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Ceramic and Specialty
Electrolytes for Energy
Storage Devices
Volume II
Ceramic and Specialty
Electrolytes for Energy
Storage Devices
Volume II

Edited by
Prasanth Raghavan and Jabeen Fatima M. J.
First edition published 2021
by CRC Press
6000 Broken Sound Parkway NW, Suite 300, Boca Raton, FL 33487-2742

and by CRC Press

2 Park Square, Milton Park, Abingdon, Oxon, OX14 4RN

© 2021 Taylor & Francis Group, LLC

CRC Press is an imprint of Taylor & Francis Group, LLC

Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot
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Trademark notice: Product or corporate names may be trademarks or registered trademarks and are used only
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Library of Congress Cataloging‑in‑Publication Data

Names: Raghavan, Prasanth, editor. | J, Jabeen Fatima M., editor.

Title: Ceramic and specialty electrolytes for energy storage devices / edited by Prasanth Raghavan
and Jabeen Fatima M.J.
Description: First edition. | Boca Raton : CRC Press, 2021. | Includes bibliographical references and
index.
Identifers: LCCN 2020053547 (print) | LCCN 2020053548 (ebook) | ISBN 9780367701444 (hbk) |
ISBN 9781003144816 (ebk)
Subjects: LCSH: Storage batteries--Materials. | Solid state batteries--Materials. | Electronic ceramics.
| Electrolytes.
Classifcation: LCC TK2945.C47 C47 2021 (print) | LCC TK2945.C47 (ebook) | DDC
621.31/24240284--dc23
LC record available at https://lccn.loc.gov/2020053547
LC ebook record available at https://lccn.loc.gov/2020053548

ISBN: 9780367701444 (hbk)

ISBN: 9780367701567 (pbk)
ISBN: 9781003144816 (ebk)

Typeset in Times
by Deanta Global Publishing Services Chennai India
Contents
Preface.......................................................................................................................ix
Editors.......................................................................................................................xi
Contributors ........................................................................................................... xiii
Abbreviations ........................................................................................................... xv

Chapter 1 Solid-State Electrolytes for Lithium-Ion Batteries: Performance

Requirements and Ion Transportation Mechanism in Solid
Polymer Electrolytes ............................................................................1
Jabeen Fatima M. J., Abhijith P. P., Jishnu N. S., Akhila Das,
Neethu T.M. Balakrishnan, Jou-Hyeon Ahn, and Prasanth Raghavan

Chapter 2 Solid-State Electrolytes for Lithium-Ion Batteries: Novel

Lithium-Ion Conducting Ceramic Materials: Oxides
(Perovskite, Anti-Perovskite) and Sulfde-Type Ion Conductors........ 19
Prasanth Raghavan, Abhijith P. P., Jishnu N. S., Neethu T. M.
Balakrishnan, Akhila Das, Jabeen Fatima M. J., and Jou-Hyeon Ahn

Chapter 3 Solid-State Electrolytes for Lithium-Ion Batteries: Novel

Lithium-Ion Conducting Ceramic Materials: NASICON- and
Garnet-Type Ionic Conductors ........................................................... 51
Prasanth Raghavan, Abhijith P. P., Jishnu N. S.,
Neethu T. M. Balakrishnan, Anjumole P. Thomas,
Jabeen Fatima M. J., and Jou-Hyeon Ahn

Chapter 4 Polymer and Ceramic-Based Quasi-Solid Electrolytes for

High Temperature Rechargeable Energy Storage Devices ................ 73
Sajan Chinnan, Nikhil Medhavi, Akhila Das,
Neethu T. M. Balakrishnan, Leya Rose Raphael, Jishnu N. S.,
Jabeen Fatima M. J., Prasanth Raghavan

Chapter 5 Quasi-Solid-State Electrolytes for Lithium-Ion Batteries................ 113

Hiren K. Machhi, Keval K. Sonigara, Saurabh S. Soni

vii
viii Contents

Chapter 6 Electrolytes for High Temperature Lithium-Ion Batteries:

Electric Vehicles and Heavy-Duty Applications.............................. 139
Leya Rose Raphael, Neethu T.M. Balakrishnan, Akhila Das,
Nikhil Medhavi, Jabeen Fatima M. J., Jou-Hyeon Ahn,
Prasanth Raghavan

Chapter 7 Electrolytes for Low-Temperature Lithium-Ion Batteries

Operating in Freezing Weather ........................................................ 161
Neethu T. M. Balakrishnan, Leya Rose Raphael,
Akhila Das, Jishnu N. S., Jou-Hyeon Ahn, Jabeen Fatima M. J.,
Prasanth Raghavan

Chapter 8 Electrolytes for Magnesium-Ion Batteries: Next Generation

Energy Storage Solutions for Powering Electric Vehicles ............... 177
Akhila Das, Anjumole P. Thomas, Neethu T.M. Balakrishnan,
Jishnu N.S., Jabeen Fatima M. J., Jou-Hyeon Ahn,
Prasanth Raghavan

Chapter 9 Aqueous Electrolytes for Lithium- and Sodium-Ion Batteries......... 193

Saurabh S. Soni and Jyoti Prasad

Chapter 10 Transparent Electrolytes: A Promising Pathway for Transparent

Energy Storage Devices in Next Generation Optoelectronics ......... 217
Anjumole P. Thomas, Akhila Das, Neethu T.M. Balakrishnan,
Sajan Chinnan, Jou-Hyeon Ahn, Jabeen Fatima M. J.,
Prasanth Raghavan

Chapter 11 Recent Advances in Non-Platinum-Based Cathode

Electrocatalysts for Direct Methanol Fuel Cells .............................. 237
Bhagyalakhi Baruah and Ashok Kumar

Chapter 12 Platinum-Free Anode Electrocatalysts for Methanol

Oxidation in Direct Methanol Fuel Cells......................................... 261
Bhagyalakhi Baruah and Ashok Kumar

Chapter 13 Ionic Liquid-Based Electrolytes for Supercapacitor Applications......... 285

Bhuvaneshwari Balasubramaniam, Ankit Tyagi, Raju Kumar Gupta

Index......................................................................................................................307
Preface
Since the commercialization of batteries began, energy storage systems have an
ineluctable role in day to day life. In 1991, Sony introduced the frst commercial
lithium-ion battery, which was considered to be a milestone that led to the revolution
of portable electronic gadgets such as cellular phones, laptops, tablets, etc. Today, a
renewable source of electrical energy is being sought to replace fossil fuels, which
has led to pollution and climate change. This initiative has forced the global market
to focus more on electric vehicles. Energy storage devices are mainly comprised
of lithium-ion batteries (LIBs), supercapacitors, and fuel cells. The performance of
these storage devices is estimated using two main parameters: energy density and
power density. The frst parameter defnes the amount of energy that can be stored in
a given volume or weight, while the second parameter describes the speed at which
energy is stored or discharged from the device. An ideal storage device should simul-
taneously deliver high energy density and high power density. The commercially
available LIBs are capable of releasing high energy density, whereas supercapaci-
tors release higher power density. The present research and development of new and
innovative component materials are progressing to address the requirements of super
gadgets. The ideal energy storage devices for long-range applications are still in their
infancy, so there are still many materials left to explore.
Even though LIBs have already been widely used in different areas, they are still
facing a lot of issues, including poor safety, short performance life, and relatively
low specifc energy. To address those issues, new battery formats, namely solid-state
LIBs, have been developed. Mainly improving the effciency of any storage device
directly depends on the performance of its components, especially the behavior of
electrodes and electrolytes on charging and discharging. Material selection is the
primary concern in developing advanced energy storage applications. The electro-
lyte is considered to be the heart of the energy storage device, and its properties
greatly affect the energy capacity, rate performance, cyclability, and safety of these
devices. Because device portability is a major requirement, safety is a key concern,
therefore, requiring the use of special electrolytic systems capable of replacing con-
ventional liquid electrolyte systems. The organic chemicals used in the liquid elec-
trolyte initiated the solid electrolyte interface formation at the anode of the LIBs,
which, on continuous cycling, formed dendritic projections extending toward the
cathode causing the devices to catch fre or explode.
The present book offers a detailed explanation of recent signs of progress and
challenges in ceramic and specialty electrolytes for energy storage devices. The
infuences of electrolyte properties on the performances of different energy stor-
age devices are discussed in detail. The detailed explanation has been classifed
under four major categories, which include a general introduction to energy storage
devices and a history of lithium-ion batteries followed by a thorough investigation on
ceramic solid and quasi-solid electrolytes and specialty electrolytes for energy stor-
age devices. The book is organized into 13 chapters. Chapter 1 discusses solid-state

ix
x Preface

electrolytes for LIBs. A detailed outlook on the performance requirements and ion
transportation mechanism in solid polymer electrolytes is investigated. This is fol-
lowed by a detailed review of solid-state electrolytes for LIBs. Chapter 2 covers
solid-state electrolytes based on oxides (perovskite, antiperovskite) and sulfde-type
ion conductor electrolytes for LIBs. Chapter 3 reviews solid-state electrolytes based
on NASICON and garnet-type ionic conductors. The following two chapters dis-
cuss specialized energy storage devices and LIBs. The subsequent eight chapters
are focused on specialty electrolytes, including electrolytes for high-temperature
LIBs, low-temperature LIBs, and magnesium-ion batteries, which are investigated
in detail. Apart from these, electrolytes for sodium-ion batteries, transparent elec-
trolytes for energy storage devices, nonplatinum-based cathode electrocatalyst for
direct methanol fuel cells, nonplatinum-based anode electrocatalyst for direct meth-
anol fuel cells, and ionic liquid-based electrolytes for supercapacitor applications are
investigated and described in detail in these chapters.
This book covers a wide range of ceramic and specialty-based electrolytes and
includes useful information for the development of various electrolytes. We truly
believe that this book will be very useful not only for researchers but also for engi-
neers developing next-generation energy storage devices. As the battery industry has
grown so much over the past 10 years, there have been a lot of new people coming
into the battery world from other industries. So, whether you are looking to learn
something about one aspect of energy storage devices to bolster your knowledge or
are entirely new and are looking to learn all about the basics, this book will be an
informative guide to add to your reference collection.

Prof. (Dr.) Rachid Yazami

Draper Prize winner 2014 for the development of LIBs
Editors
Prasanth Raghavan, PhD, is a Professor in the Department
of Polymer Science and Rubber Technology at Cochin
University of Science and Technology (CUSAT), India, and
Visiting Professor in the Department of Materials Engineering
and Convergence Technology at Gyeongsang National
University, Republic of Korea, as well as Associate Faculty at
Inter University Centre for Nanomaterials and Devices
(IUCND), CUSAT, India. He earned his PhD in engineering
in 2009, under the guidance of Prof. Jou-Hyeon Ahn, from the Department of
Chemical and Biological Engineering at Geyongsang National University, Republic
of Korea, under the prestigious Brain Korea (BK21) Fellowship. He completed his
BTech and MTech from CUSAT, India. After a couple of years as a Project Scientist
at the Indian Institute of Technology (IIT-D), New Delhi, he moved abroad for his
PhD studies in 2007. His PhD research was focused on fabrication and investigation
of nanoscale fbrous electrolytes for high performance energy storage devices. He
completed his engineering doctoral degree in less than 3 years, a record that is still
unbroken in the Republic of Korea. After earning his PhD, Dr. Raghavan joined
Nanyang Technological University (NTU), Singapore, as a Research Scientist, in
collaboration with Energy Research Institute at NTU (ERI@N) and Germany’s
Technische Universität München (TUM) CREATE, a joint electromobility research
center between NTU and TUM, where he worked with Prof. (Dr.) Rachid Yazami,
who successfully introduced graphitic carbon as an anode for commercial lithium-
ion batteries and received the Draper Prize, along with Nobel laureates, Prof. (Dr.)
John B. Goodenough and Prof. (Dr.) Akira Yoshino. After four years in Singapore,
Dr. Raghavan worked as a Research Scientist at Rice University, Texas, USA, where
he worked with Prof. Pulickal M. Ajayan, the co-inventor of carbon nanotubes, and
2019 Chemistry Nobel laureate Prof. J. B. Goodenough. Dr. Raghavan was selected
for the Brain Korea Fellowship (2007); SAGE Research Foundation Fellowship,
Brazil (2009); Estonian Science Foundation Fellowship, European Science
Foundation Fellowship (2010); and Faculty Recharge, UGC (2015). He received
many international awards including the Young Scientist Award, Korean
Electrochemical Society (2009), and Bharat Vikas Yuva Ratna Award, (2016). He
has developed many products, such as a high performance breaking parachute for
Indian Defense, fex wheels for space shuttles, high performance lithium-ion batter-
ies for leading portable electronic device and automobile industries, etc. He has a
general research interest in polymer synthesis and processing, nanomaterials, green/
nanocomposites, and electrospinning. His current research focuses on nanoscale
materials and polymer composites for printed and lightweight charge storage solu-
tions, including high temperature supercapacitors and batteries, recycling and waste
management. He has published many research papers in high-impact factor journals

xi
xii Editors

and a number of books/book chapters and has more than 5000 citations and an
h-index of 45 plus. Apart from science and technology, Dr. Raghavan is a poet, social
activist, and a columnist in online portals and printed media.

