonly, CPs are composited with conventional inorganic materials to form hybrid
electrodes to enhance electrochemical performance. A verity of conductive polymers
have been developed for the applications of electrodes, including polyacetylene (PA),

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polyaniline (PANI), polypyrrole (PPy), polythiophene (PTh), poly(para-phenylene)

(PPP), poly(para-phenylene vinylene) (PPV), polyfuran (PF), and poly(3,4-
ethlenedioxythiophene) (PEDOT) [19, 36, 37]. The molecular structures of these typical
conducting polymers are displayed in Fig. 1. In this chapter, the progress of the studies
about applications of conducting polymers in lithium-ion batteries will be reviewed in a
chronological style. There will be two major sections which try to draw outlines of the
development history of CPs in LIB cathodes and anodes, respectively. In each section,
the related studies will be divided into several timeframes, where the different developing
trends of CPs will be discussed and summarized.

Figure 1 Molecular structures of typical conducting polymers.

2. Applications on cathode materials

2.1 Before 2000: Emergence stage

After the discovery of conducting polymers in 1976, Alan J. Heeger et al. then applied
them in energy storage/conversion fields [38]. At that time, the lithium-ion batteries were
still not commercialized, thus most of studies on CPs focused on their applications in
rechargeable Li metal batteries [38-48]. In 1981, Heeger and MacDiarmid found that the
conductivity of polyacetylene (PA) could be controlled from semiconducting to the
metallic regime through an electrochemical doping process [38]. Using a solution of
LiClO4 in propylene carbonate and a lithium cathode, PA was electrochemically doped to
form [CH+y(ClO4)y-] (y=0-0.06) which had conductivities up to ca. 103 Ω-1 cm-1.

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According to this result, the [CH+y(ClO4)y-] film could be used as cathode-active material
in lightweight rechargeable storage batteries. Based on the following discharge reaction
(Eq.1),

[CH+0.06(ClO4)0.06-]x + 0.06xLi → (CH)x + 0.06xLiCiO4 (1)

A 6 % doped [CH+y(ClO4)y-] film exhibited an open-circuit voltage of 3.7 V and an initial

short-circuit current of 25 mA. The as-prepared (CH)x/LiCiO4/Li rechargeable storage
battery could reach an energy density of about 176 Wh kg-1. To our best knowledge, this
is the first work which applied conducting polymers in energy storage devices. This work
demonstrated the feasibility of using CPs to fabricate lightweight rechargeable batteries
and the potential possibility of various applications of CPs.
In following years, other conducting polymers were discovered and applied as cathode
materials in Li-based batteries, including polythiophene (PTh) [39], polypyrrole (PPy)
[40, 41, 45-47], and polyaniline (PANI) [42, 45]. In 1998, Rhee et al. used PPy film as
cathode and UV curved polymer (poly(ethylene glycol) diacrylate, PEGDA) as
electrolyte to fabricate a flexible Li-based battery [47]. The Li/PEGDA/PPy battery
exhibited the upper cut-off and lower cut-off voltages of 4.0 V and 2.8 V, respectively.
Besides, this battery could reach the initial discharge and charge capacities of 38 mAh
cm-2 and 51 mAh cm-2, respectively, at a current density of 0.2 mA cm-2.

2.2 2000-2006: Preliminary stage

When stepped into the new century, the rising of lithium-ion batteries provided more
opportunities for conducting polymers to extend their application boundaries. In this
period, conducting polymer-based hybrid materials appeared to be applied as the cathode
of Li-ion or Li-metal batteries [49-55]. Meanwhile, there was still a part of studies
focused on the synthesis of CPs-based cathodes for Li-based batteries and their
electrochemical reaction mechanisms [56-61]. Up to 2001, spinel LiMn2O4 has been
regarded as one of the most promising cathode candidates of LIBs and also attracted
much attention [62-64]. However, this material still had some problems to be solved,
such as its poor cycling stability at room temperature [62]. In 2002, Mastragostino’s team
prepared Li1.03Mn1.97O4 spinel by sol-gel method and then coated poly(3,4-
ethylenedioxythiophene) on the particles to obtain Li1.03Mn1.97O4/PEDOT composite
cathode material [49]. The conductive nature of PEDOT could improve the electronic
conductivity of the electrode. In addition, the electroactive potential range of PEDOT was
same as that of Li1.03Mn1.97O4, and the plastic property of PEDOT allowed it to act as

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binder in the electrode. Compared to the conventional Li1.03Mn1.97O4/C composite

cathode, the Li1.03Mn1.97O4/PEDOT electrode exhibited almost the same initial capacities
at different current densities. In the following studies of Mastragostino’s team, the
electrochemical performance of LixMn3-xO4/PEDOT hybrid cathodes was further
investigated [54, 55]. A barrier effect of PEDOT was demonstrated, which could prevent
direct contact of the manganese oxide with the electrolyte and its degradation products.
This effect might benefit the improvement of cycling stability of the lithium manganese
oxide cathode. After electrochemical performance tests, the results indicated that the
capacity fade of LiMn2O4/PEDOT composite electrode was slightly lower than that of
conventional LiMn2O4/C cathode [54]. Although this attempt of introducing PEDOT into
traditional cathode was not able to satisfy the cycle-life target of LIBs at that time, the
series of studies still provided a promising direction and also gained meaningful results.
Additionally, Wallace’s group insisted to improve the electrochemical performance of Li-
based batteries with CPs cathodes during this timeframe [59-61]. In 2006, they developed
polythiophene (PBiTh) as the cathode in lithium-polymer rechargeable batteries instead
of the polypyrrole (PPy) electrode they fabricated before [59]. Due to more appropriate
redox potentials, thiophene-based polymer electrodes could have better
electrochemical/structural stability and electronic conductivity than that of PPy-based
electrodes. According to this report, the as-prepared PBiTh/PF6 coated stainless-steel
mesh cathode presented a stable discharge capacity of ca. 82 mAh g-1 over 50 cycles (at
0.1 mA cm-2), which was higher than that of PPy electrode. There was another important
work reported in 2006, which opened another new gate for the CPs-based electrode
materials. In consideration of the relationship between conductivity and morphology of
polyaniline (PANI), Chen et al. synthesized PANI nanotubes and nanofibers and applied
them as cathodes of Li-based batteries [65]. The percholoric acid-doped polyaniline
(HClO4-PANI) nanotubes were fabricated by employing anodic aluminum oxide (AAO)
membranes as templates, while the HClO4-PANI nanotubes were prepared through a
spray technique with steel mesh as the templates. When applied as the cathode of Li-
based battery, the as-prepared HClO4-PANI nanotubes exhibited larger charge/discharge
capacities, better cycling stability as well as higher electrical conductivity than those of
the commercial doped PNAI powders. This study not only provided a new strategy to
improve electrochemical performance of CPs-based electrodes but also could be regarded
as the prelude of nano-era of CPs-based electrodes.

2.3 Since 2007: Fast development stage

Up to 2007, the lithium-ion batteries have developed about 15 years and various cathode
systems have been established, including LiFePO4 and LixMyOz (M = Mn, V, Co) [5-7].

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Although some of these materials have been applied in the commercial Li-ion batteries,
they still existed several problems which limited their electrochemical performance.
Generally, these materials exhibited low ionic and electronic conductivities [66]. In order
to overcome these defaults, one strategy was to reduce the particle size to decrease the
length of the lithium-ion diffusion pathway [67]. Another way was to add conductive
agent into electrode material to increase the electronic conductivity [68]. Considered
these factors, conducting polymers were ideal candidates to fabricate hybrid electrodes
combined with these conventional cathode materials. CPs could not only improve the
electronic conductivity of the electrodes but also contribute certain specific capacities for
the batteries [69]. Moreover, due to the flexibility and plasticity, CPs could easily
combine with nanosized cathode materials via some surface modification techniques [70-
72]. Therefore, since 2007, CPs-based nanosized hybrid cathodes gradually became the
mainstream of CPs-based LIB cathodes. Meanwhile, the Li-polymer batteries gradually
withdrew from the historical stage because of the flourish of Li-ion batteries. Generally,
the CPs-based nanosized hybrid cathodes could be divided into two types during this
period. One was nanoscale conventional cathode materials coated by conducting
polymers [10, 69-89], another was conducting polymer framework on where
nanoparticles of cathode materials loaded [90, 91].
At that time, LiFePO4 was one of the most important and common cathode materials for
commercial LIBs, thus a number of studies focused on how to improve the
electrochemical performance of LiFePO4 assisted with conductive polymers [71, 72, 75,
77, 78, 81]. In 2008, Manthiram et al. reported a novel microwave-solvothermal
approach to fabricate well-defined nanoparticles of LiFePO4 [71]. Then, they coated a
mixed conducting polymer (p-toluene sulfonie acid-doped poly(3,4-
ethylenedioxythiophene), denoted as p-TSA-PEDOT) on the LiFePO4 nanoparticles to
obtain nanohybrid cathode materials, as shown in Fig. 2(a). This nanohybrid electrode
exhibited good cyclability with 3 % fade within 50 cycles, which was much better than
those of pure LiFePO4 and pure p-TSA PEDOT electrodes. The enhanced
electrochemical performance of the hybrid cathode could be attributed to the mixed
electronic-ionic conductivity of the p-TSA PEDOT. In 2011, Schougaard’s team
presented a new method to prepare PEDOT/LiFePO4 composite electrode material, which
could significantly improve the fabrication efficiency[78]. They selected the intrinsic
oxidation power of Li(1-x)FePO4 instead of the external oxidant, which was the key point
of this methodology. The Li(1-x)FePO4 acted as the driving force of the polymerization
process. Firstly, the Li(1-x)FePO4 powders were synthesized by a delithiation process of
LiFePO4. Then, the polymerization of 3,4-ethylenedioxythiophene (EDOT) was realized

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by the reinsertion of lithium into Li(1-x)FePO4. The reaction equations are presented by
Eq. 2 and Eq. 3.

LiFePO4 + x/2H2O2 + xH+ → Li(1-x)FePO4 +xLi+ + xH2O (2)

Li(1-x)FePO4 + LiTFSI + EDOT→ PEDOT-LiFePO4 (3)

The as-fabricated PEDOT-LiFePO4 composite cathode displayed good cycling stability

within 30 cycles and also good rate performance.

Figure 2 a) TEM image of the small LiFePO4 nanorods after coating with p-TSA
PEDOT, ref.[71], copyright 2008 Elsevier B.V.; b) TEM image of the V2O5@PANI
core/shell nanofiber hybrids, ref.[10], copyright 2016 Elsevier Ltd.; c) SEM image of
PEDOT/LiFePO4 composite electrode, ref.[90], copyright 2012 Elsevier B.V.; d) TEM
image of PPy/LFMO composite electrode, ref.[91], copyright of Springer-Verlag Berlin
Heidelberg 2017.

Except for LiFePO4, other kinds of cathode materials were also composited with
conducting polymers to enhance their electrochemical performance. In 2014, Song and

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Lee synthesized LCO/PEDOT:PSS (LiCoO2/poly(3,4-ethylenedioxythiophene) doped

with poly(styrenesulfonate)) composite LIB cathode, where the PEDOT:PSS layers were
coated on the LCO particles like skin[82]. The PEDOT:PSS skin could act as both binder
and conductive agent, which was able to reach a higher energy density of LCO cathode.
By adjusting the PSS content and also the structural conformation (benzoid-favoring and
quinoid-favoring) of PEDOT, the electric conductivity of this composite electrode could
be controlled, resulting in different electrochemical performance. In terms of
electrochemical performance, the [email protected]:PSS electrode (3.3Q, representing
the quinoid-type PEDOT:PSS with 3.3 mol of monomeric units of PSS per mole of
PEDOT) exhibited the best results, which retained a reversible capacity over 400 mAh g-1
after 100 cycles at 1 C. In recent years, vanadium pentoxide (V2O5) has been widely
studied as cathode material for lithium-ion batteries, due to ability of the vanadium ion to
change its oxidation state (V-II) and low cost[92, 93]. In 2016, Li’s team prepared
V2O5@PANI core/shell nanofiber hybrids, which aimed to enhance the electronic
conductivity, decrease the dissolution rate in liquid electrolytes and volume changes
during ion intercalation/removal processes of the V2O5 cathode[10]. The V2O5 nanofibers
were grown on fluorine-doped tin oxide (FTO) substrates by a controlled vertical drying
method and anodic deposition process[94]. The PANI shells were then coated on V2O5
nanofibers via an electropolymerization process. The structure and morphology of as-
prepared V2O5@PANI core/shell nanofiber hybrids are presented in Fig. 2(b). The
thickness of the PANI shell was adjusted to 5 nm, 13 nm, and 32 nm by different
deposition time of 30 s, 60 s and 240 s, respectively. With electrochemical investigations,
it was indicated that the existence of PANI shell could effectively improve Li-ion storage
performance of the V2O5-based cathode, which could be ascribed to the reduced
interfacial electric resistance and inhibition of vanadium dissolution. Meanwhile, the
electrochemical performance of hybrid cathode was dependent to the thickness of the
PANI shell, that the deposition time. As a result, the sample V2O5@PANI-240s exhibited
the best cycling stability.
Creating a conducting polymer framework for conventional cathode materials was
another strategy to construct CPs-based hybrid cathodes for LIBs. In 2011, Wang et al.
reported a novel method called dynamic solid/liquid (oil)/liquid (water) three-phase
interline electropolymerization (D3PIE), which could be used to synthesize free-standing
PEDOT thin films [95]. The oil phase (dichloromethane) was hydrophobic monomer
(3,4-ethylenedioxythiophene or pyrrole), while the aqueous phase was only dopant
electrolytes. The solid phase was a platinum wire which immersed vertically across the
oil/water interface and acted as a working electrode. The polymer film grew on the
interface between the oil and water phase when an overpotential was applied to the

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electrode. As-prepared PEDOT film exhibited heterogeneous micro-nano-structure.

Based on this study, in 2015, Schougaard et al. synthesized PEDOT/LiFePO4 composite
electrode by the D3PIE method, where LiFePO4 particles dispersed in the PEDOT
matrix, as presented in Fig. 2(c) [90]. The PEDOT framework not only provided
mechanical support for LiFePO4 particles but also enhanced the conductivity of the whole
electrode, leading to improved electrochemical performance. In 2018, Zhao et al.
prepared PPy/LFMO (polypyrrole/Li1.26Fe0.22Mn0.52O2) composite LIB cathode, where
LFMO particles loaded on PPy nanowires, as shown in Fig. 2(d) [91]. The three-
dimensional electrical conduction networks built by PPy nanowires could effectively
enhance the conductivity and stability of the composite electrode. As a result, the
PPy/LFMO composite electrode presented enhanced cycling capability, initial coulombic
efficiency as well as rate performance. It reached an initial discharge capacity of 205
mAh g-1 at 1 C (1 C=200 mA g-1), and kept reversible capacities of 132 mAh g-1 and 98
mAh g-1 after 50 cycles at 1 C and 3 C, respectively.

Figure 3 a) chemical structure of the pyrrole/[(ferrocene) amidopropyl]pyrrole

copolymer, repainted according to ref.[96], copyright 2007 WILEY-VCH Verlag GmbH
& Co. KGaA, Weinheim; b) chemical structure of Ni(CH3-salen) monomer; c) multiple
roles of poly[Ni(CH3-salen)] in carbon-free cathodes, ref.[103], copyright 2018
American Chemical Society.

Since 2007, several new-type conducting polymers were developed and applied in the
cathode materials for lithium-ion battery [96-103]. In 2007, Goodenough’s team
proposed a novel method about attaching a suitable redox couple to the polymer

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backbone, in order to improve the specific capacity of conducting polymers [96]. They
anchored ferrocene groups to the PPy backbone to generate [(ferrocenyl)
amidopropyl]pyrrole (denoted as PPy/ferrocene) conductive copolymer, which chemical
structure is presented in Fig. 3(a). Incorporated this polymer with LiFePO4, the specific
capacity of this composite electrode was obviously increased. The PPy/LiFePO4 cathode
could display a specific capacity of over 130 mAh g-1 at 0.2 C, while the
LiFePO4/C/PTFE (75:20:5 in wt %) cathode exhibited less than 110 at the same
condition. PEDOT has been studied as LIB cathode material for several years and gained
much progress. In 2011, Abruna et al. synthesized some CPs which had a similar
chemical structure to PEDOT but with different heteroatoms [98]. Those polymers were
poly(3,4-ethylenedioxyselenophene) (PEDOS), and poly(3,4-ethylenedioxypyrrole)
(PEDOP), corresponding to selenium and nitrogen, respectively. The as-prepared PEDOS
and PEDOP exhibited good electrocatalytic activity to 2,5-dimercapto1,3,4-thiadiazole
(DMcT) which is also a promising cathode material for LIBs [104-106]. Based on this
study, PEDOX (X=Se, NH)/DMcT displayed a good potential to be high-performance
cathode materials for Li-ion batteries. Recently, an interesting type of conducting
polymer emerged and attracted attention as LIB electrode material, which known as the
salen-type polymer [102, 103, 107-109]. Generally, the salen-type polymer can be
synthesized by oxidative electrochemical polymerization of transition-metal complexes
with salen-type N2O2 Schiff base ligands (salen is N,N′-
bis(salicylidene)ethylenediamine), denoted as poly[M(Schiff)] (M is a transition metal,
Schiff is a salen-type N2O2 Schiff base). In 2019, Kim et al. fabricated poly[Ni(CH3-
salen)] as an additive for conventional cathodes in lithium-ion batteries, whose monomer
structure is presented in Fig. 3(b) [103]. According to this study, the poly[Ni(CH3-salen)]
played multiple positive roles in the composite cathode (poly[Ni(CH3-salen)]/LiFePO4).
As shown in Fig. 3(c), the poly[Ni(CH3-salen)] was able to i) form a 3D electronic
network, ii) accelerate charge-transfer reaction of the cathode, iii) contribute extra
specific capacity, iv) enhance the mechanical property of the electrode, v) passivate the
active materials at the top surface. Therefore, the poly[Ni(CH3-salen)]/LiFePO4 cathode
exhibited better electrochemical performance than that of the conventional
carbon/LiFePO4 cathode. Moreover, conducting polymers could separately act as binder
or conductive agent instead of constructing composites with conventional cathode
materials. This strategy also could improve the electrochemical performance of LIB
cathodes, and attracted some attention since 2007 [9, 110-114].

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3. Applications on anode materials

3.1 Before 2010: Emergence stage

The origin of conducting polymers applied in anode materials could be dated back to the
1980s before the birth of the commercial lithium-ion batteries [39, 115]. However, to our
best knowledge, there were only a few published reports about the applications of CPs on
LIB anodes before 2010 [116-119]. In 2006, Wan et al. fabricated SnCl2/PAN composite
anode via a low-temperature pyrolysis process [118]. Generally, the polyacrylonitrile
(PAN) is not a typical conducting polymer, but its electrical conductivity can be
improved after thermal treatment due to the chains undergoing cyclization to form a
conjugated-chain chemical structure [120, 121]. Based on this idea, the PAN could
enhance the conductivity of Sn-based anode and also alleviate the volume expansion of
Sn during charge and discharge processes. The as-prepared SnCl2/PAN composite anode
could remain a reversible capacity of 490 mAh g-1 after 50 cycles at a current density of
30 mA g-1. In 2007, Wallace et al. combined conducting polymer with aligned carbon
nanotube (ACNT) arrays to obtain PEDOT/ACNT composite anode material [119]. This
composite anode remained a reversible capacity of 265 mAh g-1 after 50 cycles at 0.1 mA
cm-2, which was better than other CNT-based anodes at that time [122].

3.2 Since 2010: Rising stage

Since 2010, various anode materials gained considerable progress, including alloying-
type anodes (Si, Sn, Ge, Sb) and conversion-type anodes (TiO2, Li4Ti5O12) [13, 14, 123].
Although these anodes exhibited several advantages compared with the conventional
graphite-based anodes, such as higher theoretical capacity and better rate cyclability, they
still suffered from some problems. For the alloying-type anodes, huge volumetric
expansion in lithiation process leads to fast capacity fading [124]. In terms of conversion-
type anodes, they usually have stable cyclability but their electrochemical performance is
limited by the poor electrical conductivity [123]. Based on unique properties, conducting
polymers were widely used in both alloying-type and conversion-type anodes in order to
improve their electrochemical performance.
Due to good cycling stability and rate performance, titanium dioxide (TiO2) has become
one of the most favorite anodes for Li-ion batteries in recent years [125, 126]. However,
it still has some drawbacks, such as relatively low specific capacity and electrical
conductivity. In 2010, Dziewonski and Grzeszczu prepared TiO2-PPy and TiO2-PEDOT
anodes where the conducting polymers could not only provide some specific capacity but
also enhance the conductivity of the electrodes [127]. According to this report, the
existence of PPy and PEDOT benefited the intercalation of Li ions into amorphous TiO2

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as well as the reversibility of the process, leading to better electrochemical performance

of the composite anodes. Zinc oxide (ZnO), as a newly anode material, has attracted
much attention due to its high theoretical capacity of 978 mAh g-1 [128-130]. In 2015,
Chen and Amine introduced PEDOT:PSS into ZnO/C anode, in order to improve its
conductivity and accommodate the volume change during cycling [131]. Assisted with
PEDOT:PSS surface coating, the electrochemical performance of this anode was
obviously enhanced. It maintained a reversible capacity of 748 mAh g-1 after 500 cycles
at 0.5 C and 624 mAh g-1 after 1500 cycles at 1 C. Li4Ti5O12 (LTO) has been successfully
applied in commercial lithium-ion batteries due to its excellent cycling stability [132-
134]. However, poor electron conductivity limits its rate performance [135]. In 2017, Xu
et al. coated polythiophene (PTh) on the surface of LTO particles, to obtain core-shell
structured LTO/PTh composite anode[136]. After PTh-coating, electron conductivities
LTO anode increased from 7.3×10-9 S cm-1 (pure LTO) to 1.6×10-6 S cm-1 (LTO/PTh).
Therefore, the LTO/PTh composite anode could reach a specific capacity of 157 mAh g-1
at 5 C, which was much better than that of pure LTO anode (130 mAh g-1).
Silicon (Si) has been regarded as the most promising anode candidate for the next-
generation lithium-ion batteries due to its highest theoretical capacity among all anode
materials [14]. With the great advantage, the practical performance of Si and other
alloying-type anode materials were still insufficient due to the huge volume expansion
upon lithiation, as mentioned above. Therefore, since 2010, many efforts have done
which aimed at using conducting polymers to improve the cycling stability of Si-based
(or alloying-type) anodes. Similar to what discussed in the last part (2.3), the related
studies about applications of CPs on alloying-type anodes could be divided into two
classifications, one about coating CPs on active particles [137-146], another about
loading active particles on CPs networks[147-149]. In 2012, Cui’s team coated PEDOT
on Si nanowires (NWs) to enhance the cyclic stability of electrode [138]. Si nanowires
were fabricated by Au-catalyzed chemical vapor deposition, then PEDOT was coated on
their surfaces via an electropolymerization process. The schematic morphology of as-
prepared Si NW/PEDOT composite is displayed in Fig. 4(a). Finally, this composite
anode retained a reversible capacity of 2510 mAh g-1 after 100 cycles at 0.2 C (1 C=4200
mA g-1), corresponding to a capacity retention of 80 %. Compared to the bare Si NW
anode, the capacity retention of Si NWs/PEDOT electrode increased from 30 % to 80 %.
Up to 2013, Cui’s team reported their another work about Si/CP hybrid anode for LIBs
[139]. Si nanoparticles (Si NPs) were mixed phytic acid and aniline in water, where the
phosphoric acid groups in the phytic acid molecules could bind with the SiO2 on the Si
particle surfaces via hydrogen bonding [150, 151]. Furthermore, the coated phytic acid
molecules on the Si NPs could be crosslinked with aniline monomers during

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polymerization, forming a 3D conducting hydrogel network which trapped coated Si

nanoparticles inside. As presented in Fig. 4(b), this study combined coating and loading
strategies, resulting in enhanced electrochemical performance of the Si-based anode. This
Si NP/PANI hybrid anode exhibited stable cyclability, which maintained a reversible
capacity of 1600 mAh g-1 after 1000 cycles at 1.0 A g-1. In addition, this hybrid anode
also gained good rate performance, which could keep a stable capacity of 550 mAh g-1
after 5000 cycles at a high current density of 6.0 A g-1. This study provided a novel and
promising way to fabricate high-performance Si-based anodes by a scale-up manufacture
method. In the following years, a variety of CPs-based composite LIB anodes were
synthesized and gained enhanced electrochemical performance, including Sn/PFM
(Poly(9,9-dioctylfluorene-co-fluorenone-comethylbenzoicester)) [140], Si/PEDOT:PSS
[141, 142], Si/SiOx-PEDOT:PSS [143], Si/C-PPy [144], Si/EP(EDOT-phenylene-based
conjugated polymer) [146] composite materials.
In terms of the strategy about building CPs networks for active materials, it also gained
some good results [147-149]. In 2013, Yu et al. prepared a 3D hierarchically porous
framework established by polypyrrole (PPy) and single-walled carbon nanotubes
(SWCNTs), to act as the matrix for Si nanoparticles (Si NPs) [147]. As presented by Fig.
4(c), the 3D conductive framework was formed by the nanostructured PPy hydrogel.
Meanwhile, a thin in-situ polymeric coating layer was generated on the surface of Si NPs,
which could further link with the external conductive polymeric framework. Such a
unique design could connect the separated Si nanoparticles with the conducting network,
forming an interconnected and stable nanostructure. Such structure was beneficial to
accommodate the huge volumetric changes of silicon and improved the electrical
conductivity of the whole electrode. Moreover, the addition of SWCNTs could further
enhance the stability and conductivity of the electrode, due to the roles of the wrapping
layer and conductive backbone. Therefore, good electrochemical performance of this
Si/PPy/CNT composite anode was expected. As a result, this anode achieved a reversible
capacity of ca. 1600 mAh g-1 after 1000 cycles at a current density of 3.3 A g-1,
corresponding to a capacity retention of over 85 %. When tested at a higher current
density of 8.6 A g-1, the Si/PPy/CNT composite anode still exhibited very stable
cyclability, which retained a specific capacity of 1000 mAh g-1 after 2000 cycles. In
2014, Bao and Cui applied a similar strategy to synthesize flexible hybrid anodes [148].
PEDOT:PSS, carbon nanotubes (CNTs) and active nanoparticles (including TiO2 and Si)
were used to fabricate 3D interconnected carbon nanotube-conducting polymer hydrogel
network for flexible battery electrode, as displayed in Fig. 4(d). The as-fabricated
TiO2/PEDOT:PSS/CNT composite anode displayed great flexibility. Its resistance only
presented some tiny changes after 500 bending cycles at a bending radius of 3.5 mm,

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indicating its good overall mechanical property. Besides, due to enhanced electrical
conductivity, the TiO2/PEDOT:PSS/CNT anode also exhibited good rate performance. In
case of the Si/PEDOT:PSS/CNT electrode, it could keep about 90 % of its initial capacity
after 100 cycles, while a control electrode made by mixing CNT with PEDOT:PSS
coated SiNP lost about 55% of its capacity.

Figure 4 a) Schematic of a PEDOT (blue)-coated Si NW(brown) with the molecular

structure of PEDOT shown, ref.[138], copyright The Royal Society of Chemistry 2012; b)
Schematic illustration of 3D porous SiNP/conductive polymer hydrogel composite
electrodes, ref.[139], copyright 2013 Macmillan Publishers Limited.; c) Schematic
illustration of the formation of 3D Si/PPy/CNT ternary electrode, ref.[147], copyright
2013 American Chemical Society; d) Schematic of the aqueous solution process to
fabricate flexible electrodes using active nanoparticles (e.g., TiO2 or Si nanoparticles),
CNT and PEDOT:PSS, repainted according to ref.[148], copyright 2014 WILEY-VCH
Verlag GmbH & Co. KGaA, Weinheim.