Jabeen Fatima M. J., PhD, is a Research Scientist at the

Materials Science and NanoEngineering Lab (MSNE Lab) in
the Department of Polymer Science and Rubber Technology
(PSRT) at Cochin University of Science and Technology
(CUSAT), India. Before joining MSNE Lab, she worked as a
guest Assistant Professor in the Department of NanoScience
and Technology at University of Calicut, India. She earned
her PhD in Nanoscience and Technology from the University
of Calicut, India, in 2016, with a prestigious National Fellowship JRF/SRF from
the Council of Scientifc and Industrial Research (CSIR), under the Ministry of
Science and Technology, Government of India. Her research area focuses on syn-
thesis of nanostructures for photoelectrodes for photovoltaic applications, energy
storage devices, photoelectrochemical water splitting, catalysis, etc. She earned her
MS degree in Applied Chemistry (University First Rank) after completing her BSc
degree in Chemistry from Mahatma Gandhi University (MGU), Kottayam, India.
She received many prestigious fellowships, including Junior/Senior Research fellow-
ship (JRF/SRF) from the Centre for Science and Research, Department of Science
and Technology, Ministry of India; Post-doctoral/research scientist fellowship from
Kerala State Council for Science, Technology and Environment (KSCSTE); and
InSc research excellence award. She has published many full-length research arti-
cles in peer-reviewed, international journals and book chapters with international
publishers. She serves as reviewer for many STEM journals published by Wiley
International, Elsevier, Springer Nature, etc. Her current areas of interest include the
development of fexible and free-standing electrodes for printable and stretchable
energy storage solutions and development of novel nanostructured materials and ter-
nary composite electrodes and electrolytes for sustainable energy applications such
as supercapacitors, fuel cells, and lithium-ion batteries.
Contributors
Jou‑Hyeon Ahn Akhila Das
Department of Materials Engineering Department of Polymer Science and
and Convergence Technology Rubber Technology (PSRT)
Gyeongsang National University Cochin University of Science and
Republic of Korea Technology (CUSAT)
Kerala, India
and
Department of Chemical Engineering Raju Kumar Gupta
Gyeongsang National University Department of Chemical Engineering
Republic of Korea Indian Institute of Technology Kanpur
Kanpur, India
Neethu T. M. Balakrishnan
Department of Polymer Science and Jabeen Fatima M. J.
Rubber Technology (PSRT) Department of Polymer Science and
Cochin University of Science and Rubber Technology (PSRT)
Technology (CUSAT) Cochin University of Science and
Kerala, India Technology (CUSAT)
Kerala, India
Bhagyalakhi Baruah
Department of Physics Ashok Kumar
Tezpur University Department of Physics
Tezpur, Assam, India Tezpur University
Tezpur, Assam, India
B. Bhuvaneshwari
Department of Chemical Engineering Hiren K. Machhi
Indian Institute of Technology Kanpur Department of Chemistry
Kanpur, India Sardar Patel University
Vallabh Vidyanagar, Gujarat, India
Sajan Chinnan
Department of Chemistry Nikhil Medhavi
Indian Institute of Science Education Department of Polymer Science and
and Research (IISER) Rubber Technology (PSRT)
Mohali, Punjab, India Cochin University of Science and
Technology (CUSAT)
and Kerala, India
Department of Polymer Science and
Rubber Technology (PSRT)
Cochin University of Science and
Technology (CUSAT)
Kerala, India

xiii
xiv Contributors

Abhijith P. P. Jishnu N. S.
Department of Polymer Science and Rubber Technology Centre
Rubber Technology (PSRT) Indian Institute of Technology (IIT-KGP)
Cochin University of Science and Kharagpur, West Bengal, India
Technology (CUSAT)
and
Kerala, India
Leibniz Institute of Polymer Research
and
Dresden e. V.
Department of Nanoscience and Dresden, Germany
Technology
and
University of Calicut
Kerala, India Department of Polymer Science and
Rubber Technology (PSRT)
Jyoti Prasad Cochin University of Science and
Department of Chemistry Technology (CUSAT)
Sardar Patel University Kerala, India
Vallabh Vidyanagar, Gujarat, India
Saurabh S. Soni
Prasanth Raghavan Department of Chemistry
Department of Polymer Science and Sardar Patel University
Rubber Technology (PSRT) Vallabh Vidyanagar, Gujarat, India
Cochin University of Science and
Technology (CUSAT) Keval K. Sonigara
Kerala, India Department of Chemistry
Sardar Patel University
and
Vallabh Vidyanagar, Gujarat, India
Department of Materials Engineering
and Convergence Technology Anjumole P. Thomas
Gyeongsang National University Department of Polymer Science and
Jinju, South Korea Rubber Technology (PSRT)
Cochin University of Science and
and
Technology (CUSAT)
Department of Materials Science and Kerala, India
Nano Engineering
Rice University Ankit Tyagi
Houston, Texas, USA Department of Chemical Engineering
Indian Institute of Technology Kanpur
Leya Rose Raphael Kanpur, India
Department of Polymer Science and
Rubber Technology (PSRT)
Cochin University of Science and
Technology (CUSAT)
Kerala, India
Abbreviations
[BMI] [BF4] 1-butyl-3-methylimidazolium tetrafuoroborate
[BMI][TFSI] 1-butyl-3-methylimidazolium bis(trifuoromethylsulphonylimide)
[BMIM][Cl] 1-butyl-3-methylimidazolium chloride
[BPy] [TFSI] Butylpyridinium bis(trifouromethylsulphonylimide)
[Py14]FSI 1-butyl-1-methylpyrrolidinium bis(fuorosulfonyl)imide
0D Zero-dimensional
1D One-dimensional
2D Two-dimensional
3D Three-dimensional
3D‑N‑RGO/MnO Three-dimensional nitrogen-doped graphene/MnO
AC Applied current
AFC Alkaline fuel cells
AIMD Ab initio molecular dynamics
Al‑BTC Aluminum benzenetricarboxylate
AN Acrylonitrile
AQ Anthraquinone
ATRP Atom transfer radical polymerization
Au Gold
BDC 1,4-benzenedicarboxylate
BEV Full-battery electric vehicles
BMIMBF4 1-butyl-3-methylimidazolium tetrafuoroborate
BMITFSI 1-Butyl-3-methyl bis(trifuoromethylsulfonyl)imide
BMMIM‑TFSI 1-butyl-2,3-dimethylimidazolium
bis(trifuoromethanesulfonyl)imide
BOB Bis(oxolato)borate
BPEG Triboron-based PEG
BPO Benzoyl peroxide
CA Chronoamperometry
CAB Cellulose acetate butyrate
CAGR Compound annual growth rate
CECRI Central Electro Chemical Research Institute
CH3OH Methanol
CMC Carboxymethylcellulose
CN Cyanide
CNT Carbon nanotube
CO Carbon monoxide
CO2 Carbon dioxide
CP Composite polymer
CPE Composite polymer electrolytes
CR Coin-round
Cu(OH)2 Copper hydroxide

xv
xvi Abbreviations

CuO/Ni Self-supported CuO grown on Ni foam

CV Cyclic voltammetry
DBP Dibutyl phthalate
DC Direct current
DFT Density functional theory
DMC Dimethyl carbonate
DMF Dimethylformamide
DMFC Direct methanol fuel cells
DMP Dimethyl phthalate
DMS Dimethyl sulfte
DOP Dioctyl phthalate
DSC Differential scanning calorimetry
DVIMBr 1,4-di(vinylimidazolium)butane bisbromide
EC Ethylene carbonate
ED Electrodeposition
EDLC Electrochemical double-layer capacitor
EDOT 3,4-ethylene dioxythiophene
EGDMA Ethylene glycol dimethacrylate
EMIMFSI 1-ethyl-3-methylimidazolium bis(fuorosulfonyl)imide
EMIM‑TFSI 1-ethyl-3-methyl imidazolium bis(trifuoromethanesulfonylimide)
EMITf 1-ethyl 3-methy-l-imidazolium trifuoromethanesulfonate
EMI‑TFSA 1-ethyl-3-methylimidazolium bis(trifuoromethylsulfonyl)amide
EMITFSI 1-ethyl-3-methylimidazolium triluoromethanesufonate
ETPTA Trimethylolpropane ethoxylate triacrylate
ePPO Elastomer poly(propylene oxide)
ESR Equivalent series resistance
et al. Et alia
FA Formic acid
FCs Fuel cells
FEC Fluoroethylene carbonate
FePc/N‑GP FePc immobilized on nitrogen-doped electrochemically exfoliated
graphene
FESEM Field emission scanning electron microscopy
FSI Fluorosulphonylamide
FT‑IR Fourier transform infrared spectroscopy
FTO Fluorine doped tin oxide
GCD Galvanostatic charge discharge
GCE Glassy carbon electrode
GDL Gas diffusion layer
GPE Gel polymer electrolytes
h‑BN Hexagonal boron nitride
HCHO Formaldehyde
HCOOH Formic acid
HEA Hydroxyethyl acrylate
HEC Hydroxyethyl cellulose
Abbreviations xvii

HEMA 2-hydroxyethylmethacrylate
HFP Hexafuoropropylene
HIP Hot iso-static pressing
HMPP 2-Hydroxy-2-methylpropiophenone
HQ Hydroquinone
HT High temperature
ICSD Crystal structure database
ILPE Ionic liquid polymer electrolyte
ILs Ionic liquids
IM(2o2)11TFSI 1,2-dimethyl-3-ethoxyethyl imidazolium
bis(trifuoromethanesulfonyl)imide
ITO Indium tin oxide
KOH Potassium hydroxide
LAGP Lithium aluminum germanium phosphate
LATP Lithium aluminum titanium phosphate
LCP Lithium cobalt phosphate
LED Light emitting diode
LFP Lithium iron phosphate
LGPS Li10GeP2S12
Li Lithium
LiBOB Lithium bis oxalate borate
LIBs Lithium ion batteries
LiFSI Lithium bis(fourosulphonyl) imide
Li‑ion Lithium-ion
LiDFOB Lithium difouro oxalate borate
LiPAAOB Lithium polyacrylic acid oxalate borate
LiPON Lithium phosphorous oxynitride
LiPSTFSI Lithium poly[(4-styrenesulfonyl) (trifuoromethanesulfonyl)imide]
LiPVAOB Lithium polyvinyl alcohol oxalate borate
LiRAP Li-rich antiperovskites
LISICON Lithium superionic conductor
LiSnZr(PO4) Li-tin-zirconium phosphate
LiTFSI Lithium bis(trifuoromethanesulfonyl)imide
LLT Lithium lanthanum titanate
LLTaO Lithium lanthanum tantalum oxide
LSV Linear sweep voltammetry
LTC Lithium-thionyl chloride
LTO Lithium titanate
MAH Maleic anhydride
MCFC Molten carbonate fuel cell
MCMB Mesocarbon microbead
MD Molecular dynamics
MEEP Poly[bis-(methoxyethoxyethoxide)phosphazene]
Meso NiPO Mesoporous nickel phosphate
MFC Microbial fuel cell
xviii Abbreviations