In recent years, several novel conducting polymers gained increasing popularity as

anodes for lithium-ion batteries, especially the conjugated ladder polymers (CLPs) [152-
157]. Ladder or ribbon polymers consist of cyclic subunits, connected to each other by
two links which are attached to different sites of the respective subunits [158]. The
history of synthesizing ladder polymers could be dated back to 1970s when the
poly(benzimidazobenzophenanthroline) (BBL) was synthesized by the U.S. Air Force

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Wright Aeronautical Laboratory [159]. The conjugated ladder polymers are those ladder
polymers with π-conjugated structures, which exhibit good electrical conductivity and
have been applied in various electronic devices [160-164]. With large π-conjugated
structure, rich nitrogen heteroatoms and multiring aromatics, the conjugated ladder
polymers are also promising anode materials for Li-ion batteris [152]. From 2015 to
2016, Zhang and Yan led their team to reported a series of studies about CLPs-based
anode materials for lithium-ion batteries. In 2015, they synthesized polyazaacene
analogue poly(1,6-dihydropyrazino[2,3g]quinoxaline-2,3,8triyl-7-(2H)-ylidene-
7,8dimethylidene) (PQL) and demonstrated its good lithium storage property [152]. As
shown in Fig. 5(a), the PQL was obtained by the reaction between 2,5-dihydroxy-1,4-
benzoquinone and 1,2,4,5-tetraaminobenzene tetrahydrobromide (TAB·4HBr) in 116%
polyphosphoric acid (PPA) at 190 ℃ for 10 h [165]. Applied as anode for LIBs, the PQL
could retain a reversible capacity of 1550 mAh g-1 after 100 cycles at a current density of
100 mA g-1. Moreover, the PQL exhibited an electrical conductivity of 2.1×10-3 S cm-1,
indicating a good rate performance. Tested at 50℃, the PQL anode delivered a reversible
capacity of about 500 mAh g-1 after 1000 cycles at a current density of 4555 mA g-1. In
2015, they also reported their another work about CLPs-based anodes [153]. They
synthesized BBL and its derivative, SBBL through one-pot polycondensation between
1,2,4,5-tetraaminobenzene tetrahydrobromide (TAB·4HBr) and pyromellitic dianhydride
(PMDA)/naphthalenete-tracarboxylic dianhydride (NTCDA) in polyphosphoric acid
(PPA), as displayed in Fig. 5(b) [165, 166]. In terms of electrochemical performance, the
BBL electrode retained a reversible capacity of 496 mAh g-1 after 1000 cycles at 3 C rate
(1 C=1962 mA g-1), while the SBBL gained a capacity of 320 mAh g-1 at same test
conditions (here 1 C=1888 mA g-1). Compare to the SBBL, the enhanced electrochemical
performance of BBL anode could be attributed to its part network or nonlinear structure
in the polymer chain. Up to 2016, they fabricated another conjugated ladder polymer,
called poly(1,4-dihydro11H-pyrazino[2′,3′:3,4]cyclopenta[1,2-b]quinoxalin-11-one)
(PPCQ). Similar with their previous methods, the PPCQ was prepared by a simple one-
step polymerization reaction, as presented in Fig. 5(b). This novel conjugated ladder
polymer anode also exhibited good performance in both cycling and rate tests. The efforts
made by Zhang and Yan’s team not only extended the application range of conjugated
ladder polymers but also provided a kind of promising anode material for lithium-ion
batteries.

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Figure 5 a) Synthesis of the ladder polymer PQL, repainted according to ref.[152],

copyright 2015Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim; b) Synthetic scheme
for the polymers of SBBL and BBL, repainted according to ref.[153], copyright 2015
WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim; c) Synthetic route to the ladder-
structured polymer PPCQ, repainted according to ref.[154], copyright 2016 American
Chemical Society.

Conclusions & Outlooks

Conducting polymers were synthesized in 1976 for the first time, then attracted
considerable attention in short order due to their unique electrical and physical properties.
When lithium-ion batteries were successfully commercialized in 1992, conducting
polymers were quickly applied as electrode materials. After about 30-years development,
conducting polymers have become one of the most significant branches of electrode
materials for lithium-ion batteries. A verity of conducting polymers have been developed
and applied in both cathode and anode materials for Li-ion batteries, including PA, PANI,
PPy, PTh, PEDOT, et al.
Applying conducting polymers in cathodes was always a research hotspot since the
discovery of conductive polymer, whose origin could be dated back to 1980s. During the
emergence stage before 2000, most of the studies focused on using pure CPs as cathodes

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for Li metal-based rechargeable batteries. From 2000 to 2006, conducting polymers

started to combine with the normal cathode materials to improve electrochemical
performance. Meanwhile, there was still a part of studies which aimed to build lithium-
polymer batteries assisted with conductive polymers. Since 2007, lithium-ion batteries
have gained fruitful achievements and played important roles as portable power sources
in daily life. The flourish of cathode materials also exposed several problems which
needed to be solved as soon as possible, such as low ionic and electronic conductivities.
Nanotechnology gained rocket-like development in the new century and has been utilized
to overcome the problems of LIB cathodes. Therefore, the combination of conducting
polymer and nanotechnology became a new mainstream to fabricate high-performance
composite cathodes during this period. Two different strategies for designing the CPs-
based composite cathodes appeared. One was coating the conducting polymers on
nanoparticles of the conventional cathode material, where PEDOT:PSS and LiFePO4
attracted much attention. Another strategy was to creating conducting polymer
framework to warp the nanoparticles. Due to more facile synthesis, which usually
realized by an electropolymerization process, the first trend exhibited a dominated
position among all related studies. Moreover, in recent years, several new-type
conducting polymers were synthesized and displayed the great potential to act as high-
performance LIB cathodes, including some analogs of PEDOT and salen-type polymers.
In terms of CPs-based anodes, the origin could be de dated back to the 1980s. However,
compared to the cathode materials, there were only a few studies about CPs-based anodes
for LIB before 2010. This could be attributed to the great success of carbon-based anodes
in the first ten years of the 21st century. Since 2010, the limited specific capacity of
graphite-based anodes promoted the wave of looking for high-capacity anode materials.
Various newly anode materials were synthesized and studied, including alloying-type and
conversion-type anodes. Nevertheless, most of these anodes suffered from some
drawbacks, such as the volumetric effect of alloying-type anodes and low conductivity of
conversion-type anodes. Therefore, conducting polymers embraced their golden period of
applications in LIB anodes due to the good electrical and mechanical characteristics,
which were beneficial to solve those problems above. Similar to the cathode, the studies
about CPs-based composite anodes could also be divided into two types, coating, and
loading design strategies. Aiming to improve cycling stability of Si anodes, the most
promising anode for the future LIBs, various conducting polymer/Si nanostructure
composite materials were fabricated and exhibited very competitive electrochemical
performance. In addition, assisted with conducting polymer, some conversion-type
anodes, such as TiO2 and Li4Ti5O12, also displayed enhanced electrochemical

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performance. In the last several years, the conjugated ladder polymers emerged as novel
anodes and also exhibited stable cyclability with high reversible capacity.
Due to the combined characteristics of conductor and polymer in the conducting
polymers, they could be regarded as ideal additives or modification agents for both
cathodes and anodes of Li-ion batteries. Conducting polymers can easily composite with
various conventional electrode materials because of the good plasticity, to overcome
some problems of these materials and enhance their electrochemical performance. In
many studies, the conducting polymer can act as both binder and conductive agent, which
benefits to increase the energy density of batteries. Moreover, the conducting polymers
can endow the flexibility to the electrode, thus exhibit a broad application prospect for
flexible and wearable electron devices in the future. According to Alan J. Heeger’s
classification, conducting polymers belong to the fourth generation of polymer
materials[27]. It is believed that this fourth-generation polymer will play a significant
role to promote the development of second-generation lithium-ion batteries.

Acknowledgment
This research is funded by the National Key R&D Program of China (Grant No.
2016YFB0100100), Natural Science Foundation of China (51702335, 21773279), the
CAS-EU S&T cooperation partner program (174433KYSB20150013), and Key
Laboratory of Bio-based Polymeric Materials of Zhejiang Province. S.L. acknowledges
the China Scholarship Council (CSC). P.M-B acknowledges funding by the International
Research Training Group 2022 Alberta/Technical University of Munich International
Graduate School for Environmentally Responsible Functional Hybrid Materials
(ATUMS).

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Chapter 3

2D Transition Metal Dichalcogenides for

Lithium-ion Batteries

S.V. Prabhakar Vattikuti

School of Mechanical Engineering, Yeungnam University, Gyeongsan, 712749, South Korea
[email protected]
Abstract
Transition metal dichalcogenides (TMDs) materials offer exciting prospective
applications in energy storage particularly as electrode resources for lithium-ion batteries
(LIBs), which lately received enormous consideration owing to their unique 2D layered
features appropriate for effective charge storage and conversion. However, several
important and practical challenges are still need to be resolved for LIBs to become
suitable for commercial use. This chapter presents a timely review, detailing the
perspectives on the latest advancements and future directions in using TMDs for LIBs
research. The chapter is divided into three parts: (i) TMDs materials as electrode; (ii)
TMDs based hybrids; and (iii) viewpoint and perspectives.
Keywords
Lithium-Ion Batteries, Layered Materials, Transition Metal Dichalcogenides,
Molybdenum Disulfide, Tungsten Disulfide

Contents

1. Introduction..............................................................................................64
2. MoS2-based anode materials for LIBs ...................................................66
3. WS2-based anode materials for LIBs .....................................................71
4. MoSe2 based anode materials for LIBs .................................................73
5. WSe2-based anode materials for LIBs ...................................................76
6. Other TMDs for LIBs..............................................................................77

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7. Summary and future outlooks ................................................................80

Acknowledgement ..............................................................................................81
References ...........................................................................................................81

1. Introduction
The rapidly increasing global demand for sustainable energy as well as the conventional
environmental impacts of energy consumption necessitates the need for safer and more
cost-effective energy storage technologies. Therefore, there is huge plea for safe, clean
and green sustainable energy sources. To address this issue, a huge attention has been
actively focused in the arena of energy storage as well as conversion [1]. Well
knowingly, the lithium-ion batteries (LIBs) have been comprehensively exploited in
various fields of applications and are of favored choice at this present scenario. Over the
years, lots of improvements have been taken to efficiently charged and discharged. For
instance, modern hybrid electric vehicle (MHEV) demands the deployment of high
capacity LIBs, however high energy and power density parameters are difficult to satisfy
and thus require more high energy batteries. The LIBs suffer from low powder density
and cyclic stability; hence attempts were made to improve LIBs to contain high energy as
well as to meet the desirable powder density with remarkable cyclic stability.
To date, extensive research efforts have been focused on enhancing the energy density of
LIBs by using various nanomaterials, including transition metal oxides (TMOs) or
dichalcogenide (TMDs) and metal oxides. Efficient electrodes should possess good
electronic conductivity and be adept in accommodating Li ions in a fast rate. In the
periodic table, group IV-VII are dominantly layered in nature, while, about of group VIII-
X TMDs are mostly originating in other morphological materials and have been viewed
to be possibly used for energy storage-conversion. Other morphological TMD such as
pyrite (FeS2) has appeared superior in the energy storage. This non-layered TMD FeS2 is
well recognized as a substitute for gold and confirms a cubic configuration of which the
unit cell is comprises of a face-centered Fe coupled with S ions. The Fe ions are enclosed
with adjacent six sulfur neighbors in a partial octahedral plan.
Transition metal dichalcogenides (TMDs) commonly known as MX2 (M-transition metal
i.e. Mo, W and X-chalcogen i.e. S, Se) have currently received remarkable interest
attributing to their exclusive and attractive electronic, optical and mechanical
characteristics [2], their molecular structures are shown in Fig.1. In this type of
complexes, the atoms within the layers are assembled via robust covalent bonds (X-M-X)
and the distinct sheets are attached by van der Waals connections creating a layered by
layered assembly. These features are advantageous for the diffusion of Li ions making

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TMDs a plausible anode candidate material. For instance, the TMD WSe2 has a covered
sandwich structure comprising of Se-W-Se with a far greater interlayer spacing (0.65 nm)
compared to graphite (0.33 nm), allowing the efficient diffusion of Li ions. Novel MX2
materials possess advanced inherent electronic conductivity, greater interlayer spacing
and small potential plateau compared to commercial ones, thus hold more benefits for
emerging secondary batteries. The following equations exemplify the mechanism of
Li/Na–ion storage [2].

MX2 + 4A+ +4e- ↔ M + 2A2X (A i.e. Li, and Na) (1)

Equation (1) is comprehensive with the subsequent double-step electrochemical

responses,

MX2+ xA+ +xe- ↔ AxMX2 (x<2) (intercalation) (2)

AxMX2 + (4-x) A+ + (4-x) e- ↔ M + 2A2X (conversion) (3)

Figure 1. Popular Layered Transition metal dichalcogenides (TMDs) materials for LIBs.

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A potential electrode should retain good electric conductivity and be accomplished of

accepting Li ions in a fast rate. To attain this, an efficient route is to shorten the ion
diffusion distance within a conductive matrix-like carbonaceous materials such as active
carbon and graphene. But this approach comes at the cost of electrodes tape density.
Importantly, searching materials which hold inherent high electronic conductivity and
superficial ion diffusion pathways are of crucial importance in achieving superior lithium
storage performance. Although outstanding power handling and decent gravimetric
architectures including graphene aerogels, carbon nanotube aerogels, sponges, and foams
are more highlighted in the practical situation, they are far from expectation and still need
complete understanding of the electrochemical reactions.
The mechanism of MX2 lithiation/delithiation has trigged a notable consideration in the
energy storage community. Investigators strongly agreed that on the primary discharge
process, the MX2 is reconverted into metallic M nanoparticles after interaction with the
Li ions in the Li2X matrix [3, 4]. However, no consistency has been established regarding
the fundamental knowledge underlying the chemistry of the subsequent processes.
Contrasting arguments have been documented concerning the conversion rate of MX2
into Li2X and M. It has been reported that this process is irreversible, a reaction ascribed
to Li-X batteries. While other report showed that the discharge yields of Li2X and M are
converted into MX2, suggesting a reversible conversion mechanism. With these
contrasting reports, further investigation exploring the mechanism of MX2 lithium storage
must be carried out to clarify this process.

2. MoS2-based anode materials for LIBs

MoS2 is a one of the typical layered TMDs with a maximum theoretic capacity of 670
mAhg-1 for LIBs, a value greater than the standard graphite (372 mAhg-1). The higher
capacity value of MoS2 is attributable to the relocation of its four electrons during
charge/discharge process. However, the use of MoS2 for LIBs electrode materials is
bounded by several intrinsic demerits. For example, the low electronic conductivity, a
factor attributed to its weak van der Waals interaction. This weak interaction may reduce
the transport of electrons and ions particularly between layers in a c-direction, resulting to
a capacity loss during continuous use. Among the TMDs, MoS2 is one of the well-known
van der Waals solids, which possesses distinctive physical characteristics in single-to-few
layer forms. MoS2-based materials have been widely employed as electrode materials for
LIBs and lithium-sulfur batteries (LSBs) [5]. The MoS2lattice spacing can deliver a
remarkable space for accommodating Li-ions and has a hole mobility of 741 cm2V-1S-1,
making MoS2 favorable to be employed as energy materials for LIBs. Some reports
revealed that MoS2 has been used as the cathode materials for LIBs [6, 7]. However over

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the years, the application of MoS2 has been extended from cathode to anode materials.
The applicability of MoS2 as anode materials for LIBs has drawn enormous attention,
attributing to its distinctive electrochemical behavior. For an anode material, a standard
Li ion insertion-extraction process into a perfect MoS2 can be disclosed as follows: [8]
Intercalation process : MoS2 + xLi+ + xe- ↔ LixMoS2 (4)

Conversion process: LixMoS2 + (4-x)Li+ + (4-x) e- ↔ Mo + 2Li2S (5)

S + 2Li+ + 2e- → LiS (6)

Two dimensional (2D) layered TMDs exhibited a striking difference with regards to
electronic structure as compared to a bulk three dimensional (3D) TMDs. Exfoliated 2D
TMDs nanolayers have been viewed as attractive anode materials for LIBs due to the
stacked arrangement of nanosheets that could accommodate the tidal volume generated
from cyclic reversible volume variations during Li cycling. However, optimization and
further work regarding the synthetic procedure of the 2D TMDs nanosheets and rational
intended 3D structure are of abundant significance that needs to be addressed. Currently,
MoS2-based nanocrystals with various structural models have been achieved by chemical
vapor deposition (CVD), pyrolysis, microwave colloidal synthesis, solvo-hydrothermal
reaction by strong reductant, and chemical/electrochemical route [9, 10]. Among these
procedures, the CVD in an extraordinary vacuum condition creates it challenging to
realize the progress at minimal cost due to the complexity of the synthetic procedure,
which involves high temperature and harsh environmental conditions. Furthermore, the
poor electrical conductivity of the MoS2 has been recognized to moderately limit its
exploitation for energy storing. Hence, it is required to advance a facile, modest, low-cost
and globally friendly process to obtain the TMDs-based nanoconfigurations with
admirable electrochemical behavior for LIBs.
MoS2 employed as anode for LIBs has been observed limited to use because of the
polysulfide shuttling effect which can cause fast electrode deteriorate [11]. Up to now,
several reports have been documented exploring the possible approaches in orchestrating
a well-suited MoS2 with improved characteristic conductivity such as coupling with
conductive carbon or non-carbon materials. Combining with other materials, particularly
with different OD to 3D carbon materials is a famous strategy to boost the electro-
chemical conductivity of MoS2 and to provide supports in hybrid, preserving a constant
structure during the long term and high current densities. It is undoubtedly considered as
a well-organized strategy to facilitate electro-chemical activity of carbon@MoS2 hybrids

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although the electrochemical mechanism between the MoS2 and carbon is still unclear
[12, 13].
The unique architecture of hollow carbon spheres offers an added benefit for electrode-
electrolyte interaction allowing the reduction of ion diffusion distances and the defending
of volume changes. Wan et al. [14] reported the engagement of a hydrothermally
synthesized quasi-hollow microspheres of MoS2 which are anchored on porous carbon as
anode for LIBs. These C@MoS2 microspheres demonstrated high cycling stability up to
95% capacity retention afterward 100 cycles with good rate behavior of 560 mAhg-1 at 5
Ag-1. Importantly, coupling MoS2 with three dimensional (3D) carbon materials like
graphene-aerogel paper and carbon sheet-like links is the best choice for the synthesis of
MoS2-based materials for LIBs. For example, a 3D graphene along with few-layered
MoS2 nanosheets demonstrated a remarkable capacity of 1077 mAhg-1 at 100 mAg-1 at
150 cycles. 3D graphene aerogel possesses a high specific surface area, interconnected
electron pathways and lightweight features making it a prominent scaffolding material for
electrodes [15]. In another report presented by Zhou et al. [16], in-situ synthesized MoS2
nanosheets fastened on 3D mesoporous carbon nanosheets frameworks showed superior
electrochemical properties and long-time cycling stability of 676 mAhg-1 at 2Ag-1 for 520
sequences.
Some of the non-carbonaceous materials including, TiO2, SnO2, Fe3O4, Ag, or Si, can
also improve the electrochemical performance of MoS2. For instance, TiO2 showed the
lowest volume variation (i.e. less than 4%) as compared to Li-ion, has the greatest
recycling stability in LIBs amid all transition metal oxides as well as sulfide-type anode
materials, and has been demonstrated to enhance their stability particularly at robust
current densities when coupled with MoS2-based materials [17, 18]. This TiO2/MoS2
hetereostructure demonstrates a revocable capacity of 710 mAhg-1 at 100 mAg-1 after 100
progressions and showed good stability of capacity retention. Taken together, it is
apparent that the aforementioned approaches like the crafting of MoS2 constraints,
developing special morphologies and the coupling with carbonaceous or metal oxide
materials are all capable of improving the properties and quality of MoS2-typed anode
ingredients for LIBs. To date, few studies have proposed that merging two or more of
these approaches can obtain even superior electrochemical properties than single
approach alone. This claim has been demonstrated by Yu et al. [19] by developing a
unique N-doped carbon@MoS2 box like-nanoarchitecture consisting of graded MoS2
box-like structures. Adding the N-doped carbon cells conferred an enhanced electric
conductivity together with the anchored tiny MoS2 nanosheets forming all together a
nanosheet-on-nanobox structure. As associated with the ordered MoS2 boxes, N-fixed

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carbon@MoS2 boxes facilitate enhanced charge-discharge cycling activities with cyclic

stabilities (1000 mAhg-1 at 200 cycles).

Figure 2. Representation of TMDs based electrode materials for LIBs and their
intercalation/conversion reactions.

On the other hand, an advanced C-Si supported MoS2 ternary construction consists of
few-layered C@MoS2 microspheres anchored on Si nanoparticles was reported by Kang
et al. [20]. In this report, Si nanoparticles play a significant part in enlightening the
electrochemical behavior owing to their small release potential and enormously
extraordinary reversible capacity. The carbon fascinated MoS2 microspheres serve as the
supports, thus maintaining the structural feasibilities during charge-discharge process and
also aid in optimizing the benefits of Si nanoparticles. As a result, these distinctive
hierarchical structures demonstrate superior capability of 1020 mAhg-1 at 1000 mAg-1
after 100cycles as compared to bare MoS2/C microsphere (718 mAhg-1). Similar work
has been reported by Shan et al. [21], where 3DMoS2@carbon fibers exhibited high
reversible areal capacity of 5.2 mAh cm-2 on 2.5 mA.cm-2 with superior rate behavior.

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The authors prepared carbon fibers via merely carbonizing the waste cotton employed as
carbon source hence, reflecting a cost effective and eco-friendly approach. Studies
accompanied by Xue et al. [22] and Wang et al. [23] revealed that MoS2 microsphere/N-
doped carbon demonstrated excellent reversible capacity of 715 mAhg-1 at 100 mAg-1
after 50 sequences with remarkable cycling stability and that hydrothermally synthesized
sheet-like MoS2 developed on the surfaces of carbon and TiO2 core-shell nanofibers have
great reversible specific capacity of 1460 mAhg-1 at 100 mAg-1 with rate performance of
928 mAhg-1 at 2Ag-1. This binder free anode materials are suitable for flexible LIBs.
Recent studies revealed that rational design of effective and durable anode materials are
potentially significant for high electrochemical performance of LIBs. In this view point,
many researchers have developed conductive materials that are structurally modified such
as graphene, through the introduction of noble metals or doping of non-precious metal to
improve their electrochemical reactions. For instance, Yang et.al. [24] designed MoS2/N
with S co-doped graphene via simple electrochemical exfoliation combined with
hydrothermal reactions of the precursors. A 3D interconnection of few-layered MoS2 and
graphene have been achieved by this synthetic procedure, a structure that relieves the
restacking of binary components and thereby accelerated the transport of electrons and
enhancing Li-ion storage capacity as an electrode for batteries. This anode exhibited good
revocable capability of 1012 mAhg-1 after cycling 300 times at 0.5 Ag-1. It has also
delivered a maximum energy density of 890 Whkg-1 along with the powder compactness
of 130 W kg-1.
Wang et al. [25] invented nanosized porous MoS2(1-x)Se2x hybrid encapsulated in
graphene sheets to form a mesoporous heterostructure (i.e. meso-MoS2(1-x)Se2x/rGO
hybrid) consisting of perpendicularly grown 2D sheet-like structure on graphene layers.
The meso-MoS2(1-x)Se2x/rGO hybrid possessed an improved electrochemical performance
for LIBs, ascribed to the benefits of 2D sheet-like alignment and the sulfur-selenium
joined effect. Adding Se may confer additional active diffusion path for both Li-ions and
electrons during the charge/discharge reactions by possibly broadening the positioning of
the (002) crystal plane. Moreover, the introduction of Se in MoS2 may auxiliary induce
the transition of meso-MoS2(1-x)Se2x/rGO hybrid from 2H phase to further stable metallic
1T phase of MoS2. The meso-MoS2(1-x)Se2x/rGO hybrid exhibited capable rate
performances and respectable cycling stability with an best capacity of 830 mAhg-1 at a
current density of 100 mAg-1 for 150th cycle. This hybrid maintained a capacity of 415.3
mA g-1 at enormous current density is 1000 mAg-1 creating them a prominent candidate
for different types of batteries. In a parallel study, Zhu et al. [26] was able to produce
MoS2/N-doped carbon (i.e. MoS2/N-C) from simplistic instantaneous vapor sulfurization
and carbonization of MoOx/aniline nanorods and has employed it as anode. This MoS2/N-

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C electrode displayed remarkable rate capability of 667 mAhg-1 at 10 Ag-1 and

outstanding cyclic stability of 1110 mAhg-1 at 1Ag-1. This outstanding electrochemical
performance exhibited by MoS2/N-C electrode was assigned to the synergistic effects of
MoS2 with extended interlayer spacing and N-doped carbon. In addition, the ample voids
produced by the distended interlayer spacing of MoS2 promote the diffusion of Li-ion and
can enhance the volume changes during the charge/discharge responses, creating further
active sites for Li ion storage.

3. WS2-based anode materials for LIBs

Among the graphene-like two dimensional (2D) TMDs, tungsten disulfide (WS2) has
received growing devotion owing to its good mechanical, electric, and optical
characteristics [27]. Layered WS2 is self-possessed of sandwich structure arranged via the
weak van der Waals forces and robust covalent links in-plane among S and W atoms.
This structural configuration is advantageous for lithium ion storing with a theoretical
capability of 433 mAhg-1, allowing intercalation of Li atoms in between the layered
structure easily [28]. WS2 has a great density of 7.6g cm-3 making its volumetric powder
density four folds greater than that of standard graphite [29]. WS2 is encompassed of
three arranged atomic sheets (S-W-S) detained together via weak Van der Waals strength
similar to MoS2, although the interactions among WS2 sheets are moderately weaker than
that of MoS2. In addition, WS2 owns an advanced intrinsic conductivity in comparison to
MoS2 [30]. These features can provide lithium ions more access to easily
intercalate/deintercalate. However, WS2 also suffers with low electrical conductivity as
well as undependable stability during long cycles similar to MoS2, features that limit its
application in LIBs.
In order to overcome these limitations, two methods are commonly adapted including the
coupling of WS2 with carbon-based materials and phase alteration from semiconducting
WS2 to metallic phase. Controlling the crystalline favored orientation including (001)
plane of WS2 sheets more enhanced the distribution kinetics and electrochemical activity.
Phase control of the WS2 is of important concern as this process can improve the Li-ion
transfer. In details, the metallic (1T) stage of WS2 has an octahedral synchronization that
demonstrates equivalent characteristics and microstructure as associated to
semiconducting (2H) phase of WS2, like the trigonal prismatic orientation represented by
the transversal movement of one of S atomic layer [31]. Conversely, limited studies have
been documented concerning the preparation and use of 1T WS2 in LIBs. Analogous to
MoS2, the fabrication path and approach of 1T WS2 mostly comprise alkali metal and
butyllithium intercalation, rare metal doping, pulsed laser deposition, and ammonia ions
intercalation [31]. For instance, 1T-WS2 nanoribbon was reported by Liu et al. [32] to

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have been produced via the intercalation of ammonia ions (NH4+) and the removal of 0.75
electrons per NH4+ from WS2. In addition, electron supporter substitutes like Re, Tc and
Mn can facilitate the phase transformation of WS2 by forming covalent bonds resulting in
a prominent escalation in the stable metallic WS2. Nevertheless, some inadequacies tend
to limit the request of these approaches; these include the complexity of the preparation
process and the low scale production. Therefore, there are still channels for improving the
electrochemical performances through choosing the efficient approach to achieve the 1T
phase WS2. Although WS2 has received potential consideration for its remarkable
capacity, ample resources as well as its low cost, still the dilemma on how to advance its
cycle stability and reversible capability is quite a long way for research. Phase controlled
synthesis of WS2 is thus accelerated and studied for LIBs based on the phase purity of
WS2.
Wang et al. [31] stated the employment of metallic WS2 (1T) phase material deposited
on carbon fiber cloth for LIBs. This study revealed the transversal movement of S grains
in WS2 by nitrogen (N) atoms. In this manner, the cyclic strength of metallic phase WS2
was achieved through N-W covalent bond formation. The enhanced electrochemical
performance suggested that the introduction of metallic phase might not only diminish
the preliminary discharge capability loss, then also could enhance the reversible
capability compared to the conventional semi-conducting phase of WS2 (2H).
A study conducted by Li et al. [33] demonstrated an in-situ synthesis procedure for WS2
nanosheets deposited on compact graphene oxide hollow sphere (Hs-rGO) with N-doped
graphene (NG) covering the outward layer to form NG-WS2@Hs-rGO heterostructure.
When employed as anode for LIBs, NG-WS2@Hs-rGO heterostructure showed a great
capacity of 1309 mAhg-1 at 100 mAg-1, which delivers a release capacity of 301 mAhg-1
over 320 trails. The retention capacity extents as good as 106% of the release capacity at
10th cycle. It has been shown that the internal Hs-rGO delivers a space for the majority
growth of WS2, additionally the exterior layer of WS2 deposited with NG also facilitates
extra active edges for Li ion storage aside from enhancing the conductivity. Zhou et al.
[34] employed electrospinned WS2/Carbon nanofibers (i.e. WS2/CNFs heterostrucutre) as
anode materials for LIBs. This WS2/CNFs heterostructure is composed of a single layer
WS2 consistently implanted in carbon fibers and exhibited discharge capacity of 756
mAhg-1 at 100 mA g-1, a feature credited to its enormous specific surface area that
accommodates large interfacial capacitance. The employed synthetic procedure revealed
that the intrinsic flexible quality of electro-spun nanosized fibers rendered them an
excessive probable in the deployment of binder free anodes. This procedure also is well
suitable for additional comparable 2D layered materials aside from WS2 and hence can
provide a favorable aspirant electrode for bendable LIBs. Li et al. [35] described an in-

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situ synthesis of WS2@rGO hybrid that could convey an improved capacity of 565 mAh
g-1 at 100 mAg-1 after 100 sets with remarkable rate capacity of 337 mAhg-1 at 2 Ag-1. In
other work, Liu et al. [36] demonstrated negative charged of WS2/GO nanosheets in
generating extremely effective flexible anode for LIBs assembled simply through a
vacuum filtration process of homogeneous hybrid lamellar films. This additive free
WS2/rGO flakes electrode exhibited superior cycling steadiness with worthy rate capacity
and a great reversible ability of 698 mAhg-1 at 100 mAg-1 even after 100 cycles, which
was significant larger than that of bare WS2 and rGO nanosheets of 89 mAh g-1 and 60
mAhg-1, respectively. This greater electrochemical behavior can be attributed to the
consistently altered flaky structures, where rGO nanosheets diminished the restacking of
WS2 nanosheets, thereby improving the conductivity and endured the varying capacity in
Li ion insertion-extraction reactions.

4. MoSe2 based anode materials for LIBs

Molybdenum diselenide (MoSe2) is a one of the promising anode material for LIBs with
narrow bandgap semiconductor. It consists of stacked layers of Se-Mo-Se sheet-like
crystal structure creating it a good applicant for LIBs through electrochemical
intercalation process. Unlike MoS2, MoSe2 might offer extra benefits because of the high
electrical conductivity of Se as compare to S atoms [37]. With respect to their crystal
orientation, MoSe2 has two aspects: (i) semi-conductive trigonal 2H-MoSe2 and (ii)
fusible octahedral 1T-MoSe2 phases, similar to MoS2 and WS2 materials. The 1T MoSe2
construction has a great inherent electronic conductivity to defeat the compassion to air
atmosphere by substituting a straight Li intercalation/exfoliation way with a NH4+
intercalation one. While, 2H-MoSe2 typically agonizes from minor cycling stability and
lower rate competence owing to its variability and inherent low electronic conductivity.
To alter and direct the structure of MoSe2, many strategies have been implemented such
as nanostructure design, developing of integrated electrodes, and coupling with carbon-
based conductive frameworks [38]. For instance, Mendoza-sanchez et al. [39] reported a
liquid phase exfoliated MoSe2 embedded to single-wall carbon nanotubes (SWCNTs)
electrodes fabricated via a spray-assisted method and concurrently studied their
electrochemical performance in a 1M LiPF6-EC-DMC electrolyte in a standard three-
probe cell within 3V electrochemical window. The cyclic stability of MoSe2 is enhanced
by SWCNTs. As fabricated MoSe2-SWCNTs probes demonstrated a capability of 798
mAg-1 at a 0.05C rate for eight cycles, which is much greater compared to capability of a
bulk MoSe2-carbon black probes of 557 mAhg-1 at 0.05C for first cycle. The
MoSe2/SWCNTs electrode showed capacity retaining of 58% over 100 sequences at a
0.5C rate. The enriched demonstration of the MoSe2-SWCNTs probes was credited to the

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nanosized MoSe2 nanosized-platelets and the coupling effect with SWCNTs that
facilitated mechanical strength. Furthermore, alike nano-replication approach for
perforated TMDs was effectively realistic to develop other TMDs. It demonstrated a
reversible capability above the theoretical reversible ability of MoSe2 which is 422 mAh
g-1 with respect to transformation reaction of Li ion tracked by making Mo elements in
the insoluble Li2Se matrix [40]. This is beneficial for improving the electrochemical
performance especially for lamellar arranged materials, owing to the extra interfacial Li
ion storage, consequently creating the bridge among batteries and supercapacitors at the
nanoscale. Surface alteration or alteration of the band gap by establishment of
heterojunction to improve the conductivity is more prominent strategy for proceeding
sheet-like MoSe2 as anode materials. Interestingly, nanosized MoSe2 holds slower charge
transfer conflict, restored electrochemical efficiency, and has better probable as anode
materials associated to amorphous ones. However, they may existing a similar phase
transition progression after the first cyclic charge-discharge course.
Wang et al. [41] demonstrated the conversion of MoO3/PANI composite and Se powders
in Ar gas atmosphere into nitrogen (N)-doped carbon anchored on a surface of MoSe2 by
simple heating. This synthetic method does not need a multi-step procedure or the
application of extremely toxic reducing agents. This procedure showed the important role
of PANI played in the assembly of N-fixed carbon@MoSe2 through the reduction of
MoO3 and Se while being decayed and carbonized into N-doped carbon nanorods cores.
The N-doped carbon@MoSe2 demonstrated high discharging capability of 1275 mAhg-1
with a great reversible lithium drawing out capability of 928 mAhg-1 and a coulombic
efficient of 72.8%. Even after 100 cyclic reactions, the N-doped carbon@MoSe2
electrode delivered a reversible capability of 906 mAhg-1 with a capacity retention ratio
of 97.6 %. This enhanced electrochemical performance can be pinpointed to the exclusive
core/branch nanostructure of N-doped carbon@MoSe2 and synergistic outcome between
the N-doped carbon nanorods cores and MoSe2 layer branches. In a different study, Su et
al. [42] has employed an anode for LIBs developed from 1D MoSe2/C nanorods hybrid
derived from organic/inorganic precursors of Mo3O10 (C2H10N2) with ensuing selenization
and carbon coating process. The MoSe2/C nanorods exhibited 835 mAhg-1 at 200 mAg-1
with retention of 755 mAhg-1 after 200 cycles. The remarkable electrochemical acts of
the MoSe2/C nanorod hybrid were due to the bicontinuous electron/ion pathways, small
charge transfer resistance and robust structural features and stability. In the case of bare
MoSe2, the electrochemical reaction is limited attributable to a great volume expansion
and little electronic conductivity. Therefore, the coupling of conductive materials with
MoSe2 demonstrated excellent electrochemical performance. Another study conducted by
Liu et al. [43] demonstrated sheet-like MoSe2/C hybrid and Zhu et al. [44] reported

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MoSe2 deposited on carbon fibers to form nanoheterojunction, both showed excellent

reversible capacity with stable current densities. These results indicated that the
electrochemical performance could be intensively enhanced by making the nano-
heterostructures. However, these electrodes were demonstrated to have low packing
density owing to their extraordinary specific surface area and large carbon weight
percentages.
Cui et al. [45] developed an electrospinning strategy for coupling of graphene slips into
carbon deposited MoSe2 (i.e. MoSe2/C@G heterostructure) and subsequently employed
as anode materials for LIBs. This heterostructure demonstrated superior discharge
capability of 370 mAhg-1 when 200 cycles at 0.2 A g-1 with remarkable rate performance.
Tang et al. [46] presented MoSe2 microspheres consisting of unified nanoflakes that are
covered with regular tinny N-doped carbon layer made via simplistic two-step approach
of hydrothermal reaction assisted via dopamine thermal polymerization. This MoSe2/N-
carbon hybrid presented minor polarization resistance, restored reversibility with
improved electrochemical functioning related to bare MoSe2. This hybrid provided a
good reversible capability of 689 mAh g-1 at 100 mAg-1 after 100 cycles with high rate
capacity (698 mAhg-1 at 2 Ag-1). This enhanced electrochemical functioning can be
indorsed to the combination of N-fixed carbon layer and their ordered microsphere
structure with extra active edge sites and rapid ionic/electronic transfer characteristics.
Similarly, Wang et al. [47] has developed N-fixed carbon/MoSe2 core/branch
nanostructure by configuring a combination of polyaniline (PANI) inserted to MoO3
nanorod composite and Se powder in argon environment. This hybrid demonstrated a
extraordinary reversible capability of 906 mAhg-1, and capacity retaining rate of 97.61%
at 100 mAg-1 afterward 100 cycles and capacity rate of 560 mAh g-1 at 1 Ag-1, owing to
the exclusive structure of N-fixed carbon nanorod centers and the MoSe2 nanosheet
divisions.
To obtain the heterojunctions of TMDs, coupling qualities of various TMDs have been
observed as a promising approach that alters their electronic properties and thereby
posing a possibility of application in the conversion and storage energy. For instance,
Yang et al. [48] developed a simple, low price and great yield solution-phase scheme for
making MoS2-MoSe2 p-n heterojunctions with perpendicularly developed MoSe2 through
coating with amorphous carbon. This heterojunction exhibited an advanced and efficient
electrochemical and Li-ion storage performance respectively, with a high reversible
capability rate of 676 mAhg-1 200 mA g-1 for 200 cycles. Recent studies showed that the
formation of MoS2(1-x)Se2x alloy through the addition of Se into MoS2 facilitated the
extension of the interlayer positioning for additional active diffusion of ions and electrons
in the course of charge/discharge process. However, this has also reduced the energy

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barriers to permit over the layers because of the minor distortion and the diverged electric
field in the basal levels as a result of the bigger radius exhibited by Se [49]. Wang et al.
[49] synthesized an optimal 2D layered perforated MoS2(1-x)Sex/rGO hybrid and has
shown to display a large capability of 830 mAhg-1 after 150 cycles at 100 mAg-1 and an
improved capability of 415 mAhg-1 at 1000 mAg-1. In addition, MoSe2 can also be
employed to improve the cycling and rate performance of TMCs. This has been
substantiated by Jin et al. [50] who developed an electrode material of Cu2-xSe@carbon
nanosheets covered with MoSe2 nanoparticles. This electrode material has exhibited an
enriched reversible capability of 432 mAhg-1 after 100 cycles at 100 mAg-1 with
improved rate capacity surpassing that of bare Cu2-xSe@carbon (166 mAhg-1) or pure
phase Cu2-xSe nanosheets (82 mAh g-1).

5. WSe2-based anode materials for LIBs

Tungsten diselenide (WSe2) is an energetic member of TMDs and has been regarded
valuable due to its exclusive characteristics, having a narrow bandgap of 1.6 eV,
enormous neighboring layer spacing of 0.648 nm which is two folds greater related to
graphite, and also can provide an efficient reversible ion intercalation and separation.
Further, WSe2 has shown to have a good density and large volumetric capacity. The
theoretical mass density of WSe2 is 9.32 g cm-3 causing it to possess a good volumetric
energy density which is considered extra prominent than the gravimetric energy density
due to the inadequate battery packing space [51]. Several studies have proposed that
WSe2 might be a good choice for advanced lithium-ion anode materials. Yang et al. [52]
documented the WSe2 nanoplates as a probe material for both LIBs and SIBs, which
demonstrated an established reversible capability and an extraordinary rate capability
with long cyclic life of over 1500 cycles at 1000 mAg-1. The charge-discharge process
substantially revealed the reversible conversion mechanism shown as follows:

WSe2 + 4 Li+ +4 e- ↔ W + 2 Li2Se (7)

Wang et al. [53] demonstrated an in-situ growth of hierarchical mesoporous

nanoarchitecture of WSe2 deposited on reduced graphene oxide (i.e. WSe2/rGO)
composite via facile one-step solvothermal method and consequently used as anode
materials for LIBs. The WSe2/rGO hybrid exhibited a large initial discharge capability of
744 mAhg-1 at 0.2C and maintained the capability of 528 mAhg-1 even after 80 cycles in
contrast to a pure WSe2 (549 mAhg-1) which maintained 98 mAhg-1 after 80 cycles. This
commendable electrochemical performance was attributed to its hierarchical structure.

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rGO nanosheets provide more conductivity act as the skeleton of WSe2/rGO anode
providing the efficient electron transfer and also prevented the aggregation of WSe2.
Moreover, the rGO nanosheets also facilitated the in-situ growth of WSe2 layers on the
top of graphene with high active sites permitting an effective ionic diffusion and simple
electrolyte infiltration.

6. Other TMDs for LIBs

Many types of TMDs materials exhibited nanosheets morphology however, the relatively
small electrical conductivity and weak structural stability in the electrochemical process
hindered their prospective function as anode materials. In most cases, the nanosheets
developed in the form of agglomerates mainly confer low electrochemical activity in the
anodes due to the constrained specific surface area which affects the availability of Li
ions. In order to overcome this demerit, many strategies have been taken into account
such as the development of three dimensional (3D) flower-type micro/nanospheres,
micro/nanostructures of 2D TMDs nanosheets, and coupling of TMD nanosheets in
conductive carbonaceous and polymer-carriers with high certain surface areas.
It is well established that graphene nanosheets are a remarkable conductive substrate to
dissolve and confine active materials due to its admirable conductivity, large surface area
and strong mechanical strength. However, 2D graphene sheets could not restrict active
anode materials excellently. Another mode of graphene (i.e. graphene nanoscrolls)
comprising of several rolled-up graphene nanosheets has been demonstrated to
demonstrate open-terminated tubular hollow structure which is reflected as a superior
conductive substrate in confining active materials through providing open channels for
more ion transport. Various sulphides such as TiS2 and selenides (i.e. TiSe2, VSe2, and
NbSe2) were evaluated as cathodes for LIBs [54]. However, to obtain an acceptable
energy packing, different required cathode features were sought: (i) large free energy of
reaction; (ii) a variety composition ranges; (iii) a low change in free energy over
configuration range n (mol Li/mol host); (iv) reversibility of reactions; (vi) in elevation
diffusivity; (vii) indecipherability of the functioning materials in electrolyte medium; and
(viii) good electronic conductivity. Among the TMDs explored, TiS2 is superior for these
criteria, which possesses an OCP of 2.47 V in comparison to Li metal with an power
density of 480 Whkg-1 in a half cell alignment [54]. However in the presence of oxygen,
TiS2 displayed more instability. Strikingly, VSe2 demonstrated a greater rate of capacity
(OCP of 2 V versus Li metal) than TiS2 and has high stability and good reversibility.
Zhang et al. [55] demonstrated the thermal decomposition of graphene nanoscrolls
linked by wrinkled graphene nanoslips as an efficient conductive complex for confirming
tin disulfide (SnS2) nanosheets for LIBs. During the thermal quenching, covering SnS2

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nanosheets in the nanoscolls formed a 2D/3D heterojunction. The ratio of nanoscolls and
nanosheets can be achieved by merely adjusting the quenching conditions. The elevated
SnS2/3DG possesses high specific surface area of 127.1 m2g-1 with multi mesoporous
which can efficiently hinder the aggregation of SnS2 in order to facilitate an abundant
sites for lithiation/delithiation. The SnS2/3DG hybrid demonstrated improved reversible
capacity of 1514.8 mAhg-1 at 01.Ag-1 with excellent rate capacity of 665.4 mAhg-1 at 5
Ag-1 and good cyclic stability of 1050mAhg-1 at 50 cycles.

Table: 1 TMDs based nanocomposite electrode materials for lithium ion batteries

Electrode materials Current Capacity/number of cycles Ref.

density (mAhg-1)
(mAg-1)
MoS2 nanosheets 1000 900/1000 57
MoS2 nanobelts 2000 480/100 58
MoS2@3D vertical 100 670/30 59
graphene
MoS2@rGO nanosheets 100 420/160 60
MoS2/C nanosheets 500 815/100 61
MoS2/C nanospheres 100 523/100 62
MoS2 on carbon 200 477/200 63
monolayer
MoS2/Fe3O4 2000 1033 64
MoS2/TiO2 100 710/100 65
MoS2/Ni3S2 200 568 66
MoSe2 nanosheets 1000 455/100 67
MoSe2 microspheres 200 433/50 68
MoSe2 nanoplates 42.2 380/50 69
MoSe2 sheets/carbon 100 576.7/100 70
MoSe2/Carbon 1000 1208/150 71
nanospheres
N-doped carbon@MoSe2 100 862.7 72

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Table: 2 Various TMDs materials coupled with graphene oxide electrode materials for
lithium ion batteries.
Materials Key results Ref
Layered MoS2/rGO Capacity of 750 mAhg_1 at 3 A g_1 and 1180 73
mAhg_1 after 80 cycles at 0.1 Ag_1
MoS2 nanoflakelet/rGO Capacity of 1902 mAhg-1 for 1st 74
discharging, high coulombic efficiency of
76.45%
MoS2 nanowall/Gr Reversible capacity of 700 mAhg_1 after 75
100 cycles at 0.05 Ag_1
3D flower-like MoS2/Gr Reversible capacity of 980 mAhg_1 at 0.1 76
Ag_1 and 740 mAhg_1 after 100 cycles at 1
Ag_1
Honeycomb-like MoS2/Gr Capacity of 1235.3 mAhg_1 at 0.2 Ag_1 and 77
foam 85.8% retention after 60 cycles
Flower-like Capacity of 300 mAhg_1 at 20 Ag_1 and 728 78
MoS2/Gr/CNTs mAhg_1 after 1000 cycles at 5 Ag_1
3D MoS2/C3N4/N-rGO Capacity of 800 mAh g_1 at 0.1 Ag_1 and 79
network 91% retention after 100 cycles
3D MoSe2/rGO foam Capacity of 1160 mAh g_1 at 0.1 C and 650 80
mAh g_1 after 50 cycles at 0.5 C
Perpendicular Capacity of 1001 mAh g_1 at 0.1 A g_1 and 81
MoSe2/rGO 715 mAh g_1 after 100 cycles
Ultrathin WS2/3D Gr Capacity of 766 mAh g_1 at 0.1 Ag_1 and 82
416 mAh g_1 after 100 cycles
Few-layered WS2/rGO Capacity of 400–450 mAh g_1 after 50 83
cycles at 0.1 A g_1
Quasi-3D wrinkled Reversible capacity of 1102 mAhg_1 84
MoSe2/Gr
VSe2/rGO Capacity of 632 mAhg_1 at 0.1 A g_1 during 85
60 cycles
ReS2/rGO Capacity of 918 mAhg-1 at 0.2 C 86
V5S8/graphite nanosheet Capacity of 1112 mAhg-1 at 0.1 Ag-1 787 87

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Cao et al. [56] reported the application of TiO2-B@VS2 heterojunction nanowire arrays
as additive free anode for LIBs. This TiO2-B@VS2 heterojunction holds a superior
reversible capability of 365 mAhg-1 over 500 cycles at a current density rate of 1C (335
mAg-1). Moreover, TiO2-B@VS2 heterojunction has been shown to serve a high volume
rate of 171 mAhg-1 at 10C rate assigned to the outstanding physical stability of the TiO2
nanoarrays together with the high capacity and conductivity of VS2. Various TMDs based
nanohybrid for LIBs were tabulated in Table-1 and Table-2, reflecting the significane of
2D/2D heterojunction for power storage concerns.

7. Summary and future outlooks

This chapter summarized the latest insights in the progress of graphene-type enveloped
metal dichalcogenides such as MoS2, WS2, MoSe2, and WSe2 and their hybrids as
conductor materials for LIBs. TMDs possess an extensive range of intercalation
chemistry supported by the following reasons: (i) the amplified valence of the
chalcogenide atoms facilitates the contribution of conversion metal valence, (d) paths in
covalent attachment-this has the result of decreasing the recognized control on the metal
center which fascinating metal-to-metal bond creation, and (ii) the greater diversity of the
X2- anion permits for the acceptance of arrangements in which the surroundings of X is
extremely irregular. All these materials have achieved prominent accomplishments up to
date. However numerous challenges still exist that need to be solved in the future.
Currently, the integration of TMDs with carbon medium such as graphene has shown to
enhance the energy and power densities. This process however has reduced the initial
coulombic efficiency. Furthermore, tamper with or intercalation via heteroatoms with S,
Se, C is deemed promising for improving the conductivity as well as for extending
interlayer spacing causing an enhancement in the electrochemical reactions. TMDs could
be securely employed as anode materials exclusively for high power batteries due to the
outstanding rate capability and higher cycling stability. There are still some important
hurdles that need to be addressed in order for the commercial employment of progressive
power packing gadgets based on the TMDs materials to be realized. It would be rational
to trust that more important considerate and search in this emerging field would bridge us
to new sensational outcomes for innovative high functioning rechargeable batteries. In
order to optimize the LIBs performance, two major concerns should be taken into
consideration (i) fundamental agreement the chemical reaction arising in TMD
electrodes, and (ii) fabricating innovative TMDs devices.
Major issues concerning LIBs are (i) as commercial anodes for LIBs, graphite materials
cannot encounter the continually-growing demands for high power density due to their
limited specific capacity and (ii) unsatisfactory capability rates. The electrochemical

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endowment of TMDs at large current ditch is inhibited by their inadequate electronic

conductivity regulating the reasonable power density. These materials have been
exploited as novel class of anode material for LIBs exclusively for elevated rate uses in
spite of their smaller theoretical capability. But, the studies on WS2, WSe2, and MoSe2-
based hybrids are still in their infancy. These materials possess limited cycling constancy
due to enormous volume deviations through insertion/extraction progressions of ions.
More progressive studies should give emphasis on the electrochemical functioning
mechanism, the optimization of the electrode materials synthesis, and the control and
manipulation of phase and structural stability. Especially, the procedure for the
intercalation and conversion manners should be promote evaluated to elucidate the
ongoing arguable in the transformation behavior of these transition metals and their
reversible progression. Moreover, it is essential also to further established the capacity
declining mechanism and impact of shuttle effect for TMDs. Indeed, more experimental
and modeling studies on the electrochemical phenomena in high capability electrode
materials for LIBs are need to be performed to completely understand the fundamental
degradation of electrochemical performance during the cycling process. It has been
scripted also in this chapter that the in-situ studies provided more evidences and concepts
to overcome the electrochemical degradation phenomena. Additionally, it is very
necessary to optimize and control the design schemes such as nanostructuring,
nanoporosity, surface coating and compositing for justification of electrochemo-
mechanical degradation.

Acknowledgement
This research work was supported by the National Research Foundation of Korea (NRF)
(2020R1A2B5B01002744).

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nanostructured molybdenum diselenide/graphene foam as anodes for long-cycle life
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[81] Z. Luo, J. Zhou, L. Wang, G. Fang, A. Pan, S. Liang. Two-dimensional hybrid

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[82] G. Huang, H. Liu, S. Wang, X. Yang, B. Liu, H. Chen, et al. Hierarchical
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Chapter 4

Metal Sulphides for Lithium-ion Batteries

Udaya Bhat K.1*, Sunil Meti1, C. Prabukumar1, Suma Bhat2

1
Department of Metallurgical and Materials Engineering, National Institute of Technology
Karnataka, Surathkal, 575025, India
2
Department of Mechanical Engineering, Srinivas School of Engineering, Mukka, 575025, India
*[email protected]
Abstract
Increasing demand for flimsier, thinner, flexible batteries with higher capacities
encourage present and future research for newer electrode materials with improved
features. Metal sulphide based nanomaterials, due to their unique properties have opened
a new domain for exploration in the domain of lithium-ion batteries. This review
summarizes various metal sulphides, their developmental highlights and opportunities as
the electrode materials. It offers updated knowledge on various metal sulphide systems.
Review concludes by highlighting the promises metal sulphides as electrodes for the
future lithium-ion batteries and challenges to be crossed to make it successful.
Keywords
Lithium-ion Batteries, Metal Sulphides, Improved Performance, Nanocomposites

Contents

1. Introduction..............................................................................................92
2. Demands on batteries in 21st Century....................................................93
3. Design of a lithium-ion battery (LIB) ....................................................93
4. Materials related issues in LIBs in modern era ....................................94
5. Advantages of metal-sulphides for LIBs ...............................................95
6. Metal sulphide based nanocomposites for battery applications .........96
7. Different types of metal sulphides as anode materials in the LIBs
applications .........................................................................................................97

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7.1 Layered metal-sulphides for LIBs. ....................................................97

7.2 Copper sulphides ...............................................................................98
7.3 Cobalt sulphides...............................................................................100
7.4 Molybdenum disulphide (MoS2) .....................................................101
7.5 Tungsten disulphide (WS2) ..............................................................103
7.6 Iron disulphide (FeS2) ......................................................................105
7.7 Tin sulphides ....................................................................................106
7.8 Nickel Sulphides ..............................................................................108
8. Synthesis techniques for metal sulphides ............................................109
8.1 Solid state method............................................................................109
8.2 The hydro/solvothermal method ......................................................110
8.3 Microwave-assisted hydrothermal synthesis ...................................111
8.4 Spraying-related methods ................................................................112
9. Summary ................................................................................................112
References .........................................................................................................112

1. Introduction
Increased awareness of the modern society on environmental pollution and dependence
on the uninterrupted and portable power sources drives the focus on sustainable, efficient,
economical energy production and its management. Electrical energy storage devices,
like batteries and capacitors play pivotal part in the management of environmentally
friendly sustainable energy [1]. Typical energy storage technologies for portable power
devices are fuel cells, batteries, pseudocapacitors, etc. They all work on the basis of
conversion of chemical potential into electricity [2].
Presently, batteries are the main source for powering devices which are both stationary
and mobile in nature [3]. Rechargeable batteries (or secondary batteries), such as lithium-
ion batteries (LIBs), metal-air batteries, Na-ion batteries, Mg ion batteries are all devices
working on the repeated reversible conversions of energy from chemical to electrical
ones. Among various secondary batteries, LIBs are considered to be the most important
energy storage and conversion units [4,5].