MFNC Metal free nanocarbon

MIB Magnesium ion batteries
MIL‑53 1,4-benzenedicarboxylate
MIL‑53(Al) Al, 1,4-benzenedicarboxylate
MMA Methyl methacrylate
MMPIBF4 1-n-propyl-2,3-dimethylimidazolium tetrafuoroborate
MMPIPF6 1-n-propyl-2,3-dimethylimidazolium hexafuorophosphate
MnO2 Manganese dioxide
MnO2/N‑HGSs MnO2 nanoflms directly grown over nitrogen-doped
MnPc Manganese Phthalocyanine
M–Nx Transition metal-nitrogen macrocycle
MOFs Metal organic frameworks
MOR Methanol oxidation reaction
MoS2/P‑ICPC MoS2 encapsulated interconnected porous carbon
MPc Metal phthalocyanine
MPEGA Methoxy-polyethylene glycol acrylate
MPL Microporous layer
MWCNT Multiwalled carbon nanotube
N, S@C Nitrogen and sulphur co-doped honeycomb like porous
N2H4.H2O Hydrazine hydrate
Na‑MMT Na-montmorillonite
NASICON Sodium SuperIonic CONductor
NC Networked cellulose
NCL The National Chemical Laboratory
Ni Nickel
Ni NPs/TNTs/Ti Nickel/TiO2 nanotube modifed on titanium substrate
NiCd Nickel-cadmium
Ni‑Cu‑P/C Ni-P and Ni-Cu-P alloys supported on carbon electrodes
NiMH Nickel–metallic hydride
NiO NS@NW/NF Nickel oxide nanosheet@nanowire arrays modifed on nickel
foam
NiOOH Nickel oxyhydroxide
NMC Lithium nickel manganese cobalt oxide
NMR Nuclear magnetic resonance spectroscopy
NNRs Ni/NiO nanorods
NPs Nanoparticles
NWs Nanowires
O2 Oxygen
OH Hydroxyl
OMMT Organic montmorillonite
ORR Oxygen reduction reaction
P(BMA‑St) Poly(butyl methacrylate-styrene)
P(VC‑co‑VAc) Poly (vinyl chloride-co-vinyl acetate)
P12FSI N-ethyl-N-methylpyrrolidinium bis(fuorosulfonyl)imide
PAFC Phosphoric acid fuel cell
Abbreviations xix

PAN Polyacrylonitrile
PBE Poly(bisphenyl A-co-epichlorohydrin)
PBMA Polybenzyl methacrylate
PC Propylene carbonate
PCF‑HCP Porous carbon framework obtained from N-rich hyper
crosslinked polymer
Pd Palladium
PDADMA Poly(diallyldimethylammonium)
PDAD‑MATFSI Poly[diallyldimethylammonium bis(trifuoromethane)
sulfonimide]
PDMS Poly-dimethyl siloxane
PDMS‑A Poly[dimethylsiloxane-co-(siloxane-g-acrylate)]
PDMS‑P Poly(dimethylsiloxane-co-phenylsiloxane)
PE Polyethene
PEDOT Poly(3,4-ethylenedioxythiophene)
PEDOT:PSS Poly(3,4-ethylenedioxythiophene) polystyrene sulphonate
PEFCs Polymer electrolyte fuel cells
PEG Poly(ethylene glycol)
PEG800 Poly(ethylene glycol)
PEGDA Poly(ethylene glycol) diacrylate
PEGDA‑co‑VC Poly(ethylene glycol) diacrylate-co-vinylene carbonate
PEGDM Poly(ethylene glycol) dimethacrylate
PEGDME Polyethylene glycol dimethyl ether
PEGM Poly(ethylene glycol)methyl ether methacrylate
PEI Polyethylenimine
PEM Proton exchange membrane
PEMFC Proton exchange membrane fuel cell
PEMFCs Polymeric electrolyte membrane fuel cells
PEO Poly(ethylene oxide)
PEO/PVdF Polyethylene oxide/polyvinylidene difouride
PES Poly(oligo[oxyethylene]oxysebacoyl)
PFPE Perfuoropolyether
PFPE‑diol Hydroxy-terminated perfuoropolyether
PHEMO Poly (3-{2-[2-(2-hydroxyethoxy) ethoxy] ethoxy}
methyl-3′- methyloxetane)
PHL PVdF-co-HFP-LSO
PHP PVdF-co-HFP-PPCl
PIL Polymer ionic liquid
PILGE Polymer ionic liquid gel electrolyte
Pip14TFSI 1-butyl-1-methylpiperidinium bis(trifourosulphonyk)imide
PLL PEO-LiTFSI-LLZTO
PLS Polyurethane lithium salt
PMA Polymethyl acrelate
PMMA Polymethyl methacrylate
PNIPAM/AM Poly(N-isopropylacrylamide-co-acrylamide)
xx Abbreviations

PNSE Polymer nanocomposite-based solid-state electrolyte

POEM‑g‑PDMS Poly(oxyethylene) methacrylate-g-poly(dimethyl
siloxane)
POSS Polyhedraloligomeric silsesquioxane
PP Polypropylene
PP13TFSI N-methyl-N-propylpiperidinium
bis(trifuoromethanesulfony)limide
PPC Poly(propylene carbonate)
PPCl 1-methyl-1-propylpiperidinium chloride
PPTA Poly(para phenylene terephthalamide) (PPTA)
PPy Polypyrrole
PS Polystyrene
PS−PEO−PS Polystyrene−poly(ethylene oxide)−polystyrene
Pt Platinum
PTFE Polytetrafouroethylene
PUA Polyurethane acrylate
PVA Poly(vinyl alcohol)
PVAc Polyvinyl acetate
PVA‑β‑CN Cyanoethyl-β-polyvinyl alcohol
PVC Poly(vinyl chloride)
PVdF Polyvinylidene difuoride
PVdF Polyvinylidene fuoride
PVdF‑co‑HFP Poly (vinylidene fuoride)-co-hexafuoro propylene
PVF Polyvinylformal
PVIM‑co‑PPEGMA Poly(N-vinlyimidazole)-co-poly(poly(ethylene glycol)
methyl ether methacrylate
PVIMTFSI‑co‑PPEGMA Poly(N-(1-vinylimidazolium-3-butyl)-ammonium
bis(trifuoro methanesulfonyl)imide)-co-poly(poly
(ethylene glycol) methyl ether methacrylate)
PVP Polyvinylpyrrolidone
PVP‑PEG‑PVP Poly(vinyl pyridine)-PEG-poly(vinyl pyridine)
Py14‑TFSI Lithium bis(trifuoromethane sulphonyl)imide
Py13Br N-methyl-N-propyl pyrrolidinium bromide
Py13TFSI 1-methyl-3-propylpyrrolidinium
bis(trifuoromethanesulfonyl)imide
QSEs Quasi-solid electrolytes
QSSEs Quasi-solid-state electrolytes
RAM Random-access memory
rGO Reduced graphene oxide
Rh Rhodium
RHE Reversible hydrogen electrode
Rh‑NSs/RGO Rh nanosheets-reduced graphene oxide
RT Room temperature
RTILs Room temperature ionic liquids
SC Supercapacitor
SCE Saturated calomel electrode
Abbreviations xxi

SCEs Solid ceramic electrolytes

SCN Succinonitrile
SC‑PMO Porous MnO2 by sonochemical method
SCs Supercapacitors
SEM Scanning electron microscopy
SEs Solid electrolytes
SIBs Sodium ion batteries
SICPN Semi-interpenetrating cross-linked polymer network
SiO2 Silicon dioxide
SiO2PPTFSI 1-methyl-1-propylpiperidinium bis(trifuoromethanesulfonyl)
imide
SLIC Single lithium ion conducting
SN Succinonitrile
Sol Solution
SPE Solid polymer electrolytes
SSBs Solid-state batteries
SSEs Solid state electrolytes
SWCNT Single-wall carbon nanotube
SWCNT@NPC SWCNT embedded in nitrogen and phosphorus co-doped carbon
Ta Tantalum
TBT Tetrabutyl titanate
TEG Tetraethylene glycol
TEGDA‑BA Triethylene glycol diacetate2-propenoic acid butyl ester
TEM Transmission electron microscopy
TFSI Bis(trifuromethanesulfonyl) imide
Tg Glass transition temperature
TGA Thermogravimetric analysis
THF Tetrahydrofuran
Ti NPs/ITO Ti nanoparticle-implanted ITO electrode
TiO2 Titanium dioxide
TMC Transition metal chalcogenides
TMOS Tetramethoxysilane
TMP Trimethyl phosphate
TPU Thermoplastic polyurethane
TSE Transparent solid electrolyte
TSSE Transparent solid state electrolyte
UV Ultraviolet
VC Vinylene carbonate
VIPS 3-(1-vinyl-3-imidazolic) propanesulfonate
vs. Versus
w/w Weight by weight
WCA Water contact angle
wt.% Weight percentage
XRD X-ray diffraction
ZIBs Zinc ion batteries
ϒ‑BL ϒ-Butyrolactone
xxii Abbreviations

SYMBOLS
α Alpha
A Area of the electrode
β Beta
E cell Cell terminal voltage
I Current density
δ Delta
S Deterioration rate
F Faraday constant
γ Gamma
≥ Greater than or equal to
: Is to
≤ Less than or equal to
n Number of electrons transferred
Ω Ohm
Ip Peak current density
∆Ep Peak to peak separation voltage
% Percentage
% Percentage
IF/IR Ratio of forward to backward current
Jf/Jb Ratio of forward to backward current density
® Registered trademark
ν Scan rate
E°anode Standard anode potential
E°cathode Standard cathode potential
ґ* Surface concentration
T Temperature
t Time
R Universal gas constant

UNITS
A g‑1 Ampere per gram
cm Centimeter
o
C Degree celcius/Degree centigrade
F g‑1 Farad per gram
F cm‑3 Faraday per centimetre cube
GHz Gigahertz
GPa Gigapascal
g Gram
h Hour
ions cm‑2 Ions per centimetre square
K Kelvin
keV Kilo electron volts
Abbreviations xxiii

kV Kilo Volt
KW kg‑1 Kilowatt per kilogram
kWh L ‑1 Kilowatt hour per litre
MHz Megahertz
MPa Megapascal
MPa Megapascal
m2g‑1 Meter square per gram
µWh cm‑2 Micro watt hour per centimetre square
µm Micrometer
mA mg‑1 Milliampere per milligram
mAh g‑1 Milliampere hour per gram
mW cm‑2 Milliwatt per centimetre square
mF cm‑2 Millifarad per centimetre square
mS cm‑1 MilliSiemens per centimetre
mA Milliampere
mA h Milliampere hour
mV Millivolt
mV s‑1 Millivolt per second
M Molar
nm Nanometer
% Percentage
S Siemens
S cm‑1 Siemens per centimetre
V Voltage
 1 Solid-State Electrolytes
for Lithium-Ion Batteries
Performance Requirements
and Ion Transportation
Mechanism in Solid
Polymer Electrolytes
Jabeen Fatima M. J., Abhijith P. P.,
Jishnu N. S., Akhila Das, Neethu T.M. Balakrishnan,
Jou-Hyeon Ahn, and Prasanth Raghavan

CONTENTS
1.1 Introduction ......................................................................................................1
1.2 Theory of Polymers in Solid Polymer Electrolytes ..........................................4
1.3 Ionic Conductivity and Ion Transfer Mechanism in Solid Polymer
Electrolytes .......................................................................................................7
1.4 Effect of Polymer Properties on Ionic Conductivity and Ion
Transference Number...................................................................................... 11
1.4.1 Glass Transition Temperature............................................................. 12
1.4.2 Degree of Crystallinity ....................................................................... 12
1.4.3 Crystal Growth from the Melt ............................................................ 13
1.4.4 Crystal Growth from Solution ............................................................ 13
1.5 Conclusion ...................................................................................................... 14
Acknowledgment ..................................................................................................... 14
References................................................................................................................ 14

1.1 INTRODUCTION
Lithium-ion batteries (LIBs) are the most popular among electrochemical energy
storage devices and have a monopoly on powering the electronic gadgets and zero-
emission automobile market due to their relatively high energy density, higher output
voltage, negligible self-discharge, and lack of a memory effect [1–4]. A conven-
tional lithium-ion battery comprises two electrodes, an anode and a cathode, and an

1
2 Ceramic and Specialty Electrolytes

FIGURE 1.1 Schematic representation of the structure and working principle of lithium-ion
batteries including the movement of ions between electrodes during charge (forward arrow)
and discharge (backward arrow) states.