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2. Demands on batteries in 21st Century

The first commercialized batteries are introduced by Sony to the market. Since then, the
rechargeable LIBs have made a niche market share quickly [6]. The LIBs are already
been used as the main source of energy due to their relatively high energy density,
capacity, and power density, efficient cycling stability and unimpeachable power
performance [7]. The global demand of growing power consumption has stimulated the
world to look for the next generation Li batteries with efficient storage technologies for
supporting low carbon society. The next-generation LIBs are future of energy storage
devices in the main application of hybrid electric vehicles and smart grids. Presently, the
researchers are mainly focused on exploiting new flexible, lighter and thin electrode
materials to improve energy density for LIBs [8]. The growing consumption of non-
renewable fossil fuels and environmental pollution has attracted the researchers to
explore the eco-friendly renewable energy sources, like nuclear power plants, solar and
wind. In this context the LIBs system play a pivotal role in the energy management which
can be harvested from the renewable energy sources [9].

3. Design of a lithium-ion battery (LIB)

Positive electrode (cathode), negative electrode (anode), separator and liquid electrolyte
(ion medium) are the four important components of LIBs (Fig. 1). The electrolyte
conductor medium helps in the transportation of ions between the electrodes. The
electrolyte should provide the environment for ions to diffuse with high mobility so that
the active materials (cathode and anode) will be efficiently utilized. Electrolytes can be
organic or aqueous. It is well accepted that organic lithium-ion battery has matchless
performance, flexible in design, and excellent energy density. They show characteristic
features, like longer lifetime, superior energy capacity, and weightless in comparison
with other secondary batteries which were in use [10,11]. Though LIBs with organic
electrolytes show excellent performance, aqueous rechargeable LIBs offer the benefit of
lower cost, higher safety and environmentally benign nature [10,11].
In LIB, the ion transfer reaction occurs between two active materials, anode and cathode.
In a real system, many side reactions also occur. In general, the mechanism of the active
materials in the aqueous electrolyte is complex compared to that in the organic material.
During discharge cycle in LIBs, the lithium ions transfer from the negative electrode to
positive electrode and is reversed in charging cycle. Lithium intercalation compounds,
such as LiCoO2, LiMnO4, LiFeO4, Li3V2(PO4)3 are the commonly used cathode materials
in LIBs. In LIBs, graphite and transition metal oxides are the major choices for the anode
material. Amongst these, many anode materials show good cyclic performance but low

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initial charge-discharge efficiency. Transition metal oxides have good cyclic efficiency
but highly irreversible capacity loss in the first cycle [12]. One of the potential solutions
to this problem is to develop new electrode materials. Improved electrodes allow for the
storage of more lithium ions and increase the battery capacity [13].

Figure 1. Schematic configuration of LIBs.

4. Materials related issues in LIBs in modern era

The morphology, composition and microstructure of the electrode materials are crucial
for the efficient electrochemical performance of the batteries [14,15]. The characteristic
electrode materials should have the properties, like high conductivity, increased surface
area, and short traveling distance for lithium ions. They could be tailored through the
materials processing route. Further, the use of the nanostructured materials obtained a
special recognition as they offer unique features like short diffusion lengths, high surface
area and increased electronic/ionic conductivity. These features facilitates easy
intercalation of Li-ions into/from the host electrodes in very short time [16,17].
The electrochemical batteries performance is mostly dependent on the electrode
materials. At present, commercial graphite is the predominant choice as the anode
material because of its high Columbic efficiency and flat potential profile. However, due
to graphite’s low theoretical capacity of 372 mAh g-1, poor rate capability and safety
problems limit its applicability for high energy density targets. The low power density of
LIBs is due to the slow diffusion (10-8 cm2s-1) of lithium ions in the graphite structure.
The graphite anode also has a major drawback of forming lithium dendrites which limit
its applicability in the high-power electric devices (like vehicles). Added to that the
production cost and safety concern, especially in the mass-energy storage system is high

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[11]. This has forced the researchers to explore and develop new-type anode materials
[18]. These challenges could be overcome by using numerous candidates, like metals,
semimetals, metal sulphides and metal oxides. Amongst these, metal sulphides are
considered as the best alternate candidates for the anode material over the graphite which
offers the advantage of large capacity.
It is already mentioned that charge/discharge rates of LIBs is completely dependent on
the mobility of the lithium ions and the electrons through the electrolyte and the active
electrode material. Various strategies have been followed to increase the lithium-ion and
electron transport kinetics. Also, the structural features promoting high ion and electron
transport [19,20] or by reducing the path length over which electrons and lithium ions
have to move in the batteries. With these strategies, a series of three-dimensional hybrid
electrode materials [20], which can provide high charge–discharge rates have been
developed.

Figure 2. Intercalation of Li-ions into the layers of metal sulphides.

5. Advantages of metal-sulphides for LIBs

Metal sulphides are bound to exhibit less volumetric expansion upon lithiation compared
to metal oxides. Among various metal sulphides, transition metal dichalcogenides
(TMDs) are highly promising because of their layered structure (Fig. 2). Interlayer
spacing of TMDs provide a scope for the accommodation of species, like lithium ions
[21]. Layered metal sulphides have the potential application as anode materials in LIBs
due its various advantages such as better reversible discharge capacity and cycling
performance compared to the metal oxides. The exfoliated few-layered metal sulphides
exhibits different chemical and physical properties compared to their bulk counterparts. A
large interlamellar spacing, with dimension between two layers ranging in nanometers
accommodates volumetric expansion upon lithium storage. Few-layered metal sulphides
can provide high volume ion diffusion paths and higher number of active sites for
lithium-ion storage.

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A layered metal sulphide has the potential to be used as high-power anode material due to
the fast lithium ions storage kinetics resulting from surface pseudocapacitive storage
behaviour. In addition, tailored few-layered electrodes are proficient members of being
accommodated at high current densities. The metal sulphide anodes prepared by the
intercalation are accommodating lithium ions through conversion reaction mechanism
(Fig. 2). This mechanism offers higher energy density than intercalated metal sulphides.
The mechanism of conversion reaction to store lithium ions during charging-discharging
is shown by the equations below.

MS2 + xLi → LixMS2 (1)

LixMS2 + (4 − x)Li → M + 2Li2S (2)

M + 2Li2S ↔ M + 2S + 4Li (3)

In the first discharge cycle, the Li+ ions are intercalated into MS2 (M=Mo, W, Sn, Fe) to
form LixMS2. Subsequently, the LixMS2 is decomposed into M and Li2S. During charging
cycle, a reversible reaction of Li2S converting into S and Li occurs with M remaining
unaffected [22].
Nevertheless, the main limitation of conversion reaction mechanism is that it may bring a
large volume expansion of electrode material during lithiation/delithiation in the initial
cycle. These factors results in mechanical failure of electrode materials by means of
cracking, fracture and electrode disconnection from the current collectors which results in
speedy fading of LIBs capacity. Mainly, the transition metal sulphides (TMSs) have
drawn the attention as the anode material in LIBs due to their increased specific capacity,
cheap, highly safe and environmental-friendly. The TMSs are resistant to formation of
the lithium dendrites compared with commercial graphite anodes. This is due to the high
working voltage platform of TMSs (above 1.0 V). With all these salient features, the
TMSs are competitive enough to be used as the next-generation anode materials.

6. Metal sulphide based nanocomposites for battery applications

Conventionally metal dichalcogenides (metal sulphides) are observed as competitive
materials in the applications of an anode electrode in LIBs. The limitations could be
limited electrical conductivity along with capacity loss during the first cycle. Using
combinations of heterogenous nanostructures can overcome these limitations [23]. Use of

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the sulphide/rGO or such composite makes the electrodes a highly flexible and opens up
new opportunities, like roll up devices, wearable devices, health monitoring, skin devices,
etc. These devices needs flexible power sources with high capacity and rate performance
which will allow them to be used for fairly long time and to be charged at a short time
[20,24]. A design configuration of metal dichalcogenide/rGO is found to be highly
beneficial [25]. It showed enhanced performance and delivered reversible expulsion
capability. Also, adding metal chalcogenide with rGO will alleviate volume changes
during charge –discharge cycles [26].

7. Different types of metal sulphides as anode materials in the LIBs applications

Transition metal dichalcogenides (TMDs) are candidates for recharging batteries. Several
metal oxides of the type MSx (M= Cu, Co, Zn, Ti, Sn, Mo, W, Ni, etc) are explored for
the possible application as the anode material in LIBs. Various methods are employed to
evaluate the cyclic stability of the metal sulphides in rechargeable LIBs. The metal
sulphide nanostructures and their composites integrated with carbonaceous materials (like
graphene, CNT) have shown significant improved performance on cyclic performance,
several challenges still remain. In the initial lithiation cycle, the MSx structures are
destroyed by converting to metal (M) and Li2S. These initial structures, scales of the MSx
structures, the microstructure and dispersion characteristics of metal and LiS2 in the
electrodes are the factors affecting the cyclic stability of LIBs. The lithiation of MSx
results in massive volume expansion, leading to grinding (pulverization) and
deterioration of electrode materials. This effect causes MSx to result in poor
ionic/electronic conductivity hampering their high-power performances.

7.1 Layered metal-sulphides for LIBs.

From the literature is seen that the layered structures have shown better performance
compared the other materials. MoS2, WS2, ZrS2, VS2, SnS2 are some of the layered
(sulphide-metal-sulphides) materials which are similar to the graphite structure. These
layered structures are two dimensional sandwiched sheets which are held by weak Van
der Waals force. The layered structure of MoS2 and WS2 are similar where Mo (or W) is
connected to six sulfur atoms. These structures are interconnected to give two-
dimensional (2D) layered material, as shown in Fig. 3. ZrS2 and VS2 possess hexagonal
close-packed lattice structure where Zr (or V) occupies the octahedral position in
alternating layers and sulfur occupies hexagonal position. VS4 is also layered structured
linear chain compound similar to VS2 with alternating bonding and non-bonding contacts
between octal-coordinated V centers. Each sulfur unit in the structure bridges the two
neighboring V atoms. SnS2 is also a layered structure with CdI2-type crystallographic

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characteristics. The sandwiched structure of SnS2 contains Sn atoms between the two
layers of sulfur atoms.

Figure 3. Schematic representation of layered metal sulphide structure.

7.2 Copper sulphides

The reaction involving copper sulphides with lithium offer an improved high capacity
and energy density. Hence, the copper sulphides are the best TMSs. However, the
reversibility of the copper sulphides is poor and hence nanostructuring is necessary to
improve the properties. CuS and Cu2S are the main sulphide forms of the copper. Based
on the conversion reaction (CuS + 2Li+ + 2e- ↔ Li2S + Cu), the specific capacity and
electrical conductivity are calculated to be ~560 mAh g-1 and ~104 Scm-1, respectively
[27,28]. However, the Cu2S is electrochemically more stable compared to the CuS [27].
In Cu2S, the cell volume and ionic radius of Cu+ ion (0.077 nm) is very close to the Li+
ion and Li2S (fcc). The volume expansion of Cu2S is comparable to Li2S during charge-
discharge cycles. Jache and co-workers have predicted the mechanism of reaction for
Cu2S where it is displacement reaction than conventional conversion reaction [29]. The
ex-situ techniques, such as X-ray diffractometry (XRD) and transmission electron
microscopy (TEM) are employed to study the phase transformation and electrochemical
reactivity of copper sulphides during the lithiation-delithiation cycles [30]. This TEM
analysis also showed the extrusion of copper when cell is fully discharged. This unique
electrochemical behaviour is present in Cu2S compared to other sulphide counterparts

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[31]. The addition of excess amount of copper to the copper sulphides electrodes will
significantly improve the electrochemical performance and cycling stability [32].
The reaction between Cu2S with Li is displacement reaction rather than conversion in the
copper nanodomains. One of the interesting phenomenon in copper sulphides is the
formation of macroscopic metallic Cu dendrites upon reduction [30,33]. The large copper
dendrites will surround the Li2S matrix after it is fully discharged [34]. It is already
discussed that the Li2S, Cu2S and CuS have structural similarity (like space group and
cell volume) accounting for the efficient electrochemical performances of the copper
sulphides. The biggest disadvantage in copper sulphides system is the selection of narrow
voltage window between 1.0 V to 3.0 V. This voltage range causes low releasing capacity
during cycling compared with the voltage range of 0.01 and 3.0 V [35,36]. Usage of
nano-metal sulphides and complexing are the two kinds of strategies followed to
overcome the demerits of volume expansion and electronic insulating property of the
discharge product (Li2S). However, Nanomaterials effectively address the volume
expansion and hence they are adopted for the synthesis of anode material [28].
Cu2S nanowire arrays were synthesized by following the solution synthesis method [37].
These Cu2S nanowire arrays are grown directly onto the copper metal current collector.
As discussed, nanostructures exhibit stable Li+ ion movement and increased reversible
lithium storage capability without forming the copper dendrites. The electrochemical
performance of Cu2S nanowire array was tested with voltage range of 0.05 – 3.0 V, at
room temperature. The first discharge curve had one voltage plateaus at 1.60 V and
showed a high discharge capacity of 470 mAh g-1. The first charge curve had two voltage
plateaus at 1.85 V and 2.25 V with charge capacity of 400 mAh g-1. The specific capacity
and the Coulombic efficiency of Cu2S was calculated to be 185 mAh g-1 and 96 %,
respectively. The specific capacity after 85 cycles was found to be 79 %. This value lasts
up to 100th cycle. Feng et al. synthesized reduced graphene oxide (rGO) incorporated
copper sulphide nanowires [38]. The rGO/CuS showed the reversible capacity of 620
mAh g-1 at 0.5 C (1 C = 560 mAh g-1). After 100 cycles it decreased to 320 mAh g-1 at
current rate of 4 C. The synergetic effect between the rGO nanosheets and CuS
nanowires resulted in excellent lithium storage performance. Feng et al. synthesized CuS
nanowires with dimension of 6 nm diameter by template and surfactant-free method
using dimethyl sulfoxide (DMSO)-ethyl glycol (EG) mixed solvent [39]. At 0.2 C, the
initial releasing capacity and charge capacity are 832 mAh g-1 and 518 mAh g-1,
respectively. The charge capacity of 196 mAh g-1 and Coulombic efficiency of 99.0 %
are achieved when the current is increased to 4 C. Jache et al. [29] reported charge
capability of the copper sulphide electrode with variation in electrolyte composition.
Also, it is shown that the Cu2S could be recycled 150 times with Columbic efficiency of

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over 98.0 %, with overvoltage of 200 mV at different current rates (up to 1 C). It is also
seen from the work that the performance of nanostructured copper sulphides is better
compared to the bulk counterpart.

7.3 Cobalt sulphides

Cobalt sulphides (CoSx) exhibit excellent physical and chemical properties. Various
stoichiometric cobalt sulphides (such as CoS, CoS2, Co3S4 and Co9S8) have been
explored widely for the application as electrode material in LIBs. The CoSx exhibits
many interesting features, like natural abundance, high electrical conductivity and high
theoretical capacities (CoS: 589 mAh g-1, CoS2: 870 mAh g-1, Co3S4: 702 mAh g-1 and
Co9S8: 545 mAh g-1) [40]. The crystal structure of CoS, CoS2, Co3S4 and Co9S8 is
hexagonal, cubic, spinel and cubic close-packed arrangements, respectively [22]. Among
various cobalt sulphides, Co9S8 is highly explored in the application of LIBs. Various
carbonaceous nano materials are used to prepare Co9S8 composites to improve the
conductivity and electrochemical activity. Many carbon nanostructures are used to
prepare various Co9S8 nanocomposites, such as CNT/ Co9S8 [41], graphene nanosheets/
Co9S8 [40], porous carbon nanofibers/Co9S8 [42] and carbon nanotube aerogel/Co9S8
[43]. These carbonaceous structures (like CNT, GO, etc) inhibit the aggregation of Co9S8
by providing higher number of electrochemical active sites during cycling of LIBs. Li et
al. [40] synthesized rGO/cobalt sulphide composite by following ultrasound-assisted wet
chemical method. The morphological analysis depicts that the cobalt sulphide
nanoparticles are consistently attached to rGO nanosheets. The electrochemical study on
rGO/cobalt sulphide nanoparticles shows the high reversible capacity of 994 mAh g-1
after 150 cycles at a current density of 200 mA g-1. The nanocomposite of rGO and cobalt
sulphides shows the superior electrochemical performance over pure cobalt sulphide.
Yongsheng et al. [44] developed a new cobalt sulphide encapsulated nanowire composite
within nitrogen-doped porous branched carbon nanotubes (NBNTs) for LIBs. The
NBNTs showed the reversible specific capacity of 1310 mAh g-1, at a current density of
0.1 A g-1 with Columbic efficiency of almost 100 % for 200 cycles. This outstanding rate
and cycling capability is due to the one dimensional porous Co9S8/NBNTs inter
networks. CNT confinement and nitrogen doping of cobalt sulphide nanowires offers
narrow electron pathway for individual nanoparticle and protecting the cobalt sulphide
nanowires from pulverization.
Zhang et al. [43] worked on synthesizing three-dimensional (3D) aerogel consisting of
CNT, graphene nanosheets and CoS2 nanoparticles as electrode material for LIBs. The
nanocomposite exhibited high reversible capacity of 975 mAh g-1 after 100 cycles at
current density of 0.25 A g-1. The high capacity is due to the synergetic effects of

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individual components. Liu et al. [45] synthesized the hollow cobalt sulphide
nanoparticles embedded in graphitic carbon nanocages by following top-down approach.
The composite showed superior lithium ion storage capability at working voltage range
of 1.0 V to 3.0 V and displaying higher energy density of 707 Wh kg-1. The reversible
rate capacity shown by the composite is 536 mAh g-1 at current density of 0.2 C and 278
mAh g-1 at 10 C. when the working voltage is increased from 0.01 V to 3.0 V the
capacity is found out to be 1600 mAh g-1 at current density of 100 mA g-1. Chen et al.
[46] worked on the synthesis of hollow microspheres of cobalt sulphide (CoS2). The CoS2
showed superior rate capacity of 720 mAh g-1 after 200 cycles. Jin et al. [47] synthesized
worm-like CoS2 assembled by ultrathin nanosheets with an average thickness of 2.1 nm
by using solvothermal technique, without the assistance of surfactant or template. The
CoS2 worm-like structure showed discharge capacity of 883 mAh g-1 after 100 cycles at a
current density of 100 mA g-1. The material also shows higher rate capacity of 501 mAh
g-1 at higher current density of 2000 mA g-1 after 50 cycles. Hu et al. [48] worked on the
synthesis of binder-free and self-standing cobalt sulphide encapsulated in CNT and it
showed extraordinary cycle stability and maintains 87 mAh g-1 after 6000 cycles at 1 A g-
1
. The CNT/cobalt sulphide composite exhibited discharge capacity of 315 mAh g-1 at
100 mA g-1. Zhou et al. [49] have developed mesoporous Co9S8 by solvothermal method
and subsequent high temperature annealing. The Co9S8 hollow nanoparticles have shown
high reversible rate capacity of ~1414 mAh g-1 after 100 cycles at 100 mA g-1. The
growth of carbon shell on hollow Co9S8 nanoparticles has improved the reversible
capacity of ~896 mAh g-1 after 800 cycles at 2 A g-1.
Researchers have also designed different structures of cobalt sulphides and also the
composites of cobalt sulphides to overcome the limitations of the bare cobalt sulphide.
The special architectures have shown promising performances for high discharge
capacity and better cycling rate in LIBs. These well-defined large surface area structures
of cobalt sulphides could largely reduce the diffusion paths of Li+ ions and electrons.
These features of cobalt sulphide nanostructures could result in high lithium ion storage
capacity and easy lithiation-delithiation conversion reactions.

7.4 Molybdenum disulphide (MoS2)

MoS2 is a two-dimensional layered material where a layer of molybdenum atoms is
sandwiched between the layers of sulphur atoms. This can be prepared like a sheet
consisting of single to few layers of MoS2 to offer high surface area [50]. There are
different synthesis techniques to prepare the MoS2 with different nanostructures.
Tian et al. synthesised MoS2 nanospheres by following hydrothermal method [51].
Ammonium molybdate (NH4)6Mo7O24·4H2O and sodium sulphide (Na2S·9H2O) were

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used as the source for molybdenum and sulphur, respectively. The produced material was
MoS2 nanospheres with the average diameter of 30 nm. Park et al. synthesised MoS2
nanospheres using sodium molybdate dihydrate and L-cysteine as the source method by
using hydrothermal method [52]. The galvanostatic study performed on this prepared
nanospheres has shown that the MoS2 nanospheres exhibited the charge capacity of 706
mAh g-1 at 100 mA g-1 and 658.1 mAh g-1 at 1000 mA g-1 after 30 number of cycles. This
high capacity value was attributed to its nanostructure having increased interplanar
distance and associated faster diffusion of lithium ions [52]. Guo et al. synthesized yolk-
shell MoS2 nanospheres with carbon shell [53]. The material showed the capacity value
of 1065 mAh g-1 at the current density of 0.1 A g-1. The electrochemical performance of
the material was excellent as it exhibited the high capacity of 947, 914 and 847 mAh g-1
at high current density of 1, 2 and 5 A g-1, respectively. The reason for this excellent
performance was the result of the high stability and reversibility provided by the porous
nanostructures and carbon shell [53].
MoS2 nanosheets are another significant nanostructured material. This could be prepared
by many techniques, such as hydrothermal [54], chemical vapour deposition (CVD) [55]
and solvent assisted exfoliation [56]. The MoS2 nanosheets were prepared by our group
via solvent assisted exfoliation route by ultrasonication process [57]. Some details are
given in Fig. 4 and Fig. 5. A TEM micrograph is shown in Fig.5a. It is observed that the
prepared nanosheets contain only a few layers of the MoS2. The study of XRD pattern (in
Fig. 5b) shows that the peaks belonging to the planes (103) and (105) were absent in the
exfoliated nanosheets. Liu et al. synthesized MoS2 nanosheets by following hydrothermal
method [58]. Subsequently, the prepared nanosheets were treated by oxygen plasma in
order to be used in lithium-ion batteries. Then the prepared MoS2 nanosheets were used
as the working electrode in a coin-type battery. The charge-discharge studies exhibited
the charge capacity of 1120-1180 mAh g-1 at 1 A g-1 and retained up to 600 cycles. It
retained the capacity in the range of 920-1150 mAh g-1 at 1 A g-1 even after 1000 number
of cycles. This high capacity retention of the MoS2 nanosheets was attributed to the
expansion of interlayer in MoS2 and plasma-treatment induced defects that acted as the
extra active sites for the Li-ions intercalation [58]. Xiang et al. worked on growing
vertical MoS2 nanosheets on the surface of the graphene [59]. The metallic 1T-MoS2
nanosheets on the graphene were conductive to facilitate the charge transportation. The
calculated charge capacity of the material was 666 mAh g-1 at a current density of 3.5 A
g-1.
There are many investigations on the exploration of the MoS2 based nanocomposite in
the battery domain. MoS2/graphene nanocomposites were used as the anodes. Exfoliated
MoS2/rGO composite could afford a capacity of 165 mAh g-1 after 50 cycles [60]. Qin et

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al. have shown that the MoS2/rGO nanocomposite exhibited a reversible capacity of
about 305 mAh g-1 at a current density of 100 mA g-1 after 50 cycles [61].

Figure 4. Solvent assisted liquid-phase exfoliation of MoS2 nanosheets.

Figure 5. (a) TEM micrograph of the MoS2 nanosheets prepared by liquid-phase

exfoliation; (b) XRD pattern of the exfoliated MoS2 nanosheets compared with that of the
bulk MoS2 powder.

7.5 Tungsten disulphide (WS2)

Tungsten disulphide (WS2) is a two-dimensional layered material like MoS2. The WS2 is
synthesised in different nanostructure forms, such as nanoflowers [62], nanowires [63],
nanotubes [64] and nanoflakes [65]. Cao et al. synthesised WS2 of different morphology
by following hydrothermal method [66]. The WS2 nanoparticles, nanorods, nanosheets
and nanofibers were synthesised using sodium tungastate and sulfourea as the source

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material. But the surfactant (CATB/PEG) used in the synthesis process influenced the
resultant nanostructures.
Feng et al. synthesised nanoflakes of WS2 by following hydrothermal method at the
temperature of 200 °C [65]. The produced WS2 nanoflakes was used to prepared the
anode material by mixing it with the carbon black and PTFE solution. The Li metal foil
was used as the counter electrode and LiPF6 was used as the electrolyte. The capacity of
1690 mAh g-1 was observed for the first cycle. But the passivation formed on the
electrode surface due to the degradation of the electrolyte brought the capacity to the
value of 680 mAh g-1. This value was maintained for the remaining 20 cycles.
The mesoporous WS2 structure was synthesised by vacuum assisted impregnation method
[67]. The solution of phosphotungstic acid mixed with the mesoporous silica template
was prepared. The dried mixture was undergone the sulphuration at 600 °C to form
porous WS2. The electrode prepared from this mesoporous WS2 was tested. The initial
capacity was reported as 1323 mAh g-1 at the current density of 0.1 A g-1. The capacity
was reduced to 805 mAh g-1 and it remained almost same for 100 cycles [67]. The
material also showed the capacity of 503 mAh g-1 at the high current density of 10 A g-1.
The highly porous structure of WS2 was the reason for this high capacity value that
offered high surface area for electrolyte interaction, easy diffusion for ions and short
pathways for the intercalation of lithium ions.
Du et al. synthesised oleylamine coated WS2/graphene nanosheets by following modified
colloidal synthesis method [68]. As the first step, a solution of WCl6 in oleic acid was
prepared. Then the solution was bubbled by N2 followed by the addition of OLA into the
solution. Then a small amount of CS2 was added. After that this precursor solution was
injected into a hot flask containing OLA. After injecting the precursor solution, the
solution was rapidly cooled to room temperature. The obtained OLA coated WS2
nanosheets was washed and dried. Then dispersion of OLA-WS2 was sonicated followed
by the addition of GO/ethanol to form the aggregation of OLA coated WS2/GO
nanosheets. The prepared composite was tested as the anode material in a coin-type
lithium-ion battery. The initial capacity was reported as 542 mAh g-1 at the current
density of 0.5 A g-1. It retained the capacity value of 486 mAh g−1 for another 200 cycles.
It even retained the capacity of 126 mAh g−1 at the current density of 10 A g−1. In another
investigation, Su et al. synthesised WS2/graphene component by following hydrothermal
process route [69]. It is used in sodium ion batteries and similar trend is expected in the
lithium-ion batteries also. The WS2/graphene nanocomposite anode owned a reversible
specific capacity 540 mAh g-1 and a retention capability of 280 mAh g-1 after 500 cycles.

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Wang et al. synthesised metallic (1T) WS2 on semiconductor (2H) WS2 by hydrothermal
route [70]. The synthesised WS2 (2H phase) was heat-treated in the presence of ammonia.
This induced the conversion of 2H phase into 1T phase. The presence of metallic phase
of WS2 increased the conductivity of the material. The electrode material was prepared
using 1T@2H WS2 on the flexible carbon substrate. The electrochemical results reported
the capacity value of 1130 mAh g−1 at the current density of 0.1 A g-1 for 200 cycles and
the capacity value of 510 mAh g−1 at the current density of 2 A g-1 for 800 cycles [70].