electrolyte system, as shown in Figure 1.1. The electrolyte is one of the key compo-
nents and is known as the heart of the battery, acting as the ion transport pathway
between the positive and negative electrode. The cell capacity, working temperature
range, safety, electrochemical performance, and cyclability of lithium-ion batteries
are enhanced by adopting the electrolyte system. According to their physical state,
electrolytes can be broadly classifed into liquid electrolytes, quasi-solid electrolytes,
gel electrolytes, and solid electrolytes (SEs).
Traditionally, to fabricate LIBs, a lithium salt (e.g., LiPF6, LiClO4, and LiTFSI)
dissolved in carbonate solvent (ethylene carbonate [EC], dimethyl carbonate [DMC],
propylene carbonate [PC], ethyl methyl carbonate [EMC], etc.) is used as the electro-
lyte (organic liquid electrolyte [OLE]). Even though these organic liquid electrolytes
possess high ionic conductivity and a lithium-ion transference number, they suffer
from some inherent drawbacks, such as fammability, leakage, and environmental
toxicity, which hinder their application in electric vehicles (EVs) and airplanes that
need energy storage devices with high energy densities and, more importantly, high
safety [5–8]. In this regard, replacing OLEs with safer solid electrolytes seems to be
a reliable solution for the aforementioned safety issues [9,10]. In comparison with
OLEs, SEs have outstanding advantages in terms of mechanical strength, dimen-
sional stability, thermal stability, and electrochemical stability. Furthermore, SEs
can also act as a separator between the anode and cathode to prevent internal electri-
cal short circuits by preventing the transportation of electrons during the charging
and discharging cycles of the battery, which greatly simplifes the battery fabrication.
Solid-State Electrolytes for Lithium-Ion Batteries 3

Also, thermally and mechanically stable SEs raise the possibility of using lithium-
metal as an anode for high energy density LIBs [11,12], called lithium-ion metal bat-
teries. In LIBs, to attain a high and reversible specifc energy from a lithium-metal
polymer battery (LMPB), the repetitive deposition and stripping of lithium must
remain highly reversible during the electrochemical process. The cycling of lithium-
metal is known to result in the deposition of lithium dendrites that can decrease the
life cycle of the cell and cause safety concerns. It was reported that the use of solid
electrolytes can suppress dendrite growth and improve plating morphology [13].
SEs generally have no practical use in room temperature applications due to their
low ionic conductivity and a lithium transference number below 50°C. However, the
Bolloré Company has attempted to commercialize SE-based lithium-ion batteries,
and Cui’s group at the Qingdao Institute of Bioenergy and Bioprocess Technology
has proposed a new generation of solid polymer electrolytes (SPEs) in recent years.
The major advantages of SEs in LIBs can be bulleted as follows [14–17]:

• The safety of LIBs has been greatly improved due to the absence of an
organic liquid electrolyte which has low vapor pressure and boiling point.
• The high thermal stability of SEs simplifes the casing module and cooling
system, which can reduce the weight of the battery, thereby increasing the
energy density, lowering the production cost, saving space, and simplifying
the battery fabrication.
• A plurality of electrodes can be stacked in a series as a single unit due to the
solid-state characteristics and dimensional stability of SEs, which makes
it possible to fabricate batteries with a high output voltage as a single unit
rather than stacking a number of batteries as a module.
• The wide electrochemical window (≥5 V) of SEs due to the absence of an
organic solvent makes it possible to use high-voltage electrode materials,
thereby improving the operating voltage and compacting the battery espe-
cially for powering electric vehicles.
• SEs can compensate for the volume changes of electrodes by elastic and
plastic deformation during the continuous charge and discharge cycling.
• The manufacturing and material costs of LIBs can be signifcantly reduced
by replacing the liquid electrolyte with SEs (the fabrication cost of polymer
electrolytes (PEs) is much lower than that of conventional liquid electro-
lyte-Celgard® separator systems); the use of positive temperature coeff-
cient resistors, fuses, and solid packages with superior mechanical strength
is not required (the volume expansion of the battery with temperature is
much lower due to the absence of organic solvents having lower melting
and boiling points, which in turn reduces the internal pressure of the bat-
tery build-up by the vaporization of the carbonate solvents) in SE-based
LIBs, which leads to high temperature tolerance and dimensional stability,
thereby saving on production costs.

Based on the matrix used for the preparation of SEs, they are classifed as ceramic
(inorganic solid electrolytes) and organic (solid polymer electrolytes). Inorganic
4 Ceramic and Specialty Electrolytes

solid electrolytes (such as a sodium superionic conductor [NASICON] Li–Al–Ti–

PO4) possess high ionic conductivity (can reach more than 10 –4 S cm –1 at 25°C) and
a Li+ transference number at room temperature [18,19], but they show large grain
boundary resistance, poor interface compatibility between an inorganic solid elec-
trolyte and an electrode, a relatively cumbersome fabrication process, and a large
energy barrier for lithium-ion electrolyte migration at the electrode interface. These
features cause a series of problems, especially the growth of lithium dendrites dur-
ing the charging–discharging process and an inferior plating morphology [20–22].
Moreover, inorganic solid electrolytes are too hard and brittle for fexible battery
applications and have poor processability. Recently, a number of inorganic oxide
electrolytes have been investigated, such as NASICON-type phosphates [23], garnet
oxides Li xLa3M2O12 (M = Ta, Nb, Zr) [24], and perovskite-type Li3xLa2/3–x1/3–2xTiO3
[25]. Sulfde electrolytes Li10GeP2S12 [26] and Li2S-P2S5 [25] glass-ceramics with
unprecedented conductivities of 1.2 × 10 –2 and 3.2 × 10 –3 S cm–1, respectively, have
been reported. Unfortunately, they have low thermodynamic stability, can be easily
reduced by lithium-metal, and are oxidized by high-voltage active cathode materi-
als. Also, these sulfdes produce toxic H2S on contact with moisture. In contrast with
inorganic solid electrolytes, organic solid electrolytes, commonly known as solid
polymer electrolytes, exhibit excellent interfacial compatibility with both electrodes
and favorable mechanical properties. In addition, the energy density of LIBs can
be greatly improved by using SPEs which have a much lower density than that of
inorganic solid electrolytes [27,28]. Also, they have excellent processibility, excep-
tional toughness, and are lightweight and fexible. Solid polymer electrolytes are
categorized as dry solid polymer electrolytes, rubbery electrolytes, and single-ion
conducting polymer electrolytes. This chapter systematically discusses the perfor-
mance requirements and ion transfer mechanisms of SPEs, the theory of polymers
in solid polymer electrolytes, lithium-ion conducting materials in the preparation of
SPEs, and the unique class of SPEs called single-ion conductors.

1.2 THEORY OF POLYMERS IN SOLID POLYMER ELECTROLYTES

In a lithium-ion battery, the polymer electrolyte is sandwiched between the anode
(lithium-metal, carbon, lithium titanate [LTO], etc.) and the composite cathode
(LiFePO4, LiMnO4, LiCoO2, etc.), acting as an electrolyte cum separator, which
plays a crucial role in the electrochemical performance of lithium-ion batteries.
Typically, SPEs are prepared by mixing or dissolving lithium salts in a high molecu-
lar weight polymer matrix such as polyethylene oxide (PEO), polyvinylidene difu-
oride (PVdF), or its co-polymer polyvinylidene fuoride-co-hexafuoropropylene
(PVdF-co-HFP), polyacrylonitrile (PAN), etc. The polymer acts as the host matrix
for the transmission of lithium-ions and the mechanical substrate to separate the
electrode. The performance of SPEs greatly depends on the selection of materials
such as the polymeric matrix, ion-conducting promoters, type of lithium salts, etc.
The dielectric properties, the functional group present in the monomer unit of the
polymer, the glass transition temperature, the degree of crystallinity, the affnity of
the polymer to the lithium salt, etc., signifcantly infuence the electrolyte properties
Solid-State Electrolytes for Lithium-Ion Batteries 5

and thus the battery performance. For practical application, a polymer electrolyte
for lithium-ion batteries should inherently possess the following properties [29,30]:

• High ionic conductivity: It should be a good ionic conductor (≥10 –3 S cm–1

at room temperature) and electronic insulator, facilitating lithium-ion trans-
port between the electrodes during the charge–discharge cycle, minimiz-
ing self-discharge, and avoiding an internal short circuit. Ionic conductivity
signifcantly affects the internal impedance and electrochemical behavior
of the battery, especially at higher C-rates [31].
• Dissolution ability: For solid polymer electrolytes, the host polymer matrix
should have the ability to dissolve or manufacture complexes with lithium-
ions. Certain polymers such as PEO, PVdF, and PAN have polar functional
groups, which facilitate easy dissociation of lithium salts, thereby improv-
ing the ionic transportation and producing a host polymer with a relatively
high dielectric constant [29]. A series of polymers have sequential polar
groups such as the ether group (–O–), the ester group (=O), the carbonyl
group (C=O), the fuoride group (–F), the thiol group (—S—), the nitrogen
in the imide group (—NH—), and the acrylonitrile group (C≡N) to dis-
solve/dissociate lithium salts and form polymer–salt complexes.
• High lithium‑ion transference number: Ideally, the Li+-ion transference
number should be close to unity in any electrolyte system. Restricting the
mobility of anions in an electrolyte can greatly increase the Li+-ion trans-
ference number. To reduce the mobility of anions, two main approaches
have been reported: (i) anchoring the anions by means of physical or chemi-
cal bonds to the backbone of the polymer chain (common method to pre-
pare single-ion conducting polymer electrolytes); and (ii) introducing anion
receptors [32,33] such as tri(methyl)borate (1), tris(tri-fuoromethyl)borate
(2), tris(hepta-fuorobutyl)borate (3), tris(hexa-fuoroisopropyl)borate (4),
tris(perfuoro-tert-butyl)borate (5), tris(triphenyl)borate (6), tris(hexa-fuo-
rocumyl)borate (7), tris(penta-fuorophenyl) borate (8), and tris(penta-fuo-
rophenyl)borane (TPFPB; 9) (Figure 1.2), which could selectively complex
with anions in electrolytes [34,35]. A large Li+-ion transference number can
reduce the concentration polarization of electrolytes during the charge/dis-
charge process, thereby producing a higher power density [36].
• Wide electrochemical stability window: The electrochemical window
of an electrolyte is defned as the voltage range in which the materials in
the electrolyte are neither oxidized nor reduced. In other words, it is the
difference in voltage between the potentials of the oxidation and reduc-
tion reaction. Hence, the polymer matrix, lithium salts, and any additives
used in the battery electrolyte should have an oxidation potential higher
than the embedding potential of a Li+-ion in the composite cathode and
a lower reduction potential than that of lithium-metal or graphitic carbon
in the anode. Typically, all polymer electrolytes have an electrochemical
window of ≥4 V vs. Li/Li+ which is suffcient for even high-voltage battery
electrodes.
6 Ceramic and Specialty Electrolytes

FIGURE 1.2 Structures of various trialkyl/triaryl borates and TPFPB anion receptors.
Adapted and reproduced with permission from Reference [32]. Copyright 2000 Elsevier.

• Good compatibility and adhesion with battery electrodes: Ideally, the

battery electrolyte should be chemically inert to both electrodes and should
have good compatibility with the electrodes. This is very important for a
good interface between the electrodes which, in turn, signifcantly contrib-
utes to the electrochemical performance and rate capability of the battery.
An electrolyte that has good compatibility with an electrode can form a
good interface with the electrode, thereby reducing the interfacial resis-
tance and facilitating a higher rate of charge–discharge cycling stability to
the battery.
• Excellent chemical and thermal stability: The battery electrolytes should
be inert to any battery components such as electrodes, current collectors,
battery additives if any, and cell packaging materials, which could mini-
mize dendrite formation and avoid any unwanted chemical reactions or
corrosion. Also, the electrolytes should have excellent thermal stability,
which ensures the safe operation of lithium-ion batteries even at tempera-
tures above room temperature, and avoids electrical (shorting, overcharge)
as well as a thermal runaway or battery explosion. This is easily achieved
by the selection of thermally stable or fame-retardant polymers with a
Solid-State Electrolytes for Lithium-Ion Batteries 7

high dielectric constant such as PVdF, PVdF-co-HFP, PAN, etc., as the host
matrix for SPEs.
• Good mechanical strength and dimensional stability: The mechanical
strength and dimensional stability of a polymer electrolyte are two of the
most important factors in the design of solid polymer electrolytes for large-
scale manufacture of lithium-ion batteries. Polymer electrolytes are not
hard or brittle like inorganic or glass-ceramic solid electrolytes, and have
excellent dimensional stability. Because of their viscoelastic properties and
semi-crystalline nature, solid polymer electrolytes are able to elastically
relax when stress arises during the manufacturing process, cell assem-
bly, packaging, storage, and use. Some feasible approaches to improve the
mechanical and dimensional stability of SPEs are incorporating inorganic
micro-nano-sized fllers [37], chemical cross-linking of the polymer to
make 3D network structures [38], and sandwiching between the mechani-
cally strong polymeric layers [30,39] physically supported by polyolefn
membrane.
• Sustainability: The materials used in the fabrication of solid polymer elec-
trolytes should be abundant with a low impact synthesis. Also, the con-
stituent materials should be environmentally friendly or have a negligible
impact on pollution or environmental hazards.

1.3 IONIC CONDUCTIVITY AND ION TRANSFER

MECHANISM IN SOLID POLYMER ELECTROLYTES
Typically in SPEs, the Li+-ions are dissolved in a polymer matrix and Li+-ion trans-
port occurs only in the amorphous phase of the polymer above their glass transition
temperature where polymer chain motion creates a dynamic, disordered environ-
ment that plays a critical role in facilitating ion transport [40–44]. However, in SPEs
with high lithium-ion conductivity, the polymer not only dissolves the lithium salt,
but it is also able to couple with lithium-ions. Hence, the local relaxation and seg-
mental motion of amorphous regions within the polymer chain at or above the glass
transition temperature (Tg) plays a signifcant role in the ionic conductivity of SPEs
[40,45]. In addition, the number of free Li+-cations also signifcantly affects the Li+-
transportability within the SPE. Hence, ionic conductivity of SPEs is greatly infu-
enced by the effective number of mobile ions (free ions), the elementary electric
charge, and the ion mobility. The effective number of mobile ions greatly depends on
the degree of salt dissociation in the polymer host, which is signifcantly affected by
the chemical nature of the host polymer matrix. As previously mentioned, the polar
groups in the polymer, such as –O–, =O, C=O), –F, —S—, C≡N, —NH—, etc., are
effective building blocks for dissolving and dissociating lithium salts. In polyethyl-
ene oxide, for example, the lone pair of oxygens (ether linkages) on the PEO segment
is coordinated with the lithium-ion by Coulombic interaction, helping to improve
the segmental motion and the dissociation of lithium salts into the respective anion
and cation. In the process, PEO acts as a solvent, and the lithium salt dissolves into
8 Ceramic and Specialty Electrolytes

the PEO matrix. Similarly, other atoms such as =O, —C=O, –F, —S—, —NH—,
—C≡N also play a similar role. Hence, Li+-ions are located at suitable coordina-
tion sites (e.g., –O– in polyethylene oxide, –F in PVdF or PVdF-co-HFP, —C≡N in
PAN, and –NR in polyamide) in the polar chains of the polymer. The polymer chains
undergo constant local segmental motion, which results in the appearance of free
volumes [46,47]. The challenges and perspectives of lithium-ion transport in a solid-
state electrolyte [48] are depicted in Figure 1.3. In SPEs, under the electric feld,
the migration movement of Li+-cations is from one coordination point to another
along the polymer segment, or they jump from one segment to another through these
free volumes. Hence, the mechanism of ion motion may involve the formation of
time-dependent pathways in the polymer matrix, the short-range transport of ions
temporarily attached to the polymer chain, and ion hopping between an ionic cluster
or coordination center. The Li+-ion transport mechanism of solid polymer electro-
lytes based on PEO [46,47] is shown in Figure 1.4. In 2001, this concept of ionic
conduction in SPEs was overturned by Bruce et al. [49]. In their study, they showed
that the ionic conductivity (Li+-ion conductivity) in the static, ordered environment
of the crystalline phase can be greater than that in the equivalent amorphous mate-
rial above Tg. The study also demonstrated that ion transport in crystalline polymer
electrolytes can be dominated by cations, whereas both ions are generally mobile in
the amorphous phase [50].
Based on experimental studies of ionic conductivity in PEO-based crystalline
complexes formed with six ether oxygens per cation, Stoeva et al. [51] proposed that
in the crystalline phase of P(EO)6:LiX (X = PF6, AsF6, SbF6, all these compounds are
iso-structural), pairs of PEO chains fold to form cylindrical tunnels, within which
the Li+ cations are located and coordinated with ether oxygens, while the anions are
located outside these tunnels in the inter-chain space and do not coordinate with cat-
ions. The structure of a PEO6:LiAsF6 crystalline complex suggests that Li+-ion trans-
port along the tunnels may be possible in the crystalline 6:1 complex. These Li+-ions

FIGURE 1.3 Challenges and perspectives of lithium-ion transport in a solid-state electrolyte.

Solid-State Electrolytes for Lithium-Ion Batteries 9

FIGURE 1.4 Schematic illustration of the lithium-ion transport mechanism in polyethylene

oxide (PEO)-based solid polymer electrolytes.

can migrate from one site to another along these cylindrical tunnels without the aid
of segmental motion [51]. To compare ionic conductivity in the static, ordered envi-
ronment of a crystalline polymer electrolyte with the dynamic and disordered envi-
ronment of an amorphous polymer electrolyte above Tg, Stoeva et al. [51] prepared
crystalline and amorphous forms of PEO6:LiSbF6. The variation in ionic conduc-
tivity as a function of temperature for the crystalline and amorphous PEO6:LiSbF6
materials is shown in Figure 1.5. A temperature-dependent ionic conductivity study
shows that the ionic conductivity in crystalline PEO6:LiSbF6 is higher than for the
same composition in the amorphous state, even above Tg [51]. The crystalline phase
reaches conductivity more than one order of magnitude higher than the amorphous
phase at the lowest temperatures. Nuclear magnetic resonance (NMR) studies on
these electrolytes demonstrated that PF6 ions do not move with respect to polymer
chains, indicating that the ionic conductivity is dominated by Li+-ions; that is, the
cation transport number TLi+ = 1.
Generally, ion transport in solids involves ions hopping between adjacent sites. In
the conventional view of ionic conductivity in polymer electrolytes, ions move in a
dynamic environment created by the polymer chain motion in the amorphous phase
above Tg. A crankshaft-like motion associated with short segments of the polymer
chains randomly creates suitable coordination sites adjacent to the ions, so that these
ions may hop from one site to another. Such segmental modes, involving the motion
of groups of atoms on the polymer chains, are usually relatively slow, limiting the
hopping rate and therefore the maximum conductivity.
By considering the ionic conductivity in crystalline ceramic materials such as
NaßAl2O3, RbAg4I5, the lithium superionic conductor (LISICONs) (Li14Zn(GeO4)4)
[52,53], or Li0.5La0.5TiO3 [54], it can also be claimed that ion transport is favored in
crystalline polymer electrolytes. Some of these crystalline ceramic materials display
the highest known ionic conductivities in the solid state, exceeding by 1–3 orders of
magnitude the maximum conductivity of conventional amorphous polymer electro-
lytes. For instance, RbAg4I5 has a conductivity of over 10 –1 S cm–1, and Li0.5La0.5TiO3
10 Ceramic and Specialty Electrolytes

FIGURE 1.5 Ionic conductivity (S cm–1) of amorphous (open circles) and crystalline (flled
circles) PEO6:LiSbF6 as a function of temperature. Adapted and reproduced with permission
from Reference [51]. Copyright 2003 American Chemical Society.

achieves 10 –3 S cm–1 [53,54] at room temperature. High ionic conductivity can also be
obtained in plastic crystals where ion transport is aided by rotational disorder [55]. In
their later studies [56–58], Bruce et al. [49] proposed that modifying these stoichio-
metric crystalline complexes by replacing a few mol.% of XF6 ions with monovalent
ions having very different shapes and sizes such as N(SO2CF3)2 or anions with dif-
ferent charges such as SiF62– can increase the ionic conductivity by 1.5–2 orders of
magnitude. However, the opposite results were reported by Henderson et al. after
examining the ionic conductivity of the same crystalline SPEs, P(EO)6 –LiX (X =
PF6, AsF6, SbF6) [59,60]. Sun et al. [61] have also reported comparable ionic con-
ductivities in amorphous and crystalline di-block copolymers. Even though a large
number of studies have reported on the ion transfer mechanism in solid polymer
electrolytes, more systematic microscopic studies on ionic conductivity as a function
of temperature (temperature-dependent ionic conductivity) would provide more clear
information on the ion transfer mechanism. Hence, a comprehensive description of
lithium-ion transportation in SPEs is challenging because the systems are compli-
cated and no simple structural–property correlation has yet been derived.
A good understanding of conducting mechanisms is necessary for the design of
solid polymer electrolytes with practical application in lithium-ion batteries. Solid
Solid-State Electrolytes for Lithium-Ion Batteries 11

polymer electrolytes are a complex system that contains materials with multiple con-
ducting species that make a more complex conduction mechanism. As per the equa-
tion, σ = F ∑Ni RiEi (where F, Ni, Ri, and Ei are the Faraday constant, the number
of charge carriers, the ionic charge of the charge carriers, and the ionic mobility,
respectively), the conductivity (σ) of such a complex system is primarily governed by
two parameters: (i) the number of charge carriers and (ii) the mobility of the charge
carriers.
The temperature-dependent ionic conductivity of the SPE system often fol-
lows two dominant conduction mechanisms: (i) the Arrhenius type or the Vogel–
Tammann–Fulcher (VTF) type [29,62,63]. The VTF equation was devised early in
the 20th century for describing the diffusion process in glassy and disordered mate-
rials [60] from quasi-thermodynamic models with free volume and confgurational
entropy, and its behavior can be related to ion motion coupled with the long-range
motions of the polymer segments. In general, for a polymer electrolyte, the log σ vs.
1/T curves are typically nonlinear or slightly curved, so the activation energy for the
ionic conduction Ea can be obtained using the Vogel–Tammann–Fulcher model {σ =
σ0T1/2 exp[Ea /R(T – T0)]} instead of the simple Arrhenius model (σ = σ0 exp(Ea /RT))
used for the treatment of linear Arrhenius plots. This indicates that the conduction
mechanism not only involves the increasing dissociation of lithium salt and the low-
ering of ionic coupling but also an ionic hopping motion coupled with relaxation/
breathing and/or the segmental motion of polymeric chains [64–67]. Here, σ0 is the
pre-exponential factor, which is related to the number of charge carriers Ni; Ea is
the activation energy for the ionic conductivity which can be calculated from the
nonlinear least-squares ftting of the data from plots of log σ vs. 1/T; and T0 is the
equilibrium glass transition temperature (T0 ᴝ Tg – 50 K). The materials that obey the
linear Arrhenius equation indicate that ion transport occurs in such materials via a
simple hopping mechanism decoupled from relaxation, breathing, and the segmental
motion of polymeric chains [62]. Based on ionic conductivity studies of PEO and
polyphenylene oxide (PPO) salt complexes, the ionic conductivity can be related to
frequency and temperature using the William–Landel–Ferry (WLF) equation, con-
sidering the relaxation process of polymer molecular chain motion in an amorphous
system. The expression is

log s (T ) / s (Tg ) = C1 ( T - Tg ) / C2 + ( T - Tg )

Here, s (Tg ) is the conductivity of the relevant ions at glass transition temperature Tg,
and C1 and C2 are the WLF parameters in the free volume equation of ion migra-
tion, respectively.

1.4 EFFECT OF POLYMER PROPERTIES ON IONIC

CONDUCTIVITY AND ION TRANSFERENCE NUMBER
The physical and electrochemical properties of solid polymer electrolytes are signif-
cantly infuenced by the physicochemical properties of the host matrix. The polarity
and dielectric constant of the polymers positively contribute to the dissociation of
12 Ceramic and Specialty Electrolytes

lithium salts, the Li+-ion transport number, and ionic conductivity. The presence of
certain functional groups, the glass transition temperature, crystallinity, microstruc-
ture, polymer type such as homopolymer or copolymer, constituent polymers (in the
case of polymer blends), molecular weight, etc., greatly infuence the ionic conduc-
tivity, the transportation mechanism, the transference number, the electrochemical
performance, and the rate capability of SPEs. The effect of the functional group
present in a polymer chain was discussed in Section 1.2, hence this section discusses
the effect of the other two important properties of polymers on ionic conductivity
viz. the glass transition temperature (Tg) and the crystallinity of the polymers.