7.6 Iron disulphide (FeS2)

Iron disulphide (FeS2) is widely used as the electrode material for non-rechargeable
lithium-ion batteries. Iron disulphide has two phases, pyrite with the cubic crystal
structure and marcasite with the orthorhombic crystal structure. Many researchers have
reported that FeS2, both pyrite and marcasite, as potential anode and cathode materials for
low cost battery applications [71].
The FeS2-pyrite nanorod clusters were synthesised by following low pressure
hydrothermal route by our group [72]. Ferrous sulfate heptahydrate and sodium
pyrosulfate were used as the source materials whereas sulphur was used to initiate the
nucleation of the particles. The synthesis was carried out at 70 °C at normal pressure. Fig.
6a shows the SEM micrograph of the synthesised FeS2. The FeS2 was appeared as the
clusters of the individual nanorods. The XRD patterns (Fig. 6b) of the FeS2 shows that
the peaks belongs to the pyrite-phase of the FeS2.

Figure 6. (a) SEM micrograph of the FeS2 nanorods clusters (b) XRD pattern of the
synthesised FeS2-pyrite with different time durations.

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There are many efforts to make nanocomposite using FeS2 as one of the constituent.
Biomass–carbon/FeS2 nanocomposite was synthesized using carbonization and
sulfuration and used as the cathode electrode material [73]. This composite had higher
capacity to the tune of 850 mAh g−1 at 80 cycles. Xue et al. prepared the GO/FeS2
composite by using the graphene oxide (GO), ferrous sulfate, sulphur and triethylene
glycol as the precursor materials [74]. The pyrite, FeS2 microspheres wrapped by the
reduced graphene oxide sheets were obtained by heating the precursor material and
followed by annealing. The prepared composite was used as the working electrode. The
capacity calculated from the charge-discharge studies showed the excellent value of 970
mAh g−1 at the current density of 0.89 A g−1 for 300 cycles. It retained the capacity value
of 380 mAh g−1 at the high current density of 8.9 A g−1 for 2000 cycles [74]. The
graphene oxide with the FeS2 microspheres offered higher conductivity, large surface
area and improved interaction with the electrolyte. These were reasons behind this high
and stable performance of the GO/FeS2 electrode. The FeS2 microspheres synthesised by
the hydrothermal method was tested as the cathode material for the LIB [71]. The
discharge capacity of the tested electrode material was reported as 371 mAh g−1 at 0.1 C
and 239 mAh g−1 at 1 C for 50 cycles. To improve the performance of the electrode
material, graphene was used along with the electrode material. The composite of rGO
wrapped mesoporous FeS2 particles were synthesised by facile solution reaction method
[75]. The rGO provided the high surface area and conductive path to the electrode. This
resulted in the high capacity value of 1720 mAh g−1 at the current density of 0.2 A g−1 for
700 cycles. The material retained the capacity of 340 mAh g−1 at the current density of 5
A g−1 at high temperature of 85 °C [75]. Fan et al. synthesised the marcasite FeS2/carbon
nanofibers composite by following hydrothermal method [76]. This metastable m-FeS2
microparticles/CNF composite was tested as the anode material for the lithium-ion
battery. It showed the high capacity value of 1086.9 mAh g−1 at the current density of 0.1
A g-1 and 782 mAh g−1 at the current density of 10 A g-1. The cyclic stability test showed
that the material retained the capacity of 575 mAh g−1 at 5 A g-1 after 1000 cycles. The
main reasons for this good performance were, 1) the reduced electron/ion transfer
pathways; (2) prevention of particle aggregation by the CNF; 3) structural stability
provided by the CNF [76].

7.7 Tin sulphides

SnS2 has layered structure. It consists of a layer of tin atoms located between two layers
of hexagonally close packed sulphur atoms. The large interlayer spacing and the
nanostructures of SnS2 allows insertion and removal of the lithium ions. It can easily
accommodate the volume changes associated with the cycling of lithium ions [77]. The
SnS2 has the capability of working at low voltage with high specific capacity. This

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feature has drawn the attention of many researchers to explore this material in the LIBs.
There are many reports which aimed to enhance the electrochemical performance of the
SnS2 electrode materials. Wang et al. [78] have worked on the synthesis of SnS2
nanosheets in N-methyl-2-pyrrolidone by following solvothermal method. The capacity
exhibited by the SnS2 nanosheets is more than 1200 mAh g-1 and better short-time cycling
stability. The carbon coated SnS2 also has shown the large capacity of ~600 mAh g-1 and
decent cycling stability. Chen et al. [79] prepared the SnS2/rGO nanocomposites by
reflux condensation and hydrothermal methods. The capacity of SnS2/rGO electrode is
514 mAh g-1 at 1.2 A g-1 after 300 cycles. The discharge capacity and cycling
performance of the SnS2/rGO is better compared to the SnS2/C electrode. This is because
of the introduction of rGO in the nanocomposites. Wang et al. [80] have synthesized the
carbon coated SnS2 by solid-state reaction method. The carbon coated SnS2
nanocomposite shows the reversible capacity of 660 mAh g-1 at a current density of 50
mA g-1 and maintain up to 570 mAh g-1 for 100 cycles with a degradation rate of 0.14 %.
The ex-situ characterization of SnS2/carbon coated electrode gives better performance
due to the stable morphology and structural integrity during charge-discharge cycles.
Wang et al. [81] developed a light weight, high mechanical strength and high
power/energy density flexible flower-like SnS2 nanoplates decorated on the graphene
nanosheets supported on the carbon cloth electrode. The initial capacity of the
SnS2/graphene is found to be 1987.4 mAh g-1 and specific capacity equal to 638.1 mAh g-
1
after 150 cycles. The flower-like SnS2 nanoplates decorated on the graphene nanosheets
provide high surface area, excellent electrochemical performances and reduces electrode
polarization. Liu et al. [82] demonstrated the synthesis of hexagonal sheet-like SnS2/GO
nanocomposites. The presence of small amount of GO (2.4 weight %) significantly
improved the specific capacity, rate capability and efficient cycling performances. The
initial charge and discharge capacity is 1057.9 mAh g-1 and 1449.7 mAh g-1, respectively
with Coulombic efficiency of 72.97 %. The discharge capacity still retains a good value
of 509.5 mAh g-1 even after 100 cycles. The capacity retains a value of 589.0 mAh g-1 at
50 mA g-1 current.
Wang et al. synthesised novel ultra long SnS2 nanobelts by following solvothermal
method [83]. CS2, dodecanethiol and tin(IV) chloride pentahydrate were used as the
precursor materials to synthesis SnS2 nanobelts. The nanobelts of several hundred
micrometer length was synthesised. A coin cell battery was fabricated using the SnS2
nanobelts as the working electrode, Li foil as counter electrode and LiFP6 as the
electrolyte. The charge-discharge study revealed the initial charge capacity as 640 mAh
g−1 and a steady capacity value of 560 mAh g−1 at current density of 0.1 C for 50 cycles
[83].

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Wang et al. prepared the SnS2 nanosheets assembly to be used in the lithium-ion battery
application [78]. The solvothermal method synthesised SnS2 was treated with the
dopamine hydrochloride and tris(hydroxymethyl) to produce carbon coated SnS2
nanosheets. A R2032 type coin cell was fabricated by using the c-SnS2 nanosheets as the
working electrode, Li foil and LiFP6 as the counter electrode and the electrolyte,
respectively. The carbon coating over the surface of SnS2 helped to facilitate the charge
transportation and mechanical support. The capacity of the c-SnS2 nanosheets was
reported as 1100 mAh g−1 at the current density of 0.2 A g-1 for 50 cycles.
Zhang et al. synthesised three-dimensional honeycomb, like SnS2 quantum dot/rGO
composite for the lithium-ion battery application [84]. The polystyrene (PS) nanospheres
were used as the template to synthesis 3D nanostructure. The tin (IV) chloride and rGO
were mixed with the PS nanospheres and subjected to ultrasonication. The samples were
heat treated to remove the polystyrene. Then the powder sample was mixed with thiourea
and annealed to form 3D honeycomb-like SnS2/rGO composite. The capacity value was
calculated as 862 mAh g−1 at 0.1 A g-1 and 622 mAh g−1 at 0.5 A g-1 for 200 cycles.

7.8 Nickel Sulphides

Nickel sulphides, such as NiS, NiS2 and Ni3S2 have been explored as the electrode
material for the lithium-ion battery application. The nickel sulphides have good
theoretical capacity of 550 mAh g-1 [85]. However, the cyclic performance of such
material remains poor [86]. Mi et al. prepared NiS/Ni3S2 flower-like microspheres,
nanoplates, prism-like microrod and chain-like nanostructures by using solvothermal
method [85]. In brief, the Ni foam, ethylene glycol, anhydrous ethylenediamine and
sulphur powder were used in this synthesis process. The volume ratio of ethylene glycol
and anhydrous ethylenediamine was varied to produce different morphologies. The
calculated discharge capacity of microspheres, nanoplates and 1D prism-like microrods
& chain-like nanostructures was shown as 353.1, 445.5 and 550 mAh g-1 respectively at
the current density of 40 mA g-1. The shorter path for electron/lithium ion transportation
and larger interface connection between the electrode and the electrolyte were the reason
for the high discharge capacity value of the 1D nanostructures. To improve the
performance, the nickel sulphides with various morphologies were synthesised to
suppress the volume change during the charge-discharge cycle. Xiao et al. prepared
nickel sulphide (NiS/Ni3S2) particles and interlinked nanosheets by in situ microwave
synthesis [87].
A porous 3D nickel sulphide on Ni foam was synthesised by facile solution and melt–
diffusion process [88]. The prepared material was tested as a potential cathode material

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for the LIBs. The discharge-charge study showed the initial discharge capacity of 1326
mAh g-1 and 715 mAh g-1 after 100 cycles at the current density of 0.2 C (118 mA g-1).
Tao et al. synthesised NiS nanorods/N-doped graphene composite by following
hydrothermal method. The prepared composite was tested as an anode for the LIBs [89].
The discharge-charge study revealed the charge capacity of the composite material as 687
mAh g-1, whereas the bare NiS showed the charge capacity of 575 mAh g-1 at the current
density of 50 mA g-1. But the capacity of bare NiS reduced drastically to 100 mAh g-1
after 50 cycles. This is because of the particle aggregation and electrode pulverization
during cyclic process. On the other hand, the composite NiS/N-doped graphene showed
good capacity retention of 425 mAh g-1 after 50 cycles. The reason behind this stable
capacity was the addition of N-doped graphene. It acted as the buffer during cyclic
process to prevent the volume changes. The interface resistance was also reduced due to
the high electrical conductivity of the graphene.
Dong et al. synthesised NiS nanoparticles embedded in the mesoporous N and S doped
tubular carbon structures by a combination of nickel salt impregnation and calcinations
process [90]. The synthesised NiS/NSC exhibited high surface area to the level of 200.8
m2g-1. The charge capacity of the prepared material was 715.9mAh g-1 at the current
density of 0.1 A g-1 after 200 cycles with almost 100% Coulomb efficiency. The reported
capacity value was higher than its theoretical capacity of 590 mAh g-1. The NiS particles
embedded on the carbon may promote the formation of polymer-like layer on their
surface that can contribute further capacity value during the long cyclic process. The
material showed the excellent capacity values of 446.1 mAh g-1 and 411.1 mAh g-1 even
at the high current density of 2 A g-1 and 5 A g-1, respectively.

8. Synthesis techniques for metal sulphides

8.1 Solid state method

This method utilizes two metals and sulfur. The two metals and sulfur are mixed together
and heated to high temperature under vacuum or inert atmosphere condition [91]. The
method has several disadvantages, like need of high temperatures (> 500 °C) and long
reaction time [92]. In addition, this method offers less control over the size, morphology
and structure for the synthesized nanosufides. The materials prepared with this method
are chromium chevrel phase sulphide (CrxMo6S8-y), MnS, Cr2S3, etc. In contrast, there are
several low-temperature and solution-based methods which are more popular and
promising.

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8.2 The hydro/solvothermal method

This method is simple and widely used for the preparation of metal sulphides for LIBs. In
this method, two metal salts and a source of sulfur are dissolved either in water or organic
solvent or mixture of organic solvent and water. Then the solution is heated to a designed
temperature for a particular time duration. The reaction for the hydro/solvothermal
method is carried out in a sealed teflon-lined stainless steel autoclave where the
autogenous pressure is generated inside the vessel. The pictorial representation of
hydrothermal synthesis approach is as shown in Fig. 7. These conditions are sufficient for
the nano/micro metal sulphide materials to precipitate and form a particular structure.
The hydro/solvothermal route is effective and has good control over shape, size and
morphology of the material. When metal foams are introduced as the source material, it is
possible to construct metal-containing sulphide nanostructures on the source metal foam
under hydro/solvothermal conditions. This method is environmental friendly and cost
effective. The hydrothermally synthesized metal sulphides have high crystallinity with
small crystallite size and highly uniform particles. The hydrothermal synthesis of various
MoS2-carbon based nanocomposites morphologies like nanosheets, nanoflakes,
nanoplates, nanoflowers, microspheres were reported [22].

Figure 7. Pictorial representation of hydrothermal method for synthesizing metal

sulphide nanoparticles.

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There are many reports which followed hydrothermal synthesis method for metal
sulphides and composites of metal sulphides nanostructures, due to its inherent
advantages. Nanorod like CuS and Cu2S are fabricated by the hydrothermal method
without using any surfactant and template [22,28]. The nanocomposite of CoS2/carbon is
prepared by a freeze-drying technique and hydrothermal approach with the CoS2
nanoparticles (~20nm) arranged on a spongy carbon matrix [93]. Wang et al. [81]
synthesized flower like SnS2 decorated on the graphene sheets by following hydrothermal
method. The MoS2 nanoparticles with different morphologies are synthesized by
hydrothermal approach [94,95]. The Co9S8 nano hexagonal flake crystals are synthesized
by hydrothermal route using cobalt sulphate hydrate, hydrazine hydrate solvent and
sodium sulphate [96]. The average crystallite size of Co9S8 nanocrystals is 2.5 nm. Nickel
sulphide nanoparticles (NiS and NiS2) [97,98] is synthesized by hydrothermal conditions.
Carbonaceous materials (like CNT, GO, graphene) combined with metal sulphide
nanoparticles synthesized by hydrothermal method have shown the best performance
compared to their individual counterpart. Graphene metal sulphide nanocomposites are
also synthesized and explored in the applications of LIBs. The graphene present in the
composite reduces the agglomeration of metal sulphide nanoparticles and also helps in
the electrochemical activity enhancement [99].

8.3 Microwave-assisted hydrothermal synthesis

Microwave-assisted hydrothermal synthesis technique is simple, quick and energy
efficient technique. It works on the basis of capacity to absorb microwaves by target
metal salts and transforms it into heat. The mechanism of heating can be divided into two
parts, namely ionic conduction and dipole movement. When the polar solvent (Ex: water,
ethanol, etc.) is used as the liquid medium, the microwaves induces rotation of dipoles
within the liquid. The rotation force causes the polar molecules to align and relax in the
direction of oscillating electromagnetic radiations.
CuS nanospheres interconnected by the carbon nanotubes (CNTs) have been successfully
synthesized via a facile one-step microwave-assisted method [100]. Xiao et al. [87]
synthesized CuS, NiS/Ni3S2 and FeS2 nanoparticles with different morphologies by
microwave irradiation approach method. The morphology of the nanoparticles is
dependent on the irradiation temperature. The Cu foil supported CuS particles, nanobuds
and nanosheets is synthesized with irradiation time of 20 min at 25 °C, 80 °C and 140 °C,
respectively. Conductive agent and binder material free, Cu foil supported CuS is directly
used as electrode material for LIBs. The CuS nanosheets exhibited a very good initial
reversible capacity of 588 mAh g-1 at 56 mA g-1 with a small capacity fading rate of
0.17% per cycle for 100 cycles. The rate capability of CuS is found to be very high with

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the value of 463 mAh g-1 at 2.8 mA g-1. The electrochemical performance of CuS
nanosheets is far better compared to the CuS nanoparticles due to the layered structure
and easy diffusion of lithium ion and electron into the electrode. Similarly, NiS/Ni3S2
particles and interlinked nanosheets are synthesized by microwave irradiation approach
with irradiation time of 20 min and temperature of 150 °C and 180 °C, respectively. The
FeS2 nanoparticles, interlinked nanosheets and nanosheets are synthesized at irradiation
temperature of 120 °C, 150 °C and 180 °C, respectively. Co9S8 nanoparticles are
synthesized with the same conditions keeping irradiation temperature of 180 °C. NiS
nanoparticles are synthesized by cyclic microwave irradiation approach [101]. SnS2
flower-like nanostructure is synthesized by microwave irradiation approach [102]. The
SnS2 nanostructure exhibited initial charge capacity of 412 mAh g-1 at current 1 A g-1.
Similarly, nanocomposites of MoS2/WS2-rGO and graphene/CuS are also synthesized by
microwave irradiation approach [61,103,104].

8.4 Spraying-related methods

The spray-related methods are simple approach to synthesize mainly spherical
nanoparticles. NiS2, Fe3S4, CuS, ZnS [105–107] nanoparticles are synthesized by
following spray related approach. The spray solution is prepared by mixing oleyamine
and precursors along with the suitable metal sulphide salts. The solution is sprayed on the
substrate (like SiO2, etc) maintained at either preheated or room temperature. The
substrate can be post treated for tune the morphology of the nanoparticles.

9. Summary
Lithium-ion batteries (LIBs) for 21st century applications demand high capacity and high
capacity retentions, lower weight and cost, higher voltage availability, etc. These
requirements force the research community for developing alternative battery materials.
Metal sulphides due to their large capacitive enhancement compared to conventional
materials, could be one of the modern electrode materials for the LIBs. But their
applicability is restricted by the limitations of poor cycle stability and rate performance.
This paper comprehensively reviews the research activity in the domain of metal
sulphides as the new material for the LIBs, especially from the viewpoint of demands in
21st century. Salient features in the field of research highlights and general processing
methods are reviewed.

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Chapter 5

Magnetic Nanomaterials for Lithium-ion Batteries

Mine Kurtay1, Haydar Göksu2*, Husnu Gerengi1, Hakan Burhan3, Mohd Imran Ahamed4,
Fatih Şen3*
1
Corrosion Research Laboratory, Department of Mechanical Engineering, Faculty of
Engineering, Duzce University, 81620, Duzce, Turkey
2
Kaynasli Vocational College, Duzce University, 81900 Duzce, Turkey
3
Sen Research Group, Department of Biochemistry, Dumlupınar, University, 43100 Kütahya,
Turkey
4
Department of Chemistry, Faculty of Science, Aligarh Muslim University, Aligarh-202002,
India
[email protected], [email protected]
Abstract
Nowadays, the rapid rise in technological developments has caused new devices in many
fields, from health to communication. Not only it is limited to these areas, but also the
speed of technology in individual uses has made it very easy to access many portable
devices. The fact that mobile devices can offer advanced functional services to their users
continuously is because they have a safe, long-lasting, high energy density,
rechargeability, and environmentally friendly energy source. The main applications of
lithium-ion batteries (LIB) are laptops, mobile phones, small household apparatus, and
each of us prefers these electronic devices due to their non-toxicity and energy density.
Rechargeable batteries are widely used in energy storage systems with the invention of
lead-acid batteries. Thanks to high energy/power density, long cycle life, low power loss,
and loop stability, LIBs are widely used as portable batteries in electronic devices and
electric vehicles. The LIBs are intended to be used not only in the electronic field but also
in commercial vehicles, smart grids, and large-scale energy storage. However, the
properties of LIBs need to be improved. Different and various materials have been used
to improve LIB. Among the materials used, nanomaterials are found in carbon-based
structures. The small size of the nanomaterials provides high surface area efficiency and
provides electrode and electrolyte contact. In addition, it extends the energy, power, and
service life of LIBs. In this chapter, the studies and researches carried out have been
organized in order to strengthen the LIBs based on nanomaterials for longer lasting
effects.

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Keywords
Magnetic Nanomaterial, Ion Batteries, Lithium, Energy Storage

Contents

1. Introduction............................................................................................124
2. History of LIBs .......................................................................................125
3. LIB Technology ......................................................................................126
4. LIB working principle ...........................................................................127
5. Nanomaterials ........................................................................................129
6. Nanomaterials in anode for LIBs .........................................................131
7. Nanomaterials in cathode for LIBs ......................................................133
Conclusions .......................................................................................................134
References .........................................................................................................134

1. Introduction
Nowadays, it is known that there is a rapid technological consumption in all areas from
transportation to communication, from health to defense and almost every individual has
at least one of the portable electronic devices [1]. In addition, most of the electrical
appliances we use at home with the developing technology can be used wirelessly.
Portable electronic products need to have a high energy density, safe, long life, easy to
maintain, rechargeable and environmentally friendly energy source in order to fulfill their
developed functions in a long and effective manner. Lithium-ion batteries (LIB) are
preferred in the designing of electronic devices such as laptops, mobile phones, small
household appliances due to their high energy densities and non-toxic properties [2,3].
Moreover, it is also preferred by environmentally conscious designers and consumers due
to low CO2 emissions [4].
Among nanomaterials, magnetic nanoparticles have a great interest from the researchers
because of their excellent magnetic properties [6]. The nanoparticles having a size below
100 nanometers (nm) have properties which are considered to be different and superior to
the volumetric structured materials. The nanoparticle [NP] materials offer great
advantages due to their unique dimensions and physicochemical properties [7]. In recent

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years, thanks to the studies made about nanomaterials, more robust products, better
quality, cheaper, longer lasting, lighter, and smaller in size are obtained [8].

Fig. 1. Examples for the applications of LIBs [5].

Magnetic nanoparticles have been the focus of much research [9], including magnetic
fluids recording [10], catalysis [11], biotechnology [12,13] and tissue specific targeting
[14], material sciences, photo catalysis [15], electrochemical and bioeletrochemical
sensing [16], microwave absorption [17], cation sensors [18], magnetic resonance
imaging [MRI] [19], medical diagnosis [20], data storage [21, 22], nanofluids [23, 24],
optical filters [25], defect sensor [26], magnetic cooling [27, 28], environmental
remediation [29] and, as an electrode [30], for super capacitors and LIBs [31,32].

2. History of LIBs
Lithium with a low atomic number has a higher electrode potential by comparison with
lead and zinc in conventional batteries. The development of new anode, cathode, and
anhydrous electrodes is needed for the improvement of high energy LIB systems. Gilbert
N. Lewis first discovered the LIB in 1912. The first non-rechargeable batteries emerged
in the early 1970s. The availability of rechargeable LIBs has been possible after nearly 20
years of work [33]. For many years, only nickel-cadmium batteries were available for use
in portable devices (wireless communication). In 1990, nickel-metal hydride and LIBs
with higher capacity were introduced. LIBs have become the main power-supply source

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for movable products owing to their low weight and high energy density. In 1991, Sony
commercialized the first LIB, and today the LIB is the fastest-growing battery in the
world. Lithium is the lightest metal which provides the highest energy content and has
the highest electrochemical potential [34]. The main battery systems used today are
primary manganese dioxide-zinc and rechargeable lead-acid. These battery systems with
a deep-rooted history have advanced technical service life. As long as the request for
high-performance battery systems remains, the LIB will replace existing systems.
Nowadays, there are important developments in the energy storage systems of electric
vehicles that come up more frequently in Tesla's automobiles. Samsung has opened a LIB
factory in China by making investment plans in this area. Samsung SDI offers a wide
range of applications of LIBs from hybrid vehicles to pure electric vehicles. In addition,
the creation of two different application areas, namely the high voltage and low voltage
system, is also important for meeting customer demands. Thus, energy needs are
provided for both low power and high-power segments [35].

3. LIB Technology
Rechargeable batteries are called secondary batteries. They are the electrochemical cells
that can be recharged after discharge. The advantages and disadvantages of LIBs are
shown in Table 1 [36].

Table 1. Some positive and negative features of lithium-ion batteries.

Positive Negative
• Closed cell, maintenance-free • Relatively expensive
• Long cycle life • Degradation at high temperatures
• Wide operating temperature range • Requires protection circuitry for safety
• Long shelf life and to prevent overcharge and over
• Low self-discharge rate discharge
• Quick charging ability • Not tolerant of overcharge and over-
• High power discharge capacity discharge

• High energy potential • Thermal runaway concerns

• High specific energy and energy density

• No memory effect

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The most significant flaw of LIBs is that their life starts from the date of production. A
notebook battery with a 100% charge level and a temperature of 25 °C in most cases
loses 20% of its capacity each year. This loss of capacity starts from the date of
production of the product and continues even if the battery is not used at all [37].
There are many metals which react with lithium for high capacity LIB applications.
Today, graphite is used as anode material in most commercial LIBs. The disadvantages
of the graphite used as anode material are low capacity and the occurrence of safety
problems associated with the lithium ion into the structure of the anode [38-40]. Recent
studies have focused on alternative anode materials with low cost, no security problems,
high energy density, and long cycle count [41, 42]. In addition, lithium alloyed metals are
remarkable as anode material for rechargeable lithium-ion batteries [39-40]. Among these
alternative positive electrode materials, metals such as Al, Sn, Sb, and Si, which have a
high specific capacity, and their metals capable of alloying with lithium are prominent
[43-46]. The Sn-based anode materials have a discharge capacity of approximately 990
mAh/g [47, 48]. This discharge capacity is three times the discharge capacity of the
graphite anode. However, during the charging and discharging processes, the anode
material begins to pulverize decomposition at the end of a certain battery cycle, as the tin
generates a volume expansion of approximately 400% [49-51]. Therefore, the production
studies on tin-based anode materials are centered on intermetallic nanocomposites, when
considering the active-inactive composites. Tin-cobalt-based materials are important in
terms of active-inactive nanocomposite anode materials. Valvo et al. produced tin-cobalt
anode material by the electro-spray method and argued that they improved the life of the
anode material [52]. Chen et al. produced the Sn-Co based anode material with polymer
pyrolysis method and developed anodized material which was more stable to use for
longer period [53]. Li et al. capsulized the nanoscale MxSn (M = Fe, Cr, and Ni) alloys
into amorphous carbon nanotubes (ACNTs) and formed hybrid anode hetero-structures.
As a result, they indicated that anodes with large volume change significantly reduced
electrochemical degradation, and this improved LIB performance [54].

4. LIB working principle

In a rechargeable LIB, lithium ions move into an anode from a cathode during discharge
in an aqueous or non-aqueous electrolyte and return to their poles during charging. Figure
2 shows the basic working principles of LIB.

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Fig. 2. Schematic of a typical LIB.

The half-reaction for charging takes place in the anode is given below:

LiMO2 ↔ Li1−xMO2 + xLi+ + xe− (1)

And the half reaction for charging takes place in the cathode is given below:

xLi+ + xe− + 6C ↔ LixC6 (2)

where x is a coefficient for reactions taking place the cathode and anode electrodes, and
these reactions are in moles unites [55]. A LIB comprised of anode and cathode
electrodes and operates as an energy storage device thanks to the conversion of the
electrical energy to electrochemical energy. Both cathode and anode materials used in
today's commercialized LIB systems are composite materials. The materials present on
the anode and cathode electrodes have some specials sides made up a rigid structure for
Li-ions. In the beginning, the battery system is "discharged" when all ions are on the
negative electrode side. While charging, ions reach from the cathode to the anode by
moving in the electrolyte. The transmission of electrons takes place from the cathode to
anode thanks to an external collector, and that leads to a forming electrical current. The

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chemical energy potential of the anode is higher than the cathode that leads to an
electrochemical energy storage form electrical energy. The electrochemical energy is
converted to a form of electrical energy, upon the LIB is discharged. The LIB composed
of two sections which are separated by a membrane made up of a microporous structure
that prevents the electrolytes flowing between the electrodes. The electrolyte must be
ionically conductive and electronically non-conducting, but the real properties of the
electrolyte are much more complex. In present LIB technology, capacities and cell
voltage are determined fundamentally by cathode material, which is a limiting factor for
the transport rate of Li. Therefore, the development of negative electrode materials
becomes extremely important and attracts a great deal of attention in the last decade [56].