1.4.1 GLASS TRANSITION TEMPERATURE

The glass transition temperature (Tg) is one of the most important properties of poly-
mers. It is the temperature at which the chain segments start to move while the
molecular chains remain static. Below their Tg, only vibrations of molecule atoms
or groups exist in their respective equilibrium positions. Below Tg, the polymers are
rigid and brittle, and the molecules have very little mobility. At Tg, a dramatic change
occurs in the physical properties of the polymer host, including the density, specifc
heat, mechanical modulus, mechanical energy absorption, dielectric and acoustical
equivalents, and rate of gas or liquid diffusion through the polymer. Generally, Tg
can be determined by differential scanning calorimetry (DSC) measurements. The
polymer structure, crystallinity, molecular weight, thermal history, and pressure are
considered to infuence Tg.
Generally, lowering the Tg can enhance the segmental mobility of the polymer
chains, which is the simplest and most effcient way to improve the ionic conduc-
tivity. Above Tg, the ions can move in the space provided by the free volume of the
polymer host and migrate from one coordination site to a new site along the chains.
Alternatively, the ions can hop from one chain to another under the effect of an elec-
tric feld. Because Li+-ion conductivity in SPEs at room temperature is low, strategies
have been developed to lower the Tg and enhance the conductivity. In particular, the
use of branched chains with lower Tg values compared to the host polymer chain and
the addition of nano-additives are effective approaches to improve the ion transport
capability of SPEs.

1.4.2 DEGREE OF CRYSTALLINITY

Crystallinity is the degree of long-range order in a material and has a signifcant
impact on the material properties. The crystallization of polymers is a process
associated with the partial alignment of their molecular chains. Polymers can crys-
tallize upon cooling from the melt or solvent evaporation, corresponding to the
different flming technologies used to fabricate polymer electrolytes. The proper-
ties of polymers are determined not only by the degree of crystallinity but also by
the size and orientation of the molecular chains. The degree of crystallinity can be
estimated by different analytical methods including density measurements, DSC,
Solid-State Electrolytes for Lithium-Ion Batteries 13

X-ray diffraction (XRD), infrared spectroscopy, and nuclear magnetic resonance.

In addition, the distribution of crystalline and amorphous regions can be visualized
with microscopic techniques, such as polarized light microscopy and transmission
electron microscopy [25].
The crystallization process involves nucleation and crystal growth. Nucleation
starts with small, nanometer-sized areas where some chains or their segments align.
These nucleation seeds can either dissociate or grow further depending on the
conditions. Apart from the thermal mechanism, nucleation is strongly affected by
impurities, plasticizers, fllers, and other additives in the polymer. For this reason,
crystallinity can be reduced by the addition of inorganic particles or plasticizers into
the polymer matrix. SPE membranes are generally manufactured using the solvent
casting method or a hot-press flming method, and the crystal growth is different
between the melt and the solution.

1.4.3 CRYSTAL GROWTH FROM THE MELT

Crystal growth only occurs at temperatures below the melting temperature (Tm) and
above Tg. Higher temperatures destroy the molecular arrangement and, below Tg, the
movement of molecular chains is frozen. Nevertheless, secondary crystallization can
proceed even below Tg on a timescale of months to years. The growth of the crystal-
line regions preferably occurs in the direction of the largest temperature gradient
and is suppressed at the top and bottom of the crystalline lamellae by the amor-
phous folded parts at those surfaces. In the case of a strong temperature gradient,
the growth has a unidirectional, dendritic character. In the preparation process, the
working temperature (melt and post-processing temperature), retention time, pres-
sure used in the hot-press method, material composition, and concentration greatly
affect the percentage crystallinity of the SEs.

1.4.4 CRYSTAL GROWTH FROM SOLUTION

Polymers can also be crystallized from a solution or upon the evaporation of a sol-
vent. This process depends on the degree of dilution; that is, in dilute solutions, the
molecular chains have no connection with each other and exist as separate polymer
coils in the solution. Increasing the concentration, which can occur via solvent evap-
oration, induces interactions between the molecular chains and, possibly, crystalliza-
tion, as in crystallization from a melt. The crystallinity can be controlled by several
factors such as the concentration, solvent, additives, composition, solvent volatiliza-
tion speed, and temperature. Above all, the degree of crystallinity determines the
mechanical and thermal properties, as well as the ionic conductivity, of the poly-
mer. High crystallinity, which reduces ion transportation, decreases the free volume
of the crystal because of the more compact packing of parallel polymer chains. In
conclusion, favorable ionic conductivity can be obtained by lowering the degree of
crystallinity by adding additives such as plasticizers, nanofllers, low crystalline or
amorphous polymer, and grafted polymers.
14 Ceramic and Specialty Electrolytes

1.5 CONCLUSION
Polymer electrolytes are promising candidates for next-generation energy storage
devices. The current generation relies on electronic gadgets that are powered using
energy storage devices. Among these energy storage devices, lithium-ion batteries
have a key role owing to their enhanced energy density. In the current era, society
is being mobilized by lithium-ion batteries, from health trackers to electric vehicles.
As a major energy storage device used in our day-to-day life, the safety of lith-
ium-ion batteries is of primary concern, hence major research interest is focused on
electrolytes. Gel polymer electrolytes overcome the demerits of conventional liquid
electrolytes. The ionic conductivity of the liquid electrolyte is high but safety issues
have been raised due to development of thermal energy inside the LIBs during the
continuous charge-discharge cycling, the battery lead to fring. The use of polymeric
electrolytes overcomes these issues but conductivity is decreased. The improvement
in properties such as ionic conductivity, glass transition temperature, and degree of
crystallinity will enhance the performance of electrolytes for effcient energy storage
devices.

ACKNOWLEDGMENT
Dr. M.J. Jabeen Fatima and Dr. Prasanth Raghavan would like to acknowledge the
Kerala State Council for Science, Technology and Environment (KSCSTE), Kerala,
for fnancial assistance.

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 2 Solid-State Electrolytes
for Lithium-Ion Batteries
Novel Lithium-Ion
Conducting Ceramic
Materials: Oxides
(Perovskite, Anti-Perovskite)
and Sulfde-Type
Ion Conductors
Prasanth Raghavan, Abhijith P. P., Jishnu N. S.,
Neethu T. M. Balakrishnan, Akhila Das,
Jabeen Fatima M. J., and Jou-Hyeon Ahn

CONTENTS
2.1 Introduction ....................................................................................................20
2.2 Oxide-Type Lithium-Ion Conductors.............................................................. 23
2.2.1 Perovskite Conductors ........................................................................ 23
2.2.2 Anti-Perovskite Conductors................................................................26
2.3 Sulfde-Type Lithium-Ion Conductors ............................................................ 30
2.3.1 LISICON and Thio-LISICONs........................................................... 30
2.3.2 LGPS Family ......................................................................................34
2.3.3 Argyrodites ......................................................................................... 36
2.3.4 Other New Thio-Phosphates............................................................... 38
2.3.5 Layered Sulfdes ................................................................................. 41
2.4 Conclusion ...................................................................................................... 43
Acknowledgment .....................................................................................................44
References................................................................................................................44

19
20 Ceramic and Specialty Electrolytes

2.1 INTRODUCTION
Portable energy storage devices have had a profound impact on the development of
automobiles and electronics which infuences all aspects of day-to-day life. The most
convenient form of energy storage is portable chemical energy such as batteries and
supercapacitors. Among the different sources, fossil fuel has become the dominant
chemical energy source due to its ease of storage, access, and transport. However,
there are serious environmental issues associated with the use of fossil fuels. It is
a well-known fact that carbon dioxide, which is the gas released when fossil fuels
are burned, is one of the primary gases responsible for global warming. Such gases
cause a rise in the earth’s temperature to the point that polar ice caps are melting,
low-lying lands are fooding, and sea levels are increasing which threatens the exis-
tence of many animals and plants including mankind. Fossil fuels are a non-renew-
able energy source and are being extracted at an exorbitant rate to meet demand. It
is estimated that fossil fuels will be extinct within the next 30–40 years, hence a
steep hike in fuel costs is expected in the near future. In this scenario, if an effective
alternate to oil is not found or automobiles do not switch from gasoline engines to
electrically powered engines, we will no longer be able to drive cars. To make such a
switch, it is necessary to have better energy conversion and storage devices. Among
the different energy storage devices, rechargeable batteries are the most promis-
ing as they are capable of effciently storing energy from renewable sources. On a
fundamental level, the battery cell is composed of three integral components: the
anode, the cathode, and the electrolyte/ionic conductor. The major components and
structure of a battery are shown in Figure 2.1.

FIGURE 2.1 Schematic representation of the structure and working principle of lithium-ion
batteries including the movement of ions between electrodes during charge (forward arrow)
and discharge (backward arrow) states.
Solid-State Electrolytes for Lithium-Ion Batteries 21

Recently, battery research has advanced at a rapid pace, especially in improv-

ing safety. Today’s portable batteries meet the demands of most portable applica-
tions, but a better battery is required for applications such as electric vehicles (EVs).
Lithium-ion batteries (LIBs) or lithium-metal batteries are being scrutinized as the
most promising electrical energy storage device for electric/hybrid vehicles, and hold
great promise for future transportation. The most important property for a battery
module powering an electric vehicle is thermal stability. Such heavy-duty batteries
should be safe to operate over a wide range of temperatures, where the electrolyte
plays a key role. Hence, in general, an electrolyte is specifcally designed for a par-
ticular battery application. Different types of electrolytes such as organic liquid elec-
trolytes, ionic liquid (room temperature ionic liquids [RTILs]) electrolytes, inorganic
liquid electrolytes, organic solid electrolytes (solid polymer electrolytes [SPEs]), and
inorganic solid electrolytes are used in lithium-ion batteries.
Inorganic solid-state Li-ion conducting materials have been considered for
Li-based electrolytes because they have a wide electrochemical window (0–5 V) and
are thermally stable and electronically/electrically insulating; however, their Li-ion
conductivity is not as good as organic liquid electrolytes or organic solid electrolytes.
Because of their inferior room temperature lithium-ion conductivity, inorganic solid-
state electrolytes have been excluded from large-scale battery applications and their
practical applications in thin-flm batteries are limited.
The state-of-the-art electrolyte used in lithium-ion batteries is the organic liq-
uid electrolyte, which is simply a solution of a suitable lithium salt (LiPF6, lithium
bis(trifuoromethanesulfonyl)imide [LiTFSI], LiClO4, etc.) in an aprotic solvent (eth-
ylene carbonate [EC], dimethyl carbonate [DMC], propylene carbonate [PC], ethyl
methyl carbonate [EMC], etc.). These liquid electrolytes show good conductivity (in
the order of 10 –2 to 10 –3 S cm–1 at room temperature); however, they suffer from elec-
trochemical stability issues due to the narrow electrochemical window, and thermal
stability issues due to their low fashpoint below 30°C. Electrolyte leakage, inferior
cycling stability, rate capability, growth of dendrites, and associated thermal runway
are some of the other concerns related to organic liquid electrolytes. Accordingly, the
development of an electrolyte with a wider electrochemical window and improved
thermal safety properties has become one of the most promising avenues for improv-
ing the safety and electrochemical properties of Li-ion batteries. Also, the all-solid-
state battery, comprising only solid-state electrolytes, provides good safety in
heavy-duty lithium-ion batteries and lithium-metal batteries in electric vehicles and
stationary power sources. Also, solid electrolytes with suffcient stiffness can sup-
press the growth of lithium-metal dendrites during cycling [1]. Hence, lithium-ion
conducting inorganic solid electrolytes are a promising candidate for the fabrication
of all-solid-state batteries; however, even though they have a wide electrochemical
window (>5 V) and excellent safety and shelf life, most solid-state electrolytes suffer
from low room temperature ionic conductivity which prevents them from being used
in practical applications.
In recent years, inorganic solid electrolytes have shown improved performance.
A large number of novel solid-state electrolyte lithium-ion conducting ceramic and
glass-ceramic materials have been developed with Li-ion conductivity comparable
22 Ceramic and Specialty Electrolytes

and even exceeding organic liquid electrolytes. Figure 2.2 shows the ionic con-
ductivity of different inorganic solid-state electrolytes in comparison with organic
liquid electrolytes, solid polymer electrolytes, ionic liquids, and gel polymer elec-
trolytes [2,3].
Solid-state electrolytes can address the aforementioned concerns on capacity
losses, life cycle, operating temperatures, safety, and the reliability of organic liquid
as well as gel electrolytes [4,5]. In addition, they present advantages such as the sim-
plicity of design, the absence of leakage and pollution, and better resistance to shocks
and vibrations compared with organic liquid electrolytes [6–8]. The search for solid
electrolyte materials with improved conductivity has been encouraged by the dis-
covery of lithium nitride (Li3N) which was discovered in the 1970s (Figure 2.3),
and has a very high conductivity of 6 × 10 –3 S cm –1 at room temperature. Following
lithium nitride, different classes of lithium-ion conductors including the lithium
superionic conductor (LISICON) and thio-LISICON-type, garnet-type, perovskite-
type, and sodium superionic conductor (NASICON)-type lithium-ion conductors
have been reported. This chapter discusses ionic conductivity, the electrochemical
performance and structure of typical oxide-type electrolytes (perovskites and anti-
perovskite lithium conductors) and sulfde-type lithium-ion conductors (LISICON
and thio-LISICONs, Li10GeP2S12 [LGPS] family, argyrodites, layered sulfdes), and

FIGURE 2.2 Thermal evolution of ionic conductivity (Arrhenius plot) of Li10GeP2S12,

together with those of other lithium solid electrolytes, organic liquid electrolytes, polymer
electrolytes, room temperature ionic liquids, and gel electrolytes. Adapted and reproduced
with permission from Ref. [3]. Copyright © 2011 Springer Nature.
Solid-State Electrolytes for Lithium-Ion Batteries 23

FIGURE 2.3 Crystal structure of lithium nitride (Li3N) solid-state lithium-ion conductor.

demonstrates their thermal stability and applications in all solid-state lithium-metal

batteries.

2.2 OXIDE-TYPE LITHIUM-ION CONDUCTORS

2.2.1 PEROVSKITE CONDUCTORS
A perovskite is any material with the same type of crystal structure as calcium tita-
nium oxide. The name perovskite comes from the mineral that was frst discov-
ered in the Ural Mountains of Russia by Gustav Rose in 1839, and is named after
Russian mineralogist L. A. Perovski. The general chemical formula for a perovskite
compound is ABX3, where A and B are two cations of very different sizes and X
is an anion that bonds to both. The ideal cubic structure has the B cation in 6-fold
coordination surrounded by an octahedron of anions, and the A cation in 12-fold
cuboctahedral coordination, as shown in Figure 2.4. Recently, perovskite Li+-ion
conductors and structurally related variants have attracted extensive attention based
on optimal bulk Li+ conductivities among various solid electrolytes. A large number
of studies have been reported with varying lithium ionic conductivities through the
replacement of A- and B-sites with different cations in which ionic conductivities
can reach up to 10 –3 S cm–1. The lithium-based perovskite has the general formula
24 Ceramic and Specialty Electrolytes

FIGURE 2.4 Idealized crystal structure for solid-state Li-ion conductors, (a) and (b):
perovskite general structure.

of (ABO3) type; for example, the structure of perovskite-type lithium lanthanum

titanate solid-state electrolytes can be represented as Li3xLa(2/3)–xTiO3 (LLTO) and
has a cubic structure with a space group of P4/mmm and C-mmm (Figure 2.5),
where the value of x ranges from 0.07 to 0.13 and the activation energy ranges from
0.3 to 0.4 eV [9]. The preparation conditions for LLTO are very strict and show poor
ionic conductivity (≤10 –4 S cm–1). In LLTO crystals, the Li+-ion conductivity is as
a result of the large concentration of A-site vacancies formed by four adjacent TiO6
octahedra, which facilitate the migration of Li cations through the bottlenecks [10].
Based on the adoption of different synthesis routes, and architected heterogeneous
lattice vacancies can result in different perovskite-like compounds with diverse
crystal structures, including cubic, hexagonal, orthorhombic, and tetragonal. For the
development of solid polymer electrolytes or inorganic solid-state electrolytes, it is
important to understand the crystal structure and ionic conduction mechanism in
LLTO. Yashima et al. [11] studied the Li+-ion migration path in La0.62Li0.16TiO3 and
Bohnke et al. [10] studied the ionic conduction mechanism in LLTOs. In their study,
it was found that Li cations can migrate from the 2c site on the (002) La-defcient
layer to the 2c-4f-2c or 2c-2d-2c tie line at 77 K to enhance conductivity [11], and con-
frmed that the ionic conduction mechanism of LLTOs incorporated the tilting and/
or rotation of BO6 octahedra as promoted by either rising temperatures or increasing
vacancies in the structure [10]. Recently, a poly(ethylene oxide) (PEO)-based poly-
mer composite electrolyte incorporated with Li0.33La0.557TiO3 nanowires as fller and
LiClO4 as the lithium salt has been reported with a lithium-ion conductivity of 2.4 ×
10 –4 S cm–1 at 25°C [12]. Lui et al. [13] compared the effect of LLTO morphology
(nanoparticles and nanowires) on the ionic conductivity of polymer electrolytes pre-
pared by electrospinning (Figure 2.6).
The introduction of LLTO nanowire into polyacrylonitrile (PAN) achieved higher
ionic conductivity (2.4 × 10 –4 S cm–1 at room temperature) than pristine PAN. The
composite electrolyte offers a 3D long-distance Li+-ion transmission network, which
Solid-State Electrolytes for Lithium-Ion Batteries 25

FIGURE 2.5 Idealized schematic visualization of crystal structure for A-site defcient
perovskite-type La(2/3)xLi3xTiO3.

FIGURE 2.6 Schematic illustration for the synthesis of ceramic nanowire-flled polymer-
based composite electrolytes. Adapted and reproduced with permission from Ref. [13].
Copyright© 2009, American Chemical Society.

reduces the negative effect of the agglomeration of inorganic ceramics in poly-

mers relative to nanoparticles. This work opened up a new way to develop one-
dimensional fast ion-conductive ceramic materials in solid electrolytes for lithium
batteries. Goodenough et al. [14] fabricated a 3D-LLTO/PEO composite electrolyte
using a hydrogel-derived method in which the LLTO was incorporated into the
hydrogel template and then cast with PEO after removing the template. Compared to
the traditional simple dispersion process, the use of an artifcial 3D infltration net-
work avoids the agglomeration of nano-sized LLTOs. In addition, the ultra-high spe-
cifc surface area of uniformly distributed nano-sized LLTOs provides a continuous
phase interface network as lithium-ion transport channels. However, the composite
electrolyte exhibited an ionic conductivity of 8.8 × 10 –5 S cm–1 at room temperature.
Similarly, Fu et al. prepared a 3D garnet nanofber network–polymer nanocom-
posite electrolyte [15]. In this approach, a continuous network of Li+-ion conduction
channels was formed by uniformly distributed porous Li7La3Zr2O12 (LLZO) in the
Other documents randomly have
different content
waiting for the removal of the tier of colliers that was over us, being convinced that we
should detect some derangement then. I attended Lady Raffles and party to the frames,
most uneasy all the while, as if I had a presentiment, not so much of the approaching
catastrophe to the extent it has occurred, but of what might result from the misbehaviour of
some of the men, as was the case when the Irish labourers ran away from the pumps and
the stage. I left the works at half-past five, leaving everything comparatively well: Mr.
Beamish continued on duty.[18]
Mr. Gravatt’s account is as follows: I was above with I. Brunel looking over some
prints, Beamish being on duty. Some men came running up and said to Isambard something
I did not hear. He immediately ran towards the works, and down the men’s staircase. I ran
towards it, but could not get down. I leaped over the fence, and rushed down the visitors’
stairs, and met the men coming up, and a lady, who I think was fainting. Met Flyn on the
landing-place, who said it was all over. I pushed on, calling him a coward, and got down as
far as the visitors’ barrier. Saw Mr Beamish pulled from it. He came on towards the shaft
walking. I went up to him to ask him what was the matter. He said it was no use resisting.
The miners were all upon the staircase; Brunel and I called to them to come back. Lane[19]
was upon the stairs, and he said it was of no use to call the men back. We stayed some time
below on the stairs, looking where the water was coming in most magnificently. We could
still see the farthest light in the west arch. The water came upon us so slowly that I walked
backwards speaking to Brunel several times. Presently I saw the water pouring in from the
east to the west arch through the cross arches. I then ran and got up the stairs with Brunel
and Beamish, who were then five or six steps up. It was then we heard a tremendous burst.
The cabin had burst, and all the lights went out at once. There was a noise at the staircase,
and presently the water carried away the lower flight of stairs. Brunel looked towards the
men, who were lining the staircase and galleries of the shaft, gazing at the spectacle, and
said, ‘Carry on, carry on, as fast as you can!’ Upon which they ascended pretty fast. I went
up to the top and saw the shaft filling. I looked about and saw a man in the water like a rat.
He got hold of a bar, but I afterwards saw he was quite spent. I was looking about how to
get down, when I saw Brunel descending by a rope to his assistance. I got hold of one of
the iron ties, and slid down into the water hand over hand with a small rope, and tried to
make it fast round his middle, whilst Brunel was doing the same. Having done it he called
out, ‘Haul up.’ The man was hauled up. I swam about to see where to land. The shaft was
full of casks. Brunel had been swimming too.
The first alarm, as I heard it, was as follows: Goodwin, in No. 11, said to Roger, in the
next box, ‘Roger, come, help me.’ Roger said, ‘I can’t, I have my second poling down, and
my face will run in.’ In a little time Goodwin said, ‘You must come,’ which Mr. Beamish
directed him to do. Roger turned round and saw Goodwin through a sheet of water. Corps,
a bricklayer, went to help Goodwin: he was knocked down. Roger made his way alone,
calling to Mr. Beamish, ‘Come away, sir, ‘tis no use to stay.’ Roger saw Corps fairly
washed out of his box like a lump of clay.

Sir Isambard’s journal continues:—

 May 19.—Relieved as I have found myself, though by a terrible catastrophe, of the
worst state of anxiety, that which I have been in for several weeks past, I had a most
comfortable night. Isambard and Gravatt descended with the diving-bell, and stood upon
the tails of Nos. 10, 11, and 12.
May 20.—Having descended into the hole and probed the ground, I felt that the staves
were in their places, and that the brickwork was quite sound. It is evident that the great
hole has been a dredging spot. A large mass of bags full of clay, and united together with
ropes, was let down. The Rotherhithe curate, in his sermon to-day, adverting to the
accident, said it was a fatal accident, that it was but a just judgment upon the presumptuous
aspirations of mortal men, &c.! The poor man!
May 23.—Went with the diving-bell to examine the ground and the bags, which do
apparently well, but it is working rather in the dark. It cannot, however, fail of making a
much better stratum than that we had before. The plan is therefore good.

On the 30th a raft was sunk over the shield, and the water in the shaft
was brought so low that the last flight of steps was visible. However, on the
next day the river broke in again; and as it was found that the raft was open
at the west side, it was raised and towed on shore.
June 5.—There is much danger in getting out of the diving-bell, the bags are so loose in
some places. One might sink and be swallowed, which had very nearly happened to-day.
Isambard and Pinckney being down, the latter lost his hold. The footboard being
accidentally carried away, he could not have recovered himself had not Isambard stretched
out his leg to his assistance.
June 17.—Visited by Charles Bonaparte. Isambard took him into the arch with the
yawl. Isambard fell overboard.[20]

On June 19, a general meeting of the proprietors was held, to consider

the position of the company. Sir Isambard addressed the meeting, and also
presented a long report, in which he entered very fully into the
circumstances of the recent accident and the causes which led to it. He then
described the means he had taken to restore the works by sinking bags of
clay and gravel. He adds: ‘I have already succeeded in closing the hole
through which the water first penetrated, and feel confident that the second
opening which afterwards appeared is also stopped, but a short time is
necessary to elapse for the new ground over the shield to settle and
consolidate. It has already supported a head of water of thirty-five feet.’
 June 25.—At 7 P.M. made preparations to re-enter the shield. Isambard, mustering the
men who had been the last to quit the frames, told them they would be the first to take
possession of them again—a precedence due, as he said, to them. Rogers, Ball, Goodwin,
Corps, and Compton, were accordingly ordered to trim themselves for the expedition,
provided with a phosphorus box, and dressed in light clothes, to be fit for a swim.
At about ten o’clock, Isambard and Mr. Beamish, accompanied by Ball and Woodward
(miners), went down with the punt, and got to the large stage, the head of the crane just
emerging. It was found impossible to get into the frames, as a mound of clay and silt closed
the entrance. The centering was in place and quite sound, and of course the brickwork.
Finding that they could not get nearer, they gave three cheers, which were rapturously
answered by the men at the mouth of the Tunnel. Having placed candles upon the ground
that closed the entrance, and upon the head of the crane, they returned. Isambard, having
promised that the men who had left the frames last should be the first to re-enter, returned
with them. This is a great day for our history!
June 27.—Mr. Beamish was able to get to the frames, which he found firm and
undisturbed.