5. Nanomaterials
Nanomaterials are used to develop the speed properties of solid-state electrodes used in
batteries. Nanomaterials should be elaborated in an electrode that sustains the diffusion
length, besides ensuring electrical and mechanical contacts during the strain, carries out
structural stresses, supporting structural stresses, and support a longer service life.
Various methods have been used to prepare non-self-supporting nanometric materials
[57-60]. With these approaches, nano-sized materials (rods, wires, spheres, etc.), which
have improved electrochemical properties and need to be further processed in an
electrode film have been obtained. New electrode configurations have emerged to
maintain the benefits of electrochemistry on a nanoscale and to obtain high-speed
capabilities [61]. The use of nanomaterial electrodes in LIBs enables the development of
energy, power, and cycle life. Nanoparticles or nanopowder electrode materials, which
are thin versions of micron-sized electrode powders in lithium-ion batteries, have been
used for a long time. Carbon black is the best example of nanomaterials used in LIBs
since time immemorial [57]. However, carbon black is the nanomaterial that does not
store electrical energy and has only a passive conductivity enhancing properties to
increase the power capacity. However, remarkable performance developments can be
achieved for two reasons by designing the electrode's active energy storage component as
a nanoparticle:
• Short diffusion lengths of lithium-ion moving from the particle core to the
electrolyte,
• High electrode-electrolyte contact area caused by high surface areas of the particles
[62].
In nanoscale particle size electrodes, the mechanical stresses are significantly reduced
due to the volumetric expansion and contraction during charge and discharge. Studies

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have shown that particles should be smaller than a certain critical radius. Thus, instead of
plastic deformation, elastic deformation, which allows the structure to be recovered
without deterioration occurs [63]. Nanomaterials are used to maximizing the service life
with minimum energy density in nanopowder form, nanostructured films with wire, rod,
or column morphology [64-66].
Nanosize Li-ion storage electrode materials can provide various processing advantages
during operation. Many materials made of lithium and other transition metals are used as
lithium-ion cathode materials. Then, heat treatment is carried out under different
conditions to obtain the desired phosphate or oxide composition. If the heat treatment is
not applied correctly, the performance of the material may be reduced by causing a
heterogeneous composition in the materials. During the process of forming nanomaterials
by heat treatment, a homogeneous thermal profile should be maintained in all parts of the
material. Thus, the production of non-heterogeneous compounds will be facilitated
without the need for the application of intensive energy processing methods. It is hoped
that nanomaterials will provide new generation high-speed battery formats for
components such as sensors, RFID, and ultra-thin and flexible devices that can be used in
medical applications [67, 68].
The major disadvantage of LIBs is the low power density due to high polarization taking
place at the excess charge and discharge rate. The high polarization occurs due to weak
electrical-thermal transmissions and low diffusion rate of Li-ion through the electrolyte
and electrode interfaces. The development of high-energy rechargeable LIBs is
important for the improvement of portable electronic devices and electric vehicles [69,
70]. The limited specific capacity of cutting-edge technology negative and positive
electrode materials is the biggest barrier to high-energy LIBs [71, 72]. Developing new
materials having high thermal-electronic conduction, and a larger surface and a low
diffusion to use in electrodes is very important to overcome this problem. Nano-scale
electrode materials have many advantages than conventional materials: (i) increased Li-
ion input/output ratios owing to the short transport path; (ii) reversible Li insertion and
removal without destroying the electrode material structure; (iii) increased contact area
with electrolyte reduces intercalation-related volume changes; (iv) improved electron
transport properties [73, 74]. Carbon nanotubes (CNTs) are used as anode or an additive
for both positive and negative electrode materials to fulfill the above multifunctional
requirements for LIBs [75-82].
Multi-walled carbon nanotubes (MWCNT) have been widely used owing to their
excellent mechanical properties, electrical conductivity, high flexible structure, and high
surface area. In addition, carbon nanotubes are rapidly replacing electrochemical energy
storage systems, particularly in the development of LIB electrodes [83]. The conductivity

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network structure of the MWCNT with high conductivity helps the Sn materials to
maintain their structure during the cycle. Moreover, the high conductivity and surface
area of the MWCNT increase the capacity of the lithium to accommodate on the
electrode surface and help to make the reaction faster between lithium and the active
material [84].

6. Nanomaterials in anode for LIBs

The use of nanomaterials in the anode of LIBs provides advantages such as low cost, high
charge, and discharge rate, and energy density. Composite materials are used, or surface
modification is applied to develop the stability of nanometer materials. For LIB systems,
researches are being done to develop alternative anode materials that will provide higher
energy density.
Positive electrode materials for LIBs should
(1) be able to store a larger amount of lithium reversibly,
(2) have electrochemical potential values of lithium extraction/insertion that are closely
above lithium metal (0 V vs. Li+/Li),
(3) have high ionic and electronic conductivities,
(4) have a small variation of the electrode structure with lithium storage,
(5) be abundant in non-toxic and earth,
(6) be economical for the manufacturer,
(7) be stable with the electrolyte in a wide range of electrochemical window.
Because of their high gravimetric capacities, lithium and its alloys formed with different
metals are used as anode materials. Experimental studies have been carried out on lithium
using as anode metallic or semi-metallic elements such as Ag, Al, Bi, Si, In, Au, Sn, Pb,
Mg, Sb, Zn, Cd, Ge, As, Pt [85]. In addition, nano compounds have a great interest as
positive electrode materials owing to their high theoretical capacity, abundant in nature,
and environmentall friendliness [86]. Concerning anode materials, Si is considered the
next generation anode because of its higher capacity than the traditional graphite anode,
low operating potential, high abundance and environmentally friendly nature [87]. When
Ge tested as a positive electrode for LIBs, it has indicated large capacity, high initial
coulombic efficiency, and long cycle life owing to its self-healing mechanism and
practical applicability [88]. Liu et al. in their study, porous micro/nano lithium cerium
oxide (Li2CeO3) with baseball morphology were prepared by precipitation and thermal
annealing. The prepared Li2CeO3 (approximately 1μm diameter) was made from 5nm

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nanoparticles. As anode of lithium-ion batteries, the Li2CeO3 synthesized in the

micro/nanocomposite structure provided a high discharge capacity of 582.7 mAhg-1 after
100 cycles at 0.5 mAcm-2 [89]. The 3D porous nano/micro ZnFe2O4 was prepared by
sintering at 800°C in an air atmosphere after chemical precipitation. It is determined that
ZnFe2O4 prepared as a positive electrode material for LIBs, displays high specific
capacity, good cycle stability, and excellent speed capacity [90]. Silicone is an alternative
as a high-performance anode material because it has a very high specific capacity and
abundance. In the study, carbon-encapsulated nano-Si on graphite hybrid composite
(nano-Si / G / C) was carefully designed and obtained with an easy and scalable process.
The produced nano-Si / G / C anodes exhibit high cyclic stability with varying field mass
loads ranging from 0.968 to 4.28 mg-cm-2. Thanks to their superior properties, nano-Si /
G / C composites have a high potential for use in lithium-ion batteries [91]. In another
study, the mesoporous carbon and composite structures consisting of nano-sized Fe3O4
(10-20nm) particles were synthesized by a two-step method. The Fe3O4/C composite
displayed a high specific capacity of 1498 mAhg-1 and a recycled capacity of 717 mAhg-1
after 100 cycles of 100 mAg-1 currents, and it achieved excellent cycle performance [92].
VBO3 composite nanoparticles (VBO3@G) on graphene plates were synthesized as
positive electrode material for LIBs. Graphene layers helped to form nanoparticles and
provide an excellent conductive 3D network. It was found that the composite exhibited a
good cycle performance with an initial charging capacity of 779 mAhg-1 at 0.1 C and
maintained at 610 mAhg-1 after 100 cycles [93]. Jia et al. reported the superior cycling
stability and speed performance of the CuO electrode in LIBs. The CuO NL anodes
provided a special capacity of 320 mAhg-1 after 800 cycles and exceptionally high-speed
performance. This was direct result of the unique synergistic effects of hierarchical pores
and vibrating nanostructures. This study supported the development of electrode
materials for long-life energy storage devices [94]. Metal sulfides are considered as
electrode materials in batteries because of their high theoretical capacity. Wang et al.
proposed a different strategy for producing CoS and Co9S8 electrodes for advanced
LIBs. As a result of the study, it was determined that porous cobalt sulfide/carbon
composites, especially CoS/C/CNT (CoS-0.4C) and Co9S8/C/ CNT (Co9S8-0.8C),
which were mounted as LIB anodes, exhibited superior lithium storage properties [95].
The nano-porous nano-silicon (npn-Si) anode for the LIB reduces the problems
associated with pulverization and large-volume expansion during the charge-discharge
cycle. The study shows that the Na salt of the carboxymethyl cellulose (Na-CMC) and
alginate (Na-Alg) have good cycle stability and speed performance [96]. In another study,
nickel silicate (Ni2SiO4, NSO) was synthesized as a high-capacity anode material for
rechargeable LIBs. The results were evaluated as a promising positive electrode
candidate for LIBs due to NSO nanosheets, excellent rate capability, and good loop

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stability [97]. The nanocomposite consisting of multi-walled carbon nanotubes modified

from hematite nanoparticles has been tested as anode material of LIBs [98]. For LIBs, it
is extremely important to develop graphite alternative anode materials at low temperature
(below 0 ° C) for safety and capacity [99]. A multi-phase composite consisting of
TiO2/TiN/graphene was designed to improve the ionic and electronic conductivities and
improve the electrochemical performance at low temperature. The nanocomposites
produced showed excellent rate and superior electrochemical performance in low
temperature (0, -10 and -20 °C) lithium-ion batteries. Therefore, the prepared
nanocomposites have the potential for use in LIBs [100].

7. Nanomaterials in cathode for LIBs

The negative electrode materials used in LIBs are generally spinel or layered crystal
structure. Cathodes determine the capacity and cycle life of LIBs. In LIBs, LiMO2 type
structures (M: Co, Ni, Mn, V) are used as cathode active substances [101-106]. These
structures are suitable for Li+ during charging and discharging [107]. The cathode active
substances should be readily prepared and have high operating voltage, high binder
efficiency, high capacity, chemical stability, and long cycle life. In addition, the operating
voltage should not change much during discharge [108]. In recent studies, the emphasis
has been focused on cathodes with cheaper, environmentally friendly, high capacity, and
cycle life instead of commercially available cathodes. The reaction surface area and the
capacity value increase due to the small particle size in the active cathode material.
Ni et al. synthesized bismuth oxyfluoride impregnated CMK-3 nanocomposite. The
bismuth oxyfluoride nanoparticles produced have shown cycle stability and high capacity
when used as the cathode of LIBs [109]. Graphene/a-MnO2 nanocomposite cathodes
were produced, and the charge-discharge properties of Li-O2 cells with composite
cathodes were investigated by Çetinkaya et al. This study showed that graphene/α MnO2
nanocomposite cathodes on nickel foam can be used as cathodes for Li-O2 batteries
[110]. The structure and electrochemical activity of the electrocatalysts are important for
lithium-oxygen batteries. Mn and Ru oxides were synthesized on multi-walled carbon
nanotubes (RuO2-MnO2/MWCNTs) and used as a cathode [111]. In another study, a
nanocomposite of V2O5 / acetylene black (V2O5/C) was synthesized for use as negative
electrode material in LIBs. Stable electrochemical performance of V2O5/C
nanocomposite showed that it can be used as a cathode material for LIBs [112]. Te
nanotubes developed on solvent-free, and carbon substrates provide excellent rate
capability due to their electrochemical performance and synergistic effect. The results
showed that the Te / CFC can be used for energy storage and portable electronic devices
in rechargeable Li-Te batteries [113]. Poly-(1,4-anthraquinone)/carbon nanotube

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(P14AQ/CNT) nanocomposite has been developed to improve the rate performance of

LIBs. Results showed that The P14AQ/CNT composite used as a cathode material for
LIB had excellent rate performance and cycle stability [114]. Cubic spinel lithium
manganese oxide (LiMn2O4) is a hopeful cathode material for large-scale LIBs. Ultra-thin
1D LiMn2O4 nanorods can be used as a promising cathode nanocomposite because they
reduce Li-ion diffusion with their morphology and crystal structure [115]. Multi-walled
carbon nanotube (MWCNT) -LiV3O8 nanocomposites were produced by the sol-gel
method with no additive. The electrochemical performance of MWCNT - LiV3O8
nanocomposites was significantly improved [116]. As a summary, many types of nano-
based materials have been used for many types of applications [117-135] and battery
systems have also very important application areas for this type of nanomaterial.

Conclusions
With the development of the industry, the cost-efficient and efficient storage of energy
from renewable resources have become an important issue. Rechargeable batteries are
widely used in energy storage systems with the invention of lead-acid batteries. Thanks to
its high energy/power density, long cycle life, low power loss and cycle stability, LIBs
are widely used as portable batteries in electronic devices and electric vehicles. However,
the development of electric vehicles is limited since the energy density of LIBs is not
high enough. Despite their remarkable successes in commercial applications, there is a
need to improve the properties of LIBs for large-scale energy storage in hybrid vehicles
and smart grids. Therefore, it is focused on new generation batteries with high energy
density in studies.

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Chapter 6

Recent Advances in Nanomaterials for

Li-ion Batteries

K. Chandra Babu Naidu1*, N. Suresh Kumar2, Rajender Boddula3, S. Ramesh1,

Ramyakrishna Pothu4, Prasun Banerjee1, M.S.S.R.K.N. Sarma1, H. Manjunatha5, B. Kishore6
1
Dept. of Physics, GITAM Deemed to be University, Bangalore -562163, India
2
Dept. of Physics, JNTUA, Anantapuramu-515002, A.P, India
3
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for
Nanoscience and Technology, Beijing 100190, PR China
4
College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, PR
China.
5
Dept.of Chemistry, GITAM Deemed to be University, Bangalore -562163, India
6
Dept. of Mechanical Engineering, GITAM Deemed to be University, Bangalore - 562163, India
*[email protected]
Abstract
This chapter provides the information about different materials for the fabrication of Li-
ion batteries. Further, the basic structure of Li-ion batteries is discussed. Subsequently,
the electrochemical energy storage efficiency of various Li-ion batteries is described as a
function of distinct electrochemical parameters.
Keywords
Li-ion batteries, Electrochemical properties, Advanced materials, Specific capacitance

Contents

1. Introduction............................................................................................149
2. Structure and working of Li-ion battery .............................................150
3. Electrochemical behavior of various materials for Li-ion batteries .152
Conclusions .......................................................................................................157
References .........................................................................................................157

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1. Introduction
Rapidly growing technology of the current world requires the electrical energy storage
for systematic run of digital electronic devices (DED), hybrid electrical vehicles (HEV),
and aerospace vehicles. For this purpose, the most commonly used electrical energy
storage devices are capacitor, battery, pumped hydropower, supercapacitor, flywheels,
and compressed air [1]. Out of these energy storage elements, the batteries have good
recognition owing to their efficient power density, thermal stability and energy density
parameters. This efficiency of various electrochemical parameters mainly depends on the
battery chemistry as well as its design [1]. However, in case of Li-ion batteries, the life-
extension, inexpensive, energy density, cyclic retention and charging speed are more
advantageous than the other batteries/electrical energy storage devices [2]. Therefore,
these Li-ion batteries are quite useful in the computers, smart mobiles, power tools, grid
energy storages, electronic machines, fitness bands, and portable electronic objects [1].
Although, the abundance of lithium is limited on the earth surface, the Li-ion batteries
have acquired considerable attention in the electric vehicles, and aerospace machines [1].
It is noticed that the Li-ion batteries will have a state of charge (SOC) ranging from 20 –
80 % in order to avoid deep discharge and overcharge [2].
Munson [4] showed the voltage versus capacity trend of Li-ion batteries at different
temperatures of 25 oC, 0 oC and -20 oC at a constant current of 2.3 A. This is depicted in
Figure 1. It is understood that the Li-ion batteries revealed low capacity (%) at high
voltages. On the other hand, the capacity is gradually increased to high percentage at the
intermediate voltages (for different temperatures). Subsequently, the capacity is further
enhanced to higher value of 80 – 100 % between the voltages of 2.0-2.5 V. From this, it
is confirmed that the efficiency of Li-ion batteries is very much preferable at room
temperature (25 oC), whereas the electrochemical performance is come down while
moving towards low temperatures. However, in the current world, the usage of electric
vehicles, laptops, smart mobiles, and other portable electronic objects is extensively made
only at room temperature rather than the lower temperatures. Therefore, the Li-ion
batteries are well suited for electrical energy storage in the above mentioned electronic
devices/machines.

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Figure 1:Li-ion battery performance (voltage versus capacity) at different temperatures.

2. Structure and working of Li-ion battery

It is a known fact that the efficiency of electrical energy storage of batteries typically
depends on the design of anode, cathode, and electrolytes. The schematic representation
of the structure of Li-ion battery is provided in Figure 2 [1]. In general, the storage of
electrical energy is a dependent parameter of chemical components of different
electrochemical potentials within the batteries. Zhaoxiang et al. [1], considered a familiar
and commercial Li-ion battery material. This material is divided into pairs called LiCoO2
and graphite. In order to elucidate the charging and discharging process of a static
battery, the lithium cobalt oxide and graphite materials are treated as cathode and anodes
respectively. It can be obviously seen in Figure 2. In Figure 2, cathode, anode,
electrolyte, separator, and current collector components are noticed. The current collector
is employed in order to transport the electrons from electrodes to the terminals of battery.
Likewise, the separator which reveals normally porous structure can prevent the shorting
of cathode (+ve electrode) and anode (-ve electrode). In the same fashion, the electrolyte
provides the transportation of ions in order to keep the constant charge during the
charging or discharging process. Moreover, the carbon additive along with binder is

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mixed to the present electrodes of LiCoO2 and graphite for making the electron transfer
in a convenient way and to achieve mechanical integrity during the cell fabrication. The
cathode and anode materials can be prepared using the following chemical reaction.
Herein, the forward arrow mark indicates the charging while the backward arrow mark
shows the discharge mechanism.

LiCoO2 Li1-xCoO2 + xLi+ + xe- (Cathode) (1)

C6 + xLi+ + xe- LixC6 (Anode) (2)

It is clear that the lithium ions are transferred from cathode to anode during the charging
process while the same ions will be transferred in opposite direction during the discharge
process. The bulk form of the prepared Li-ion batteries for electric vehicles and
smartphones is provided in the Figure 2.

Figure 2:Structure of Li-ion battery and internal components.

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3. Electrochemical behavior of various materials for Li-ion batteries

It has been an established fact that the Li-based materials, metals, phosphates, oxides,
sulfides, fluorides, thin films, silicates, metal oxides, ferrites, perovskites, nanosheets,
nanorods, nanofibers, composites, polymers, nanobelts, nanoparticles, nanowires,
nanoboxes, microboxes, nanotubes, etc. The electrochemical performance of each kind of
material is listed in Table 1. The materials along with the electrochemical parameters are
extracted from the references provided in Table 1 [5 – 36]. Among the lithium-based
materials, it is noticed that the compounds such as Li22Si5, Li-metal, Li-ion polysulfide,
Li9Al4,and Li2S recorded the highest specific capacitance values of 4200, 3860, 2430,
2235 and 1672 mAh/g respectively [see Table 1]. The Li22Si5 showed the extreme
capacity (4200 mAh/g) at very low voltage (Li/Li+) of 0.4 V. However, it has one
disadvantage of quick degradation of that material owing to the high expansion, and solid
electrolyte interface layer growth. Likewise, Li-metal revealed high specific capacity
(3860 mAh/g) at low voltage of 0.03 V. It provided the flat potential curve. Besides, the
defect observed this metal has limited Coulombic efficiency. Li-ion polysulfide
expressed the capacity of 2430 mAh/g. This material showed the high energy density of
450 Wh/kg with good capacity retention about 70 % for 240 cycles (for charge and
discharge). Li9Al4 also exhibited high capacity. The big advantages of this compound are
good availability, cheap and environmental free. But the disadvantage is limited cycle
life. Li2S is having high abundance by providing high capacity at 0.4 V. However, due to
limited cycle life, it has less significance over the rest of Li-based compounds.
Furthermore, it is observed that the phosphorous, carbon, silicon, metal oxides and their
composites showed considerable electrochemical performance for Li-ion batteries (see
Table 1). In view of this, the NiP2 and pristine C3N acquired the capacity of 1000 and
1071 mAh/g respectively. Pristine C3N provides good electronic properties and cycle
performance due to low energy band gap of 0.39 eV and small energy barrier gap of 0.27
eV. The SiN0.79 expressed high capacitance of 1500 mAh/g with an excellent cyclic
retention for 2000 cycles. Similarly, the different forms of metal oxides like MoO2, α-
MoO3 nanobelt (nb), and MoO3 nb/C attributed the capacity of 1607, 1000, and 1000
mAh/g respectively. Herein, the MoO2 has retention for 50 cycles. The α-MoO3 nanobelt
(nb) and MoO3 nb/C offer current density of 50 and 0.1 mA/g respectively. Concerning
with the composites, the MnO/rGO (graphene oxide) nanocomposite and
MnO/C@MRGO attained the capacitances of 2358 and 1178 mAh/g respectively. The
MnO/rGO showed the capacity retention of 570 mAh/g for 100 cycles. The current
density about 100 mA/g is recorded for MnO/C@MRGO to offer good cyclic retention.
The iron oxide and its based composites revealed significant capacitances for Li-ion
batteries. For instance, the Fe2O3/SWCNT (single-wall carbon nanotube), Fe3O4/N-doped

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graphene and 3D-α-Fe2O3 exhibited the specific capacitance of 1243 (at current density of
50 mA/g), 1188 (at current density of 3000 mA/g) and 1157 mAh/g respectively. Herein,
the Fe3O4/N-doped graphene interestingly performed good capacitive retention for 1000
cycles. 3D-α-Fe2O3 offered cyclic retention at current density of 650μA/cm2 for 500
cycles (0.13 % capacity fading/cycle). The iron oxide nanorods/Ti attributed 562 mAh/g
with high cyclic retention for 50 cycles while the same iron oxide after doping with
carbon nanotubes showed low capacitance of 375 mAh/g at current density of 3000 mA/g
by possessing considerable cyclic retention for 1000 cycles. As a whole, it is confirmed
that the doping of various metals and CNTs to iron oxides reduced the specific
capacitance and offered good cyclic retention for larger number of cycles. In the case
film-based materials like CoN film offered capacitance of 990 mAh/g when compared
with other films mentioned in Table 1.
The cobalt oxides and their composites played a vital role to perform the Li-ion battery
applications. Different forms of Co3O4 are presented in Table 1 pertaining their specific
capacitances. It is found that the Fe2O3/Co3O4 double-helled hollow microcubes and
nanoporous TiO2/Co3O4compositesshowed the highest and lowest capacitances about
1687 and 998 mAh/g respectively. The Fe2O3/Co3O4 double-helled hollow microcubes
acquired the size about 20-30 nm with Coulombic efficiency of 74.4 %. For this
composite, the capacity retention is about 30 % after 50 cycles. From the overall analysis
of the data on the electrochemical performance of various materials mentioned in Table
1, it is understood that the Li-based materials offered high specific capacitance values
with good cyclic ability. This is attributed to the effective ionic motion within Li-based
materials. On the other hand, the Co-based material composites also exhibited good
electrochemical ability. Thus especially, the Li-ion batteries are well suited for energy
storage applications in computers, solar cells, smart mobiles, power tools, grid energy
storages, electronic machines, fitness bands, and portable electronic objects. In addition
to this, Li-ion battery materials have applications in aerospace. Although the availability
of Li-ion battery sources is limited on the earth surface, they have provided applications
as the energy storage devices in different fields. Normally, owing to reduced capacity at
low temperatures and high temperature cycling of the positive electrode and good energy
density and specific energy along with excellent cyclic life of the cathode, the Lithium-
ion batteries played a vital role in aviation, which have been used in the systems such as
emergency lighting, ELTs, aircraft backup power supplies, cabin doors, UPS
(uninterrupted power systems). In drones and fighter jets, these are used in engine start
batteries. In addition, these batteries are also used in modern devices such as mobile
phones, tablets (USB type-c fast chargers), IoT devices, DSLR cameras, AR/VR devices

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etc. (see Figure 3). Figure 3 shows the locations of Li-ion batteries in a plane with the
suitable usage of it within aerospace [1].

Table1. Various parameters of Li- ion batteries

Sample Specific capacity (mAh/g)

LiMn2O4 [5] 154

LiCoO2 [5] 295
LiNiO2 [5] 296
LiNi0.8Co0.15Al0.05O2 [5] 300
LiNi1/3Mn1/3Co1/3O2 [5] 299
LiFePO4 [5] 178
Li2S [5] 1672
Li7Ti5O12 [5] 175
Li22Si5 [5] 4200
Li22Sn5 [5] 993
Li9Al4 [5] 2235
LiC6 [5] 372
Lithium metal [5] 3860
3D- LiFePO4/graphene composite [6] 96.7
sepiolite mineral [7] 125
g-C3N4 sheet [8] 199.5
Li4Ti5O12 [9] 161
dual-carbon framework (SnO2@C/rGO) [10] 844.1
MnO/rGO nanocomposite [11] 2358
Li-ion polysulfide [12] 2430
graphene-modified mesoporous anatase TiO2 205
(M-TiO2-GS) film [13]
MnO/C [14] 525
MnO/r-GO [14] 665.5
MnO/C@MRGO [14] 1178
CoO (nano/micro) [14] 1144
CoO/C [14] 755
NiO/MWCNT [14] 800
NiO (110) [14] 700
CuO (nano/micro) [14] 651.6
CuOnanorod [14] 654
CuO/Cu [14] 706
SnO [14] 790
SnO2-NiO/C [14] 614
SnO2-NiO/Ag 826
SnO2/sulfonated graphene [14] 928.5
MoO2 [14] 1607
Mixed MoO2 [14] 930.6
WO3 film [14] 626

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WO3/graphene [14] 656

WO3/carbon cloth [14] 662
MoO3 nanoparticle [14] 630
α-MoO3nanobelt (nb) [14] 1000
MoO3nb/C [14] 1000
Zn-doped Fe2O3 [14] 580
Fe2O3nanorods [14] 763
Fe2O3nanorod/Ti [14] 562
Fe2O3/CNT [14] 375.5
Fe2O3/SWCNT [14] 1243
α -Fe2O3nanorod [14] 908
Fe3O4/N-doped graphene [14] 1187.74
Fe3O4/Fe/C [14] 600
Ti-doped Mn3O4 [14] 557.8
Mn3O4/VGCF [14] 950
CoN film [14] 990
SiN0.79 [14] 1500
MnF2/CNT[14] 203
MgS/C [14] 530
FePy (y = 1, 2, 4) [14] 300
FeSnP (Fe51Sn38P11) [14] 427
CoxP (x = 1, 2) [14] 630
CoP/r-GO [14] 960
NiP2 [14] 1000
P-rich Ni3P [14] 550
SnSb [14] 700
CeO2/FeO3/Mn-rGO composite [15] 420
β-FeOOH nanorods-BC (biomass carbon) [16] 660
Si/C composites [17] 426.1
MoO3-encapsulated FeF30.33H2O composites [18] 215.7
LiNi0.6Co0.2Mn0.2O2-based (NCM-622) cathode [19] 123
LiNi0.5Mn1.5O4 [20] 114
Li3/8Sr7/16Ta3/4Hf1/4O3 (LSTH) [21] 142
3D-α-Fe2O3 [22] 1157
Mo3Nb2O14 [23] 329
(SnxCo100-x)50C50 [24] 400
LiFePO4-carbon black films [25] 146.7
BiVO4 microspheres [26] 590
GeP [27] 400
Li1+x(Ni0.8Co0.2)1-xO2 [28] 225
LiCoO2 [29] 160
LiCo1/3Ni1/3Mn1/3O2 [30] 140
Pristine -C3N [31] 1071
hierarchical NiOmicrotubes [32] 770
Li1.123Mg0.010Ni0.2Co0.2Mn0.467O2 [33] 308
Sm2O3 coated Li[Li1/6Mn1/2Ni1/6Co1/6]O2 [34] 186

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N-doped TiO2/reduced graphene oxide [35] 270

Hierarchical Co3O4 [36] 1324
Co3O4 nanoboxes [36] 1447
Polyhedral Co3O4 [36] 1374
Fusiform Co3O4 [36] 1326
Dumbbell-like Co3O4 [36] 1719
Co3O4 nanorods [36] 1171
Co3O4 octahedra [36] 1338
Co3O4 nanowires [36] 1027
Co3O4 nanotubes [36] 1261
Co3O4 nanoparticles /hollow carbon spheres [36] 1249
Co3O4 /C nanocapsules [36] 1468
CNF/ Co3O4 nanopyramidcoreshell NWs [36] 1173
Co3O4 /PCNF [36] 1187
Co3O4 /FLGS [36] 1417
Co3O4quantumdots/graphene [36] 1630
Co3O4/CoO/graphene [36] 1158
CuO/ Co3O4 core/shell NW arrays [36] 1633
porous hierarchical Co3O4/CuO [36] 1229
Co3O4 -α-Fe2O3 branched NWs [36] 1534
Fe2O3/ Co3O4 double-helled hollow microcubes [36] 1687
hierarchicallyFe2O3@ Co3O4 nanowire array [36] 1587
Co3O4 @TiO2 CSNFs [36] 1034
Nanoporous TiO2/Co3O4 Composite [36] 998
Co3O4 /NiO/C core/shell nanowire arrays [36] 1426

Figure 3:Usage of Li-ion battery in plane.