A small tarpaulin was now spread over the frames, and operations
commenced for cleaning them. This was a most difficult and dangerous
work, especially as the water was still so high that the frames could only be
approached by boats. The men, even the best hands, were at first greatly
alarmed at the danger they were in; but the example set by Mr. Brunel and
Mr. Beamish produced, as Sir Isambard notes, the best effect, and they soon
became reconciled to their situation.
July 7.—Very uncomfortable in the frames; the candles cannot burn, the ventilation
cannot act. Isambard went several times to-day down in the diving-bell. On one occasion
the chain slipped through the stoppers, but most providentially it jammed itself tight before
being altogether run out. The consequence might indeed have been fatal. Can there be a
more anxious situation than that which I am constantly in? Not one moment of rest either
of mind or body. Mr. Beamish always ready. Poor Isambard always at his post too,
alternately below, or in the barges, and in the diving-bell.

On July 11, Sir Isambard thought that matters had so far advanced that a
large tarpaulin, which it was proposed to sink over the frames, ‘would have
its full effect.’ It was accordingly sunk on the following day, under the
superintendence of Mr. Brunel. Sir Isambard adds to his account of the
operation—‘This reflects great credit on Isambard, and the apparent facility
with which it was effected evinces his presence of mind, for a single faux
pas would have spoilt the whole.’[21]
 July 21.—During the early part of the night an alarm was given, by Fitzgerald calling
for clay wedges, and exclaiming that the whole of the faces were coming in altogether.
Rogers collected a quantity of wedges to go to the frames, but no boat was to be seen. He
called to the men in the frames, but received no answer. Taking the small boat in the east
arch, he reached the frames, but found nobody, nor any appearance of derangement in the
ground. Conjecturing they might be drowned, he explored further, and saw the four men
stretched on the small stage, not drowned, but sound asleep!
July 26.—Water nearly out of the arches. For the first time we could walk to the frames
—a most gratifying circumstance indeed! Two months and eight days.
September 30.—How slow our progress must appear to others; but it is not so, if it is
considered how much we have had to do in righting the frames and in repairing them; what
with timbering, shoring, shipping and refitting—all these operations being in confined
situations, the water bursting in occasionally, and the ground running in: in short, it is truly
terrific to be in the midst of this scene. If to this we add the actual danger, magnified by the
re-echoing of the pumps, and sometimes (still more awful warning!) the report of large
pieces of cast iron breaking, it is in no way an exaggeration to say that such has been the
state of things. Nevertheless, my confidence in the shield is not only undiminished—it is,
on the contrary, tried with its full effect, and it is manifest now that it will soon replace us
in good ground, and in a safe situation. No top staves have given way. That is our real
protection.
October 17.—At 2.15 A.M. Kemble, having first called upon Gravatt, came to Isambard
in a hurry, and, quite stupefied with fright, told him that the water was in. Says Isambard
—‘I could not believe him. He said it was up the shaft when he came. This being like
positive, I ran without a coat as fast as possible, giving a double knock at Gravatt’s door in
my way. I saw the men on the top, and heard them calling earnestly to those whom they
fancied had not had time to escape. Nay, Miles had already, in his zeal for the aid of others,
thrown a long rope, and was swinging it about, calling to the unfortunate sufferers to lay
hold of it, encouraging and cheering those who might not find it, to swim to one of the
landings. I immediately, I should say instantly, flew down the stairs. The shaft was
completely dark. I expected at every step to splash into the water. Before I was aware of
the distance I had run, I reached the frames in the east arch, and met there Pamphillon, who
told me that nothing was the matter, but a small run in No. 1 top, where I found Huggins
and the corps d’élite. They were not even aware that any one had left the frames. The cause
of the panic was one of the labourers; hearing the man in No. 1 call for Ball, he ran away,
jumping off the stage, crying, “Run, run, murder, murder; put the lights out.” His fellow-
labourers followed like sheep, making the same vociferations.’
November 10.—Isambard gave his entertainment to nearly forty persons, who sat at
table in the Tunnel. Nothing could exceed the effect for brilliancy. About 120 men partook
of a dinner in the adjoining arch.

As the year drew to a close, the difficulty of working the silt increased,
and with this difficulty increased also the expense of maintaining the staff
of men required. On December 18, Mr. Brunel, writing for his father, who
was absent from town for a few days, thus describes the nature of the soil
through which they were then passing.
The state of the ground over Nos. 1, 2, and 3 top has caused considerable delay,
particularly this week, although not such as to give any cause of anxiety as to our future
rate of progress, or to have any serious effect except the increased expense incidental to
this delay. My father desired me to describe to the Board the causes of these difficulties.
There is a considerable spring at this point, and a corresponding soft part in the bed of the
river, which seems to indicate the rising of the spring. The ground in the neighbourhood is
affected by this spring in rather a peculiar manner: at the half-flood tide the pressure is
greatest: dry hard clay oozes with great force through openings hardly observable, the silt
and water running by starts. At high-water the pressure and quantity of water begin to
diminish and on the ebb-tide the ground is hard and dry, and can be worked with ease. On
the flood-tide there are as many as twelve and fifteen of the best hands, besides myself (or
one of my assistants) and the foreman, engaged entirely at one face.

On January 1, 1828, Sir Isambard returned to London; and on the 12th,

when about 600 feet of the Tunnel had been completed, a second irruption
occurred, which put a stop to the works for seven years.
The particulars of this accident are thus described by Mr. Brunel, in a
letter to the Directors of the Company:—
I had been in the frames (shield) with the workmen throughout the whole night, having
taken my station there at ten o’clock. During the workings through the night, no symptoms
of insecurity appeared. At six o’clock this morning (the visual time for shifting the men) a
fresh set or shift of the men came on to work. We began to work the ground at the west top
corner of the frame: the tide had just then begun to flow; and finding the ground tolerably
quiet, we proceeded by beginning at the top, and had worked about a foot downwards,
when on exposing the next six inches, the ground swelled suddenly, and a large quantity
burst through the opening thus made. This was followed instantly by a large body of water.
The rush was so violent as to force the man on the spot, where the burst took place, out of
the frame (or cell) on to the timber stage behind the frames. I was in the frame with the
man, but upon the rush of the water I went into the next box (or cell), in order to command
a better view of the irruption, and seeing that there was no possibility of then opposing the
water, I ordered all the men in the frames to retire. All were retiring, except the three men
who were with me, and they retreated with me. I did not leave the stage until those three
were down the ladder of the frames, when they and I proceeded about twenty feet along the
west arch of the Tunnel. At this moment the agitation of the air, by the rush of water, was
such as to extinguish all the lights, and the water had gained the height of our waists. I was
at that moment giving directions to the three men, in what manner they ought to proceed in
the dark to effect their escape, when they and I were knocked down, and covered with a
part of the timber stage. I struggled under water for some time, and at length extricated
myself from the stage, and by swimming and being forced by the water, I gained the
eastern arch where I got a better footing, and was enabled by laying hold of the railway
rope, to pause a little, in the hope of encouraging the men who had been knocked down at
the same time with myself. This I endeavoured to do by calling to them. Before I reached
the shaft the water had risen so rapidly that I was out of my depth, and therefore swam to
the visitors’ stairs, the stairs for the workmen being occupied by those who had so far
escaped. My knee was so injured by the timber stage that I could scarcely swim, or get up
the stairs, but the rush of the water carried me up the shaft. The three men who had been
knocked down with me were unable to extricate themselves, and I am grieved to say, they
are lost; and I believe also two old men, and one young man, in other parts of the work.

This statement Sir Isambard embodied in a report to the Directors of

January 28, which was circulated among the proprietors.
As soon as the first excitement caused by the irruption had ceased, Mr.
Brunel directed the diving-bell to be prepared in order to ascertain the state
of the shield and the extent of the disturbance of the bed of the river caused
by the rush of water into the Tunnel.
He was, however, so seriously injured that he could not actively
superintend the preparations, but his orders were given with his usual
clearness, calmness, and decision; and as soon as the barge containing the
diving-bell was properly moored over the Tunnel, he was carried out and
laid upon a mattress on the deck of the barge, that he might direct what was
to be done.
As evening came on he became so much worse that he was taken into
the cabin; but everything which took place was reported to him.
At length, the bell being ready, it was lowered early on the Sunday
morning, but the chain not being long enough, proceedings were delayed
until a longer chain could be obtained.
As, however, a chain of the right size and length could not be obtained,
the strongest cable which could be procured in the neighbourhood was
substituted for the chain. A controversy then arose between the assistant
engineers and the foremen as to the sufficiency of the strength of the cable;
and it was agreed to consult and to abide by the opinion of Mr. Brunel, who
was then lying in great pain in the cabin.
No answer could be obtained from him for some minutes, and then he
only said, ‘Don’t go down.’ This not being satisfactory to the advocates of
the sufficiency of the cable, it was agreed to lower the bell empty, which
was done, and it was brought up safely; but just as it was swung over the
barge, the rope broke and the bell fell on to the stage.
The next day Mr. Brunel was taken home, when it was found that,
besides the injury to his knee which he received while endeavouring to save
the lives of the three men who were with him,[22] he had received serious
internal injuries, which kept him under medical treatment for several
months.
When he was able to return to Rotherhithe all hope of continuing the
works was for the time abandoned. When they were resumed, in 1835, he
was entirely engrossed in the independent pursuit of his profession; and,
with the exception of a few occasions when he acted for his father, he had
no further connection with the Tunnel.
It is not, therefore, necessary to continue the narrative in detail; but a
brief summary of the subsequent history of the enterprise may be interesting
to those who are unacquainted with it.
The Tunnel was cleared of water, and efforts were made, unfortunately
without success, to raise funds for the completion of the undertaking. Great
enthusiasm was exhibited by the general public and by many eminent
persons, including the Duke of Wellington; but the money was not
forthcoming, and nothing was left but to brick in the shield, and wait for
more favourable times.
It was not till the beginning of 1835 that the Company was able, by the
aid of a loan from Government, to recommence the works. The old shield
was removed and a new one substituted, in which considerable
improvements were introduced. Slings connecting the frames were added,
which enabled each frame to support its neighbours when necessary, and
important alterations were also made in the arrangements for keeping the
frames at the right distance from one another, and for giving greater facility
of adjustment to the various parts.
Before the Wapping side was reached there were three more irruptions of
the river, namely, August 23, November 3, 1837, and March 21, 1838; but
in October 1840 the shaft on the Wapping shore was commenced. It differed
from the Rotherhithe shaft, in being sunk the whole depth without
underpinning, and was made of a slightly conical form, to reduce the
friction in sinking, and had a larger quantity of iron hoops introduced into
the brickwork, in order to increase its strength. When this structure had
been sunk to the required depth (70 feet), the excavation of the Tunnel was
resumed, and at last the shield was brought up to the brickwork of the shaft.
The operation of making the junction between the Tunnel and the shaft was
one of much difficulty, but it was at length satisfactorily accomplished, and
the Tunnel was opened to the public on March 25, 1843—eighteen years
and twenty-three days after the commencement of the work.[23]
Sir Isambard Brunel, whose health had for some time been failing, now
retired altogether from his professional labours. After passing a few years in
peaceful and happy seclusion, surrounded by those he loved, and watched
over by their affectionate care, he died on December 12, 1849, in his 81st
year, having been spared to carry to completion his greatest work, and to
see his son following in his footsteps with a success which must have
exceeded his most sanguine expectations.

The education Mr. Brunel received from his father was well calculated to
form the foundation of his future career. During the later and more arduous
part of the contest, which was ended by the irruption of January 1828, he
held both the nominal and actual post of Resident Engineer of the Thames
Tunnel; but from the commencement of the works, when he was only
nineteen years old, he had been, as stated by Sir Isambard, ‘a most valuable
coadjutor in the undertaking.’ While placed in this responsible position he
acquired habits of endurance and of self-reliance, and learnt to act with
promptitude and decision in the application of those measures which
experience had shown to be effective in each particular class of emergency.
But beyond all other advantages