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Conclusions
The Li22Si5, Li-metal, Li-ion polysulfide, Li9Al4, and Li2S recorded the highest specific
capacitance values of 4200, 3860, 2430, 2235 and 1672 mAh/g respectively. the
Fe2O3/Co3O4 double-helled hollow microcubes and nanoporous TiO2/Co3O4 composites
showed the highest and lowest capacitances about 1687 and 998 mAh/g respectively.
This chapter concludes that the Li-based materials offered high specific capacitance
values with good cyclic ability owing to the motion of ions within Li-based materials and
their composites. Secondly, the Co-based materials have recorded the significant
electrochemical activity with high cyclic ability. Therefore, the Li-on batteries have
acquired applications in computers, smart mobiles, power tools, grid energy storages,
electronic machines, fitness bands, and portable electronic objects as the energy storage
devices.

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Chapter 7

Silicon Materials for

Lithium-ion Battery Applications

Sarigamala Karthik Kiran1, Martha Ramesh2, Shobha Shukla2 and Sumit Saxena2
1
Centre for Research in Nanotechnology and Science, Indian Institute of Technology Bombay,
Mumbai, MH, India - 400076
2
Nanostructures Engineering and Modeling Laboratory, Department of Metallurgical
Engineering and Materials Science, Indian Institute of Technology Bombay, Mumbai, MH, India
- 400076
Abstract
Silicon, a hard brittle crystalline solid is tetravalent metalloid and prominently well
known in the semiconductor community. Although silicon has been a material of choice
for energy generation in silicon solar cells, its high theoretical lithium storage capacity
makes it one of the most promising anode materials for development of high performance
Li-ion batteries. Unfortunately, silicon exhibits large volume expansion leading to severe
problems associated with structural integrity of the electrode and capacity retention.
Several silicon nanostructures have been explored to mitigate shortfalls of using bulk
silicon as electrode material. In this chapter, we discuss various promising designs,
utilizing various nanostructures as a possibility to mitigate the issues related to the use of
silicon in Li-ion batteries. The formation of axial heterojunctions, and core/shell
nanostructures is discussed. Processes such as etching based metal assisted
electrochemical, co-precipitation, magnesiothermic reduction, and chemical vapour
deposition techniques are briefly discussed. The structural, electrical and electro-
chemical properties of different nanostructures grown by these methods are also
summarized.
Keywords
Silicon Anode, Li-ion Battery, Nanostructures, Core Shells, Capacity, Stability

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Contents

1. Introduction............................................................................................162
1.1 Overview on lithium battery technology .........................................163
1.2 Silicon as anode for lithium batteries: .............................................166
1.2.1 0D nanostructures ............................................................................172
1.2.2 1D nanostructures ............................................................................173
1.2.3 2D nanostructures ............................................................................175
1.2.4 3D-nanostructures ............................................................................176
2. Electrochemical performance of silicon based nanostructures.........178
Conclusion.........................................................................................................188
References .........................................................................................................188

1. Introduction
We are largely dependent on use of fossil fuel to meet our current energy requirements.
The combustion of these fuels for transport, industrial and domestic purposes has not
only affected human health but also adversely affected the entire ecosystem [1].
Additionally, it takes millions of years and extreme conditions to convert fossilized
matter into fuel inside the earth. This process of generation of fossil fuel finds no match
to the rate of extraction, which is anticipated to render the earth depleted of fossil fuel in
decades to come [2]. Unfortunately, no technology is available today to replace the use of
fossil fuels entirely. It is believed that technologies like hydrogen fuel, water, wind, and
solar may collectively overcome the dependency on fossil fuel [3,4]. Most alternative
forms of energy generation are focussed on generation of electricity. It is not only
challenging to store but also requires significant infrastructure to transmit. Some
interesting initiatives using solar power have been explored to make high energy density
fuels from renewable resources [5]. However, these may be more expensive in terms of
energy generation/storage and require huge infrastructure to transport and store them
safely. The problem with such renewable power sources is that they might not be
produced at the time when needed, especially during periods of peak energy demand [6].
Further, the environmental factors also play an important role in generation of energy
using natural resources [7]. Thus in order to provide steady power supply using
renewable energy sources, energy storage seems the best way forward.

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While several strategies have been explored to store energy in various forms, storage of
energy electrochemically in form of batteries and supercapacitors forms one of the most
explored and preferred energy storage technique [8]. The term battery was coined by
Benjamin Franklin for multiple Leyden jars, in analogy to battery of cannons. However,
the history of batteries is believed to be more than 2000 years old when prehistoric
batteries in form of Parthian batteries were excavated near Baghdad. However, first
modern batteries are supposed to have made their mark in mid of 17th century with
advent of Leyden jars. Although early batteries showed great promise for experimental
purposes, they could not find large scale applications due to voltage fluctuation and their
inability to provide large current for long durations [9]. Lead-acid battery invented by
Gaston Plante in 1859 is one of the oldest known rechargeable battery. Although the
lead-acid battery had a very low energy-to-weight ratio and a low energy-to-volume ratio,
it could provide huge surge current requirements. This made them attractive for
automobile applications where high current is needed for automobile starter motors [10].
While several discoveries were made over years by many innovators like Galvini, Volta,
Davy, Cruickshank and Daniell. Waldemar Jungner in 1899 provided a breakthrough by
developing Ni-Cd cells which changed the perception of storage of energy by providing
portable energy sources [11]. For many years Ni-Cd batteries remained the flagship for
portable energy devices. However, careless disposal of these batteries resulted in
environmental hazards which restricted its usage since 2006 by European Union. While
the success story of Ni-Cd batteries was unfolding, yet another initiative made its
headway lead by an American physicist and Nobel Laureate, Professor John Goodenough
which could compete with the Ni-Cd batteries in making available portable energy. These
batteries worked on the principle of migration of Li+ ion between the electrodes. It was
first commercialized by SONY in 1991.

1.1 Overview on lithium battery technology

Lithium forms the element of choice for battery applications due to the following reasons
[12,13]. (a) Its ability to readily lose its outermost electron makes it highly reactive
resulting in easy flow of current in a battery application. (b) It has lower reduction
potential as compared to any other element in the periodic table. (c) Last but not the least,
its availability in significant amounts in natural resources. Lithium metal batteries refer to
battery systems comprising of metallic lithium as anode with all possible materials
combination for cathode and an electrolyte [14]. Although they offer high charge
density, high operating voltages (1.5V to 3.7V) and longer life, the downside is higher
cost per unit cell. One of the earliest developments in this area was made by Whittingham
in 1970's while working for Exxon. He used titanium (IV) sulfide and lithium metal as
electrodes for making a lithium battery [15]. This however could not see the light of the

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day as it not only required controlled environment for fabrication but also it was
economically not feasible. Further metallic lithium being a highly reactive element,
ignites spontaneously on exposure to atmosphere due to spontaneous reaction with water
and oxygen. This raised serious safety concerns on operation and use of such battery as a
power source [16]. The inability to use metallic lithium due to its stability issues resulted
in exploration of non-metallic lithium batteries using lithium ions. These batteries are
commonly used as rechargeable batteries till today due to their high energy densities and
economic feasibility [17]. They also provide wide operating voltages of about ~3.6 volts
making a single cell sufficient to power most portable devices. These characteristics of Li
ion batteries have raised the market demand and also paved a new path to many
innovations in the areas of materials research, engineering and technology. It has finally
placed this technology in an esteem position as a battery of the future [18].
The energy-density of Li-ion battery primarily depends on specific capacity of the
electrode materials. The energy density and longer cycling life of these batteries can be
enhanced by increasing the specific capacity of cathode and anode materials [19-21]. The
specific capacity of cathode has been improved to 160 and even to 200 mAhg-1 with new
material systems such as LiMn1-xMxO2 [22], Li[NixCo(1-2x)Mnx]O2 [23], defective Li–Mn–
O spinel structures [24], olivine LiFePO4 [25], when compared to the traditional LiCoO2
material (135 mA.h.g-1).
Various modification techniques, such as coating or compositing, elemental doping and
combination with mesoporous materials have been explored for preparing nanostructured
cathode materials [26]. These materials have both positive and negative effects on the
electro-chemical properties of the cell. Some of the drawbacks include poor cycling
stability, low conductivity and cationic disorder. Low electrical conductivity is one of the
major problems that lead to poor electrochemical performance of cathode materials. The
use of composite or coated materials with high conductivities serves two purposes,
1) Improves the overall conductivity of the entire composite material
2) Prevents the reunion of the particles, which facilitate short reaction pathways for
insertion or extraction of lithium ions [27].
However, the preparation process of nanocomposites is often critical. It requires
significant time to achieve a good dispersion, controllability and good yield of
nanoparticles in the composite. However, it becomes an expensive and low cost-
competitive initiative [28].
Several multiple redox mechanisms have been identified in transition metal oxides for
charge storage which is termed as conversion reaction [29]. Multiple charge carrier pairs
are produced during the redox process of nanocrystals. Subsequently it results in

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enhanced energy conversion efficiency (electrical to chemical energy and vice versa).
Such electrode materials include iron oxides, which are relatively abundant and easy to
prepare. The lithium storage in the negative electrodes is also based on the reversible
redox reactions that produce high specific capacities. However, the high conversion
efficiency and reversibility is only possible in nanoscale particles. Hence, engineering
novel nanostructures would probably be an effective strategy to produce high-
performance LIBs based on the anodes (Fig. 1).

Figure 1. Different Li storage mechanisms of anode materials. (Adopted with permission

from ref [30]. © 2017 Elsevier)
Lithium ion batteries involve three charge transfer reaction mechanisms:
a) Intercalation/de-intercalation:
This process refers to the reversible insertion/extraction of lithium to/from a solid host
network. These solid networks may have different crystal structures such as layered,
spinel or olivine. The intercalation processes do not usually result in a huge change in
volume. This accounts for the stability of spinel Li4Ti5O12 and graphite as electrodes
during the charge/discharge cycles. Additionally, these provide desirable properties such
as low cost, abundant availability, low de-lithiation potential vs. Li, high electronic
conductivity, and good ion diffusivity. [31] However, intercalation processes are usually
not very efficient in terms of guest ions compared to host ions. Graphite, for example, can
store one Li-ion for every 6 carbon atoms and results in relatively poor theoretical
gravimetric capacity (372 mAh g−1) [32]. This acts a bottleneck in meeting the high
energy demands for applications in automobile industry. This has led to exploration of a

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large number of materials to achieve high energy densities, improved storage capacity,
and improved cycle characteristics.
b) Conversion reaction mechanism:
Conversion materials store Li ions according to the following mechanism:

(b.n )Li+MaXb+ (b.ne-)↔ aM +bLinX (1)

Here, M represents a transition metal and X represents an anion, which is usually oxygen
in the case of anodes. This class of materials tends to have a lot of beneficial properties,
in particular, they show a high capacity (e.g. MnO2 with 755mAh g −1 [33]), are
inexpensive and environment-friendly. However, they also show significant drawbacks
such as low Coulombic efficiency (CE), unstable solid electrolyte interface (SEI) and
poor cycling stability [34].
c) Alloying/de-alloying:
This forms the third process due to which Li storage can take place and the reaction
proceeds according to the following general mechanism,

M +yLi ↔ LiyM (2)

where M corresponds to either Si, Ge, Sn or Pb. Storing Li in materials by alloying shows
very high (theoretical) capacities, as well as high energy densities and safe operations,
but they show severe problems when it comes to cyclic stability and capacity retention.

1.2 Silicon as anode for lithium batteries:

Amongst all anode materials, silicon (Si) has attracted significant attention for Li-ion
batteries. Si is a well-known and abundantly available semiconductor. It finds
applications in solar cells, microprocessors, and liquid crystal displays. Additionally, Si
has superior properties, such as high theoretical specific capacity of 4,200 mAhg-1 and
high volumetric capacity of 9,786 mAh cm-3 [35, 36]. It offers storage capacity which is
10 times as compared to carbon based materials. Si additionally shows some beneficial
intrinsic properties, such as low delithiation potential vs. Li/Li+ (0.4V) compared to most
other anode materials, which results in a high working voltage and energy density [37].
Since the potential is higher than that of graphite (0.05V vs. Li/Li+), it is less likely to
form Li dendrites at high current densities. The dendrites often lead to short circuit and
ignition or explosions [38] in the cell.

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In a conventional Si-Li cell, shown in Fig. 2 (a-b), the silicon electrode sits on the top of
a separator and is patterned to provide access points to contact the lithium cathode. These
access point allows electrons to transfer from negative to the positive terminal as shown
in Fig. 2a, completing the circuit. The porous membrane separator is soaked in a non-
aqueous liquid electrolyte. The Li+ ions de-intercalate from the anode during the
discharging cycle, pass through the electrolyte and are inserted into the cathode. The
electrons flow from the anode to the cathode through the external circuit and powers the
load attached across the cell. A reverse process occurs during the charging cycle on
applying a potential across the battery. Lithium ion batteries work on the principle of
reversible shuttling of Li+ ions. The difference of electrochemical properties of the
electrodes and their inherent properties play a crucial role in determining overall
performance of the batteries.

Figure 2. (a) Assembled Si-Li coin cell schematic and (b) Charge-discharge mechanism
schematic.
Silicon can either be amorphous (a-Si), poly-crystalline (p-Si) or crystalline (c-Si), with
the latter showing the highest electronic conductivity of all the three. c-Si undergoes a
phase transition upon first lithiation, changing from a crystalline to an amorphous state,
and remains amorphous during entire cycling. A combination of focused ion beam time-
of-flight secondary ion-mass-spectrometry and auger electron spectroscopy was used by
Bordes et al. to investigate Si particles during the first lithiation process [41]. The first
5% of Li form a solid-electrolyte interface (SEI), followed by a two-phase lithiation,
characterized by a sharp edge between the alloy shell and the pure Si core. Fast diffusion
pathways for the Li penetrate the pure Si core due to sub-grain boundary pathways as
shown in Fig. 3. After 70% lithiation, the core-shell structure disappears and the particle
starts to disintegrate [41].

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Figure 3. Schematic of alloying mechanisms of a Si particle during first lithiation. A two

phase mechanism with a sharp boarder between core (pure Si) and shell (alloy) and Li
diffusion pathways penetrating the core has been observed. (Adopted with permission
from ref [41]. © 2016 ACS)

A clear boundary between the lithiated and pure Si phase is observed in transmission
electron micrographs as shown in Fig. 4 suggesting anisotropic lithiation in c-Si along
with facet formation during the first lithiation. The c-Si remains amorphous after full
lithiation and further cycling occurs in an isotropic, single phase mechanism (Fig. 4) [42].

Figure 4. TEM images of a Si nanoparticle during the first lithiation, showing a two
phase mechanism. The schematic shows the isotropic lithiation of a-Si compared with the
anisotropic lithiation with facet formation of c-Si during the first cycle. After full
lithiation, c-Si remains in an amorphous state. During further cycling, lithiation is
isotropic and a one-phase mechanism. (Adopted with permission from ref [39]. © 2017
RSC)

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The ability of Si to store large amounts of Li results in huge volumetric changes up to

420% during lithiation/de-lithiation [43]. This results in strong capacity fading and cell
failure, mainly due to the following three effects as suggested in Fig. 5. Pulverization and
cracking of the anode material occurs due to stress induced by the volume change upon
lithiation/delithiation. This leads to loss of electric contact of the active material with the
conducting framework or the current collector resulting in capacity fading upon cycling
[44]. Delamination and morphology changes are a result of structural change upon
cycling. During lithiation, the Si particles or structures expand and impinge on each
other, whereas during delithiation they contract leading to loss of conductive contact [45].
On a larger scale, the whole electrode expands and contracts, which can cause cell failure
[43]. Unstable Solid-Electrolyte-Interface (SEI) formation can be attributed to
irreversible Li-ion consumption due to their reduction on the electrode surface and
leading to building up of SEI. This layer is conductive for Li and covers the active
material, which further prevents the SEI build up and results in a smooth and thin SEI
layer [46].

Figure 5. Schematic showing three main effects i.e. pulverization, delamination and
unstable SEI formation that contribute to capacity fading and cell failure (Adopted with
permission from ref. [39]. © 2017 RSC)

However, due to the large expansion of Si during lithiation, the SEI cracks open and
expose fresh Si. Subsequently, electrolyte gets consumed and an inhomogeneous SEI
with high resistance is formed. However, a thin, smooth and stable SEI is crucial to
obtain little loss in capacity during cycling [47].

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In order to address these issues and enhance the performance of anode materials various
strategies have been explored. Fig.6 shows an overview of the most common ones. The
main goals are to compensate or accommodate the huge volume change of Si during
cycling, facilitate electrochemical reactions by providing fast and short lithium ion
diffusion pathways, maintain a high surface to volume ratio as well as good electronic
connectivity with the current collector and ensure a smooth, thin and stable SEI formation
[39].

Figure 6. Overview of different approaches to enhance anode performance and

counteract the problems associated with Si as an anode material. Most of them
incorporate in one way or another field of nanoscience. (Adopted with permission from
ref [31. © 2015 Elsevier)

As lithium atoms are added to the Si lattice, lattice expansion occurs and alloy formation
starts to set in. Once the alloy is formed completely, the volume of the new fully lithiated
alloy increases by four fold of the original Si lattice. This may trigger development of
cracks and failing of the electrode results in the loss of electrical contact. In order to
mitigate these issues, different approaches have been explored to achieve better
electrochemical performance by using novel silicon nanostructures in the form of nano-
/micro-Si particles, thin films, nanotubes, nanowires, bulk porous morphologies and yolk-
shell silicon nanostructures as shown in Fig. 7. Scanning electronic microscopy along

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with theoretical calculations have been employed to investigate these processes [48-52].
Silicon nanocomposites are being explored to improve the mechanical stability of the
electrodes [53-56].

Figure 7. Most common nano-structures found in novel anode designs. (Adopted with
permission from ref [57]. © 2017 Springer)

Anodes based on pure Si nanoparticles do exhibit a large surface area, leading to

unwanted side reactions and extensive SEI formation. Often, these effects are
counteracted by implanting the nanoparticles into a stabilising and/or conducting matrix
or grid [58]. This however may result in electrochemical aggregation as the nanoparticles
tend to accumulate upon many cycles of expansion and contraction and disconnect from
the current collector. 1D nanorods, nanowires and nanotubes provide good conductivity
due to the 1D transport channel along them, and hence they are usually directly grown on
the current collector [58]. Furthermore, the space between the nanorods can
accommodate volumetric change, all of which leads to a high cycling stability as well as
a high reversible capacity [59]. Nanotubes additionally provide accessible channels for
electrolyte transport and short lithium ion diffusion pathways, as well as internal space
for volume expansion. The high specific surface of 1D structures unfortunately leads to
more irreversible reactions and thus to a higher SEI build up [58]. 2D thin films and

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nanoplates generally show a high capacity retention upon cycling, but they tend to crack
upon the first lithiation and hence show strong capacity fading during the first cycle. It
has been observed in the case of thin films that their decreasing thickness increases the
reversible capacity and cycling stability [39]. Si nanosheets exhibit very short lithium
diffusion pathways, little volume expansion and are highly compatible with other
materials [58]. 3D Si-based porous structures and networks can accommodate volumetric
changes due to their porous character and thus maintain structural integrity while having
a much higher tap density. Thus theoretically a much higher volumetric capacity, than
nanostructures of lower dimensionality is achieved. 3D structures also provide fast
lithium diffusion through their pores, but similar to 0D and 1D approaches, composites
usually show better performance than pure Si structures [39, 58].

1.2.1 0D nanostructures
The term 0D nanostructures is generally used to represent nanocrystals, nanoparticles,
nanodots, or quantum dots. These can be synthesized using different techniques such as
molecular beam epitaxy (MBE), sputtering, laser ablation, and chemical methods [60–
62]. A variety of nanostructured Si or Si-C materials have been explored as anode
materials [63-67]. Si/Carbon core-shell composite synthesized shows a capacity retention
of 74% after 1000 cycles [68]. However, synthesis of hierarchically-structured Si-anodes
are often elaborate and involve complicated treatment like pre-coating or selective
etching [69-70]. These processes may require use of hazardous chemicals like HF and
severe conditions like high temperature [71,72]. These complicated synthesis procedures
add to the production costs and undermines the commercial attractiveness of silicon
[73,74]. On the other hand, carbon-based hosts have poor mechanical stability. This leads
to fracture, thereby resulting in continued exposure of fresh surface of the Si core to the
electrolyte, which causes sustained capacity loss after numerous cycles [75]. Although
the introduction of a protective metal oxide layer (e.g., SiOx, TiO2, TiO2-xFx and Al2O3)
is expected to increase the interfacial and structural stability of Si-based composites in
the low potential range, these coating materials usually show poor electrode kinetics [76-
80]. Therefore, it is important to design a Si-based composite, functionalized with a
coating layer that is conducting (both ionically and electrically). In contrast to other
techniques, co-precipitation is one of the most convenient techniques for either
preparation of nanoparticles or the incorporation of trace elements into nanospheres with
a narrow size distribution, during solid solution formation and recrystallization. In
addition, the co-precipitation technique does not require costly equipment, stringent
reaction conditions, or complex procedures [81]. In some cases, crystalline nanoparticles
can be obtained directly by co-precipitation without calcination or post annealing process.
Surface defects form a matter of concern for battery applications. Surface passivation of

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nanocrystals occurs during wet chemical synthesis, this results in suppression of

interfacial defects and carrier recombination at the surface [82].
Another approach which has been explored in the recent past has been the use of Metal-
organic frameworks (MOFs) [83, 84]. Some of the low cost potential candidates include
Prussian blue and its analogues (PBAs) primarily due to possibility of achieving highly
reversible insertion and extraction of ions. These have been widely used as water colours
and catalysts [85-88]. KMFe(CN)6 compounds (where M = Mn, Fe, Co, Ni and Zn) when
used as cathodes in silicon batteries do not show capacity loss after 30 cycles [89].
MnFe(CN)6 demonstrated specific capacity of 295.7 mAh g-1 after 200 cycles as the
anode for lithium ion batteries [90]. However, limited success with lower capacity of
PBA anodes [91-92] lead to exploration of core-shell Si-based nanocomposites in lithium
ion batteries for confining the volumetric change and enhancing the electronic
conductivity of Si anode.
The schematic for synthesis of PBAs@Si nanocomposites using co-precipitation method
at room temperature is shown in Fig.8. Na4Fe(CN)6 and MnCl2 are used as ion source in
the presence of Si NPs suspension. The [Fe(CN)6]4- anions chemisorb onto the surface of
silicon nanoparticles forming SiO2 core. The silicon nanoparticles act as nucleation sites
resulting in formation of PBAs on the surface of silicon nanoparticles. Subsequent
reaction with [Fe(CN)6]4- results in the further growth of PBAs on the PBAs@Si crystal.
The color of the sample changes gradually from pale yellow to yellow-green.

Figure 8. Schematic for the synthesis of PBAs@Si-450 nanocomposite. (Adopted with

permission from ref [93].© 2018 ACS)

1.2.2 1D nanostructures
Nanowires, nanotubes, and nanopores are commonly referred to as 1D nanostructures due
to large aspect ratio. These have been grown and fabricated using variety techniques such
as chemical vapour deposition, molecular beam epitaxy, laser ablation and metal-

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catalysed chemical etching (MACE) to name a few [94-101]. MACE is an interesting

technique to grow Si nanostructures [102-104]. In this process, the noble metals spots are
deposited on silicon surface using techniques like thermal evaporation [102-105,106],
sputtering [107], electron beam evaporation [108], electroless deposition [109] and spin
coating [110]. The substrate in MACE do not act as catalyst but as electron donors, so
that it can be etched to assist in the formation of nanostructured patterns [111].
The MACE mechanism for the preparation of Si NPs and Si NWs is briefly described
below. The Ag+ ions deposited on the silicon surface capture electrons from the valence
band of Si and forms metallic Ag nuclei. The electron transfer from silicon to silver ions
occurs due to the higher electro-negativity of the silver ions. The silver nuclei so formed
assists in preferential reduction of silver ions resulting in deposition of more metallic
silver and growth of silver nuclei. However, during the process excessive local oxidation
occurs beneath the silver particles resulting in formation of SiO2. The underlying SiO2
beneath the metallic silver nuclei dissolves leading to formation of pits and subsequently
deepening occurs resulting in formation of straight, non-interacting cylindrical pores
orthogonal to the Si surface as seen in Fig. 9. Further dissolution of the thin pore walls
the adjacent pores merge leading to formation of large quantities of silicon nanowires on
the silicon surface. In this process, the morphology of the produced silicon nanowires
depends crucially on the etching parameters such as solution concentration, temperature
and metal species in the HF solution.
The following reactions are involved [102-104]:

HF → F- +H+

Si +6F→SiF 2-6 +4e-

AgNO3→Ag++NO3-

Ag++e-→Ag0(s)

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Figure 9. Schematic of MACE for the preparation of Si NPs and Si NWs.

1.2.3 2D nanostructures
2D nanostructures are commonly known as thin films, nanoplatelets and nanosheets. The
2D nanostructures have typically been synthesized using chemical decomposition of
silanes [112, 113] or sputtering [114, 115]. Template based method to synthesize silicon
nanosheets have been explored recently. However, the process leads to small sheets with
low yield and have poor electrochemical properties [116]. In another approach the silicon
nanosheets were produced using sand and the resulting silicon sheets were broken into
smaller nanosheets. The sheets so produced showed formation of stacked structures
resulting in detrimental effects such as lower Coulombic efficiencies and drastic capacity
decays in performance of the cell [117]. Natural clays containing silicates with layered
structures have also been explored to produce 2D silicon nanosheets by exfoliating then
using molten salts [118, 119]. Unfortunately, multiple elements present in the clay makes
it difficult to remove these other elements.
Hydrolyzed tetraethyl orthosilicate (TEOS) as the silica source with NaCl particles as
templates have also been used to synthesize 2D silicon nanosheets. The schematic is
shown in Fig. 10. This process involves in situ synthesis of SiO2 nanosheets accompanied
with reduction of Mg. SiO2 nanosheets are formed using the surface of NaCl particles as
template and the TEOS as the silicon precursor.

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Figure 10. Schematic showing synthesis of silicon nanosheets using NaCl particles as
template and the hydrolyzed TEOS as the silica precursor followed by magnesiothermic
reduction. (Adopted with permission from ref [120]. ©2018 Elsevier)

It is hypothesized that large surface area of recrystallised NaCL contributes to the

formation of large SiO2 nanosheets via a self-assembly process on the surface of NaCl.
The nanocomposites of the so produced silicon nanosheets with rGO exhibit cycling
stability and improved rate performance.

1.2.4 3D-nanostructures
Several variants of 3D silicon nanostructures in the form of yolk-shell and core-shell
morphologies have been explored. One of the most common approaches is the synthesis
of carbon coated silicon in form of core-shell assemblies. Such an arrangement enables in
overcoming the low conductivity and structural instability arising from large volume
changes and high resistance of silicon [121–125]. The presence of carbon layer assists in
decreasing the resistance of silicon particles significantly resulting in sustenance of
reversible capacity of Li-Si alloys. However, the breaking of carbon shell in such an
arrangement seriously hampers the reversible Li extraction which not only results in
increased electrode resistance but also leads to fading of the reversible capacity. The
movability of the core in a yolk-shell structure in a silicon/carbon system enables in
providing space for more volume expansion and provides an effective solution for
volume expansion during the lithiation process. In a recent development Si micro

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particles were encapsulated in conformally synthesized multi-layered graphene cages.

The graphene cage allows the silicon micro particles to fracture and performs as a
flexible buffer during cycling thereby retaining the electrical conductivity of the material.
This enabled in achieving a high tap density along with high cycling stability [126]. It has
also been observed in independent investigations that chemically inert graphene layer
reduces the irreversible consumption of lithium ions and rapidly increases the Coulombic
efficiency by forming a stable SEI film as compared to pyrolytic carbon [127]. This is
suggestive of much higher flexibility and electrical conductivity of graphene as compared
to that of pyrolytic carbon. This high flexibility of graphene sheets effectively balances
the volume strain resulting during the galvanostatic cycling while high electrical
conductivity enables in decreasing the internal resistance of the cell [127,128].
The schematic in Fig. 11 shows the synthesis of the spongy nanographene functionalized
Silicon (Si@SG) composite. [129].

Figure 11. Schematic showing synthesis of Si@SG nanostructures. (Adopted with

permission from ref [129]. ©2018 Springer)

The spongy nanographene shells were synthesized from CVD technique using nickel
based templates. The presence of large number of graphene sheets stacked on silicon not
only allows better electron conductivity but also allows fast migration of Li+ and
electrolyte ions near the silicon surface providing reduced mass barrier effects. The
porous frameworks also allow to absorb the volume stress due to expansion of the silicon
lattice during charging and discharging of the cell. These morphologies are different as
compared to conventional mixture of rGO shells over silicon as shown in Fig. 12 (a) and

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(b). Thus this approach enables in mitigating the issues related to conductivity, volume
expansion and mass transfer in silicon anodes.

Figure 12. Schematic representation of (a) volume buffering (top) and mass transfer
(bottom) mechanisms of the functional SG shell, (b) conventional mixture of rGO sheets
and Si, (Adopted with permission from ref [129]. © 2018 Springer)

2. Electrochemical performance of silicon based nanostructures

A comparative study on the performance of Si based nanostructures is evaluated using
electrochemical testing of the anode material. These studies provide comprehensive
understanding of charge transfer mechanisms and structural stability of nanostructures
during the electrode cycling. Further various research works on synthesis of composite
nanostructures of Si with different carbon materials, as well as the effects of metallic and
non-metallic doping is also discussed. Surface modification of Si is one such strategy to
strengthen the core of the Si nanomaterial to inhibit volume expansion and augment the
mechanical stability to the material. In this technique, both ionically and electrically
conductive layer is coated to prevent the electrolyte from persistent decomposition on the
anode.
The galvanostatic voltage profiles of prepared Si with Prussian blue nano-architectures
(PBAs). PBAs@Si and PBAs@Si-450 (sample treated at 450०C), as well as pure Si is
shown in Fig. 13(a&b). The initial discharge capacities obtained from the galvanostatic
profiles for pure Si, PBAs@Si and PBAs@Si-450 are approximately 3510mAh g-1,
1899mAh g-1 and 2155mAh g-1respectively. The initial Coulombic efficiencies for the
sample treated at 450०C is higher compared to [email protected]; Coulombic efficiencies are
in the order of, pure Si>PBAs@Si>PBAs@Si-450. Thus, the reduction in initial specific
capacities and Coulombic efficiencies are mainly attributed to the reduction in silicon

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content. The annealing process helps in effective nitrogen doping of the samples. It is
also hypothesized that the reduction in Coulombic efficiency of the nitrogen doped
sample (PBAs@Si-450) is comparatively less which could be ascribed due to electrolytic
degradation.

Figure 13 (a) Galvanostatic voltage profiles and (b) dQ/dV curves of pure Si, PBAs@Si,
and PBAs@Si-450 for the first cycle at 0.07 A g-1. (Adopted with permission from ref
[93]. © 2019 ACS)

The irreversible loss in capacity is also observed as SEI peak in the dQ/dV plots shown in
Fig. 14 (a&b). The trivial irreversible oxidation reactions occurring are realized from SEI
layer formation and also from the formation of crystalline Si during the de-lithiation
process of amorphous LixSi alloys [130]. Besides, the reduction peaks are accounted for
the reversible lithiation of silicon and carbon /transition metals in PBAs derived shell
[131]. The broad peak (0.6~0.8 V appears for PBAs@Si) during the first cycle suggests
the formation of a SEI film layer on surface of the active material [132]. The other two
subsequent cycles for PBAs@Si and PBAs@Si-450, in the dQ/dV curves are indicative
of better cyclic reversibility. Further no significant peak shift is observed in the curves
over 200 cycles which shows the enhanced cycling stability. The presence of mesoporous
nature of the PBA-derived metal atoms and the SEI layer formation during nitrogen-
doping over the carbon can be accounted for the stable behaviour. It is also unambiguous
that the loss mechanism for PBAs@Si and PBAs@Si-450 is mechanical loss of the active
material. The PBAs@Si-450 shows an outstanding rate capacity and structural stability
(Fig.14c), a reversible charge capacity of 1450 mAh g-1 is attained at a current density of
0.14 A g-1 and even at a current density of 0.42 A g-1 a specific charge capacity of 1136

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mAh g-1 is recovered. Further the electrode kinetics is evaluated using the
electrochemical impedance spectroscopy (EIS), as shown from Fig. 14d. It is apparent
that the electrolytic and charge transfer resistances (Rct) for pure Si electrode is higher
compared to the other samples. Even though the Rct of PBAs@Si-450 is greater than
PBAs@Si during first cycle, subsequently after 200 cycles the charge transfer resistance
is reduced. This mainly occurs due to the electrode cracking process or the presence of
active particles which enhance the number of active sites for the electrochemical
reactions.

(a) (b)

(c) (d)

Figure 14. Electrochemical performances of pure Si, PBAs@Si and PBAs@Si-450. (a, b)
dQ/dV curves of PBAs@Si and PBAs@Si-450 at 1st, 50th, 100th, 150th, 200th cycle. (c)
Rate performance of pure Si, PBAs@Si and PBAs@Si-450 at various current densities
ranging from 0.14, to 14 A g−1 and finally back to 0.42 A g−1. (d) EIS plots of pure Si,
PBAs@Si and PBAs@Si-450 after 1 cycle and after 200 cycles. (Adopted with permission
from ref [93].© 2019 ACS)

Fig. 15 represents SEM micrographs of silver assisted chemically etched Si nanowires for
an etching time of 10 min with a depth of 6 µm. The Si NWs and Ag particles (at the root
regions) can be seen in the Fig. 15 inset. It is also seen that the etch front is not even, but
it is likely that there is large distribution of shapes and different alignments of the Ag

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nano particles which is due to the fact that the contact area of the Ag particles defines the
etching profile [133]. It is also imperative that this effect may also arise when an Ag film
is used instead of Ag particles. The space between the silver nanoparticles also results in
nanowires, whose thickness is in the range of 90 nm - 300 nm. Moreover, Si micropillar
scan also be seen with some porous sites at their top. This has happened because of the
lateral etching of residual silver nanoparticles with sizes below 50 nm.

Figure 15. SEM micrograph of a sample after the etching process. Inset shows zoomed
image of the formed Si NWs, with Ag particles at the bottom. (Adopted with permission
from [135]. © 2019 Springer)

The walls of the Si micropillars present roughness given by the shape of the Ag particles.
By means of a longer etching duration, micropillars with smoother walls can be yielded
but the top most regions would be dissolved.
Similarly, the surface morphologies (Fig. 16 (a&b)) and the internal structure of 1D
porous Si nanowires (PSiNWs)(Fig. 16 (c-f)) is shown which gives the comprehensive
relation with the fabricated nanowires and their electrochemical properties. The cross-
sectional surface in Fig.16a suggests that the 1D-PSiNW arrays are uniform over the
entire surface. The magnified image (Fig. 16b) suggests that the width of perpendicularly
arranged arrays of SiNWs in the range of 60.0-500.0 nm has mesoporous openings which
are evenly spread over the length of each nanowire. Even after treatment with
hydrofluoric acid the length of the as-prepared 1D-PSiNWs are still ~7.0 µm.
Transmission electron microscopy (TEM) images (Fig.16(c-f)) shows that the NWs are

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highly porous at the surface, with both pore diameter and wall thickness around 7 nm.
The obtained selected area electron diffraction (SAED) patterns (Fig.16c) and lattice
fringes presented (Fig.16f) reveal that the porous NWs has polycrystalline structure and
monocrystalline properties as well.

Figure 16. SEM (a,b), TEM(c,d), and HRTEM (e,f) images of 1D-PSiNW arrays etched.
(Adopted with permission from ref [136]. ©2018 MDPI)

The electrochemical behaviour of 1D-PSiNWs were analysed using charge-discharge

profiles as shown in Fig.17a. The initial capacities obtained during the discharge and
charge for the anodes are 4487.2 mAh·g−1 and 2534.5 mAh·g−1 respectively, with 56.5%
initial Coulombic efficiency. The irreversible loss of capacity was resulted due to SEI

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layer formation on the surfaces of the nanowires. Further to investigate stability of

nanowires, cycle life performance is performed (Fig.17b) at various current density
values. It turns out that nanowires exhibited a high capacity of 2061 mAh·g−1 over a
thousand cycles. The Coulombic efficiency was much greater (99.7%) with a rate
capability over a voltage window of 0.01V -2.0 V (Fig.17c). The specific capacity
obtained during discharge is about 2706.5 mAh·g−1 at 0.4A·g−1 while retaining the
capacity of 1667.0 mAh·g−1 at 4 A·g−1. After cycling for 5000 cycles the anode still
holds a higher specific capacity (586.7 mAh·g−1) when compared to graphite (Capacity
~372.0 mAh·g−1) (Fig. 17d).

Figure 17. Results of electrochemical performance for 1D-PSiNWs anodes. (a)

Galvanostatic charge/discharge profiles between 0.01V and 2.0 V vs. Li/Li+ for the first,
10th, 50th, 100th cycles at a current densities of 1.0 Ag-1. (b) cycling performance of the
as-prepared 1DPSiNWs anodes at a current densties of 1.5 Ag-1 (c) rate performance of
as prepared 1DPSiNWs anodes at a current densties of 0.4/1/2/4 Ag-1 (d) electrochemical
performance of the as-prepared of 1DPSiNWs anodes with 5000 cycles at current
densities of 16 Ag-1.(Adopted with permission from ref [136].© 2018 MDPI)

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(c) (d)

Figure 18. (a) SEM, (b) TEM image of Si NTAs and (c) Porous Si NTAs fabricated by
three template directed method. (d) Galvanostatic charge-discharge profile performed
and (e) cycle stability of Si NTAs performed at C/20. (Reprinted with permission from ref
[134]. ©2017The Electrochemical Society)

Some other alternative routes to synthesize ultrathin crystalline silicon nanotube arrays
(Si NTAs) were adopted using a three step template directed method [134]. The
schematic process for synthesis of Si NTAs is also shown in Fig. 18c. The morphological
studies (SEM and TEM shown in Fig. 18 (a&b respectively)) gives a clear understanding
of the vertical growth of nanotube arrays. The Galvanostatic charge-discharge profile and
cycle stability of the Si NTAs performed at C/20 in a potential window of 0.01 - 1.75 V
vs Li/Li+, respectively (Fig. 18d and 18e). The discharge profiles obtained for the
SiNTAs show four small plateaus at 1.2 V, 0.7 V, 0.5 V and 0.4 V. These plateaus
correspond to Li+ reaction with electrolyte decomposition species to form SEI interface, a
reaction which involves iron oxide present in stainless steel (SS) and alloying reaction of
silicon. While the regions at 0.38 V and 0.5 V during initial charging process corresponds
to the de-alloying mechanism of silicon. The Si NTAs/Li cell shows a large discharge
capacity of 3095 mAh.g-1 which is due to the 3D porous structure that can accommodate

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large volume changes during cycling. The irreversible reaction of Li+ with FeO and ZnO
sacrificial template (not completely dissolved) used for synthesis process of the NTAs
leads to a large fade in discharge capacity. During the cyclic stability test a gravimetric
capacity of 1670 mAh.g-1 was obtained after 30 cycles.
Graphene coated templates are also widely used nowadays in the field of energy storage
as graphene provides high surface enhancement. The Si coated graphene structures are
also considered to be potential candidates with excellent stability during cycling and also
a right choice to solve the degradation issues of silicon [137, 138]. The structure of silica
coated graphene (Si@SG) shown in Fig.19(a). The micrograph reveals that each silicon
particle is individually wrapped in the sponge like nanographene (SG) matrix. It
resembles a flower-like structure of the Ni nanosheet template retaining several layers of
nanographene sheets as shown in Fig.11. The Fig.19(b) shows the diffraction fringes
whose interlayer spacing is calculated to be approximately 3.5 Å. Further the
electrochemical studies on graphene composite matrix were investigated by fabricating a
coin cell. It delivers a high reversible discharge capacity of 2330 mAh·g−1 (2532 mAh·g−1
when considering silicon alone) at 0.250 A·g−1 and retains a high capacity of 1385
mAh·g−1 (1505 mAh·g−1 with silicon alone) after 510 cycles at 0.500 A·g−1as shown in
Fig.19(c). It suggests superior cycling performance with the hierarchical graphene matrix
(Fig. 19(d)). The capacity obtained during the discharge is about 1470 mAh·g−1 is
obtained after twenty cycles. The fade in capacity is only 5% even after 510 cycles.
Moreover, the Coulombic efficiency (CE) reported for the Si@SG composite is 83.4%
for the first cycle, denoting an excellent initial CE, which is rarely reported elsewhere
[139].
As far as material conductivity is considered reduced graphene oxide can be used to
increase the conductivity of anodes [140]. Compared with most conventional rGO-
modified silicon composite electrodes (obtained by physical mixing or chemical
modification), the as-synthesized Si@SG composite shows a much higher cycling
stability even if at a higher charge-discharge current density, which may represent a
strong indication that the new porous nanographene shell possesses both an excellent
volume-buffering ability and a lower mass (Li+) transfer resistance. However, among the
reported Si/graphene composites, only silicon micrometer particles wrapped by both
carbon and rGO achieves almost zero capacity loss after 160 cycles [141]. Similarly,
silicon nano particles encapsulated with nitrogen doped rGO graphene and carbon
nanotubes exhibits high specific capacity and good stability [142]. This suggests that a
further contribution to the improved capacity, in addition to the effects of the higher
conductivity and the more stable SEI layer, may also come from the carbon component.

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Figure 19 (a) TEM image of monolithic Si@SG composite, (b) High-magnification TEM
image of individual silicon unit wrapped with sponge-like nanographene (left), and High-
resolution TEM images of the edge (right), (c) Charge–discharge curves corresponding
to the initial, 2nd, and 10th cycles at a low current density of 250 mA·g−1, and to the
50th, 150th, 250th, 350th, and 510th cycles at a high current density of 500 mA·g−1 and
(d) Cycling performance ( lithiation capacity) of Si, Si@Ni-G, and Si@SG samples at a
current density of 500 mA·g−1, and CE of Si@SG composite measured during 510 cycles.
All electrodes were initially cycled at 250 mA·g−1 (for the first 10 cycles) and then at 500
mA·g−1 in subsequent cycles. (Adopted with permission from ref [129]. © 2018 Springer)

In comparison to various nanostructured composites of Si based electrodes reviewed in

this work so far, it can be asserted that the materials with the highest capacities are not
necessarily the best implementation in a real lithium ion battery. Further there is no exact
correlation between performance and specific dimensionality; however, it seems as if the
use of carbon, especially in the form of CNTs and graphene as a conductive and
supportive matrix, tends to improve the cycling stability and Coulombic efficiency. Also,

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composites and hierarchical structures of Si based anodes seem to exhibit a very stable
performance compared to simple structured approaches. While structures of the latter
category are often easier to synthesize, it still might be more fruitful to further explore the
possibilities of Si/C based hierarchical composite structures. In fact, most recent works
actually tend to go down that road. It should be noted that there won’t be one anode that
suits all needs and purposes, but rather different materials for either high capacities, ultra-
long lifetime or high energy output. This is also reflected in the summary of the materials
reviewed in this work (Table 1), where each material shows specific weaknesses and
strengths. Finally, despite all the challenges and problems that still need to be overcome,
silicon-based anode materials are one of the most promising anodes for the next
generation Li-ion batteries and would enormously boost their performance compared to
the current cells.

Table 1. Comparison showing various nanostructures of Si and its composites in all the
three dimensions and their performance as anode material for Li battery

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Conclusion
Silicon is extensively used as an anode material for the lithium-ion battery technologies.
The high theoretical capacity makes it an interesting material to be widely used in battery
applications. From the past few decades, there is tremendous research on nanostructured
materials to address the serious problems associated with the Si anode volume expansion
and to obtain a stable capacity. However, its commercial application at industrial level is
still limited due to several issues related to its nanostructures.

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Keyword Index TiO2 Nanostructure ................................ 1
TiO2 Nanotube Arrays............................ 1
Advanced Materials ........................... 148 Transition Metal Dichalcogenides ....... 63
Anode................................................... 28 Tungsten Disulfide ............................... 63

Capacity ............................................. 161

Cathode ................................................ 28
Conducting Polymer ............................ 28
Core Shells ......................................... 161

Electrochemical Fabrication .................. 1

Electrochemical Properties ................ 148

Graphene ................................................ 1

Hydrothermal ......................................... 1

Improved Performance ........................ 91

Ion Batteries ....................................... 123
Layered Materials ................................ 63

Magnetic Nanomaterial ..................... 123

Metal Sulphides ................................... 91
Molybdenum Disulfide ........................ 63

Nanocomposites................................... 91
Nanostructures ................................... 161

Silicon Anode .................................... 161

Specific Capacitance.......................... 148
Stability .............................................. 161

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About the Editors
Dr. Inamuddin is currently working as Assistant Professor in the Chemistry Department,
Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia. He is a permanent
faculty member (Assistant Professor) at the Department of Applied Chemistry, Aligarh
Muslim University, Aligarh, India. He obtained Master of Science degree in Organic
Chemistry from Chaudhary Charan Singh (CCS) University, Meerut, India, in 2002. He
received his Master of Philosophy and Doctor of Philosophy degrees in Applied
Chemistry from Aligarh Muslim University (AMU), India, in 2004 and 2007,
respectively. He has extensive research experience in multidisciplinary fields of
Analytical Chemistry, Materials Chemistry, and Electrochemistry and, more specifically,
Renewable Energy and Environment. He has worked on different research projects as
project fellow and senior research fellow funded by University Grants Commission
(UGC), Government of India, and Council of Scientific and Industrial Research (CSIR),
Government of India. He has received Fast Track Young Scientist Award from the
Department of Science and Technology, India, to work in the area of bending actuators
and artificial muscles. He has completed four major research projects sanctioned by
University Grant Commission, Department of Science and Technology, Council of
Scientific and Industrial Research, and Council of Science and Technology, India. He has
published 171 research articles in international journals of repute and eighteen book
chapters in knowledge-based book editions published by renowned international
publishers. He has published 105 edited books with Springer (U.K.), Elsevier, Nova
Science Publishers, Inc. (U.S.A.), CRC Press Taylor & Francis Asia Pacific, Trans Tech
Publications Ltd. (Switzerland), IntechOpen Limited (U.K.), Wiley-Scrivener, (U.S.A.)
and Materials Research Forum LLC (U.S.A). He is a member of various journals’
editorial boards. He is also serving as Associate Editor for journals (Environmental
Chemistry Letter, Applied Water Science and Euro-Mediterranean Journal for
Environmental Integration, Springer-Nature), Frontiers Section Editor (Current
Analytical Chemistry, Bentham Science Publishers), Editorial Board Member (Scientific
Reports-Nature), Editor (Eurasian Journal of Analytical Chemistry), and Review Editor
(Frontiers in Chemistry, Frontiers, U.K.) He is also guest-editing various special thematic
special issues to the journals of Elsevier, Bentham Science Publishers, and John Wiley &
Sons, Inc. He has attended as well as chaired sessions in various international and
national conferences. He has worked as a Postdoctoral Fellow, leading a research team at
the Creative Research Initiative Center for Bio-Artificial Muscle, Hanyang University,
South Korea, in the field of renewable energy, especially biofuel cells. He has also
worked as a Postdoctoral Fellow at the Center of Research Excellence in Renewable
Energy, King Fahd University of Petroleum and Minerals, Saudi Arabia, in the field of

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polymer electrolyte membrane fuel cells and computational fluid dynamics of polymer
electrolyte membrane fuel cells. He is a life member of the Journal of the Indian
Chemical Society. His research interest includes ion exchange materials, a sensor for
heavy metal ions, biofuel cells, supercapacitors and bending actuators.
Dr. Rajender Boddula is currently working with Chinese Academy of Sciences-
President’s International Fellowship Initiative (CAS-PIFI) at National Center
for Nanoscience and Technology (NCNST, Beijing). He obtained Master of Science in
Organic Chemistry from Kakatiya University, Warangal, India, in 2008. He received his
Doctor of Philosophy in Chemistry with the highest honours in 2014 for the work entitled
“Synthesis and Characterization of Polyanilines for Supercapacitor and Catalytic
Applications” at the CSIR-Indian Institute of Chemical Technology (CSIR-IICT) and
Kakatiya University (India). Before joining National Center for Nanoscience and
Technology (NCNST) as CAS-PIFI research fellow, China, worked as senior research
associate and Postdoc at National Tsing-Hua University (NTHU, Taiwan) respectively in
the fields of bio-fuel and CO2 reduction applications. His academic honors
include University Grants Commission National Fellowship and many merit
scholarships, study-abroad fellowships from Australian Endeavour Research Fellowship,
and CAS-PIFI. He has published many scientific articles in international peer-
reviewed journals and has authored around twenty book chapters, and he is also serving
as an editorial board member and a referee for reputed international peer-reviewed
journals. He has published edited books with Springer (UK), Elsevier, Materials Research
Forum LLC (USA), Wiley-Scrivener, (U.S.A.) and CRC Press Taylor & Francis
group. His specialized areas of research are energy conversion and storage, which
include sustainable nanomaterials, graphene, polymer composites, heterogeneous
catalysis for organic transformations, environmental remediation technologies,
photoelectrochemical water-splitting devices, biofuel cells, batteries and supercapacitors.
Dr. Mohammad Faraz Ahmer is presently working as Assistant Professor in the
Department of Electrical Engineering, Mewat Engineering College, Nuh Haryana, India,
since 2012 after working as Guest Faculty in University Polytechnic, Aligarh Muslim
University Aligarh, India, during 2009-2011. He completed M.Tech. (2009) and Bachelor
of Engineering (2007) degrees in Electrical Engineering from Aligarh Muslim
University, Aligarh in the first division. He obtained a Ph.D. degree in 2016 on his thesis
entitled “Studies on Electrochemical Capacitor Electrodes”. He has published six
research papers in reputed scientific journals. He has edited two books with Materials
Research Forum, U.S.A. His scientific interests include electrospun nano-composites and
supercapacitors. He has presented his work at several conferences. He is actively engaged

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in searching of new methodologies involving the development of organic composite
materials for energy storage systems.
Prof. Abdullah M. Asiri is the Head of the Chemistry Department at King Abdulaziz
University since October 2009 and he is the founder and the Director of the Center of
Excellence for Advanced Materials Research (CEAMR) since 2010 till date. He is the
Professor of Organic Photochemistry. He graduated from King Abdulaziz University
(KAU) with B.Sc. in Chemistry in 1990 and a Ph.D. from University of Wales, College
of Cardiff, U.K. in 1995. His research interest covers color chemistry, synthesis of novel
photochromic and thermochromic systems, synthesis of novel coloring matters and
dyeing of textiles, materials chemistry, nanochemistry and nanotechnology, polymers and
plastics. Prof. Asiri is the principal supervisors of more than 20 M.Sc. and six Ph.D.
theses. He is the main author of ten books of different chemistry disciplines. Prof. Asiri is
the Editor-in-Chief of King Abdulaziz University Journal of Science. A major
achievement of Prof. Asiri is the research of tribochromic compounds, a new class of
compounds which change from slightly or colorless to deep colored when subjected to
small pressure or when grind. This discovery was introduced to the scientific community
as a new terminology published by International Union of Pure and Applied Chemistry
(IUPAC) in 2000. This discovery was awarded a patent from European Patent office and
from UK patent. Prof. Asiri involved in many committees at the KAU level and on the
national level. He took a major role in the advanced materials committee working for
King Abdulaziz City for Science and Technology (KACST) to identify the national plan
for science and technology in 2007. Prof. Asiri played a major role in advancing the
chemistry education and research in KAU. He has been awarded the best researchers
from KAU for the past five years. He also awarded the Young Scientist Award from the
Saudi Chemical Society in 2009 and also the first prize for the distinction in science from
the Saudi Chemical Society in 2012. He also received a recognition certificate from the
American Chemical Society (Gulf region Chapter) for the advancement of chemical
science in the Kingdome. He received a Scopus certificate for the most publishing
scientist in Saudi Arabia in chemistry in 2008. He is also a member of the editorial board
of various journals of international repute. He is the Vice- President of Saudi Chemical
Society (Western Province Branch). He holds four USA patents, more than one thousand
publications in international journals, several book chapters and edited books.

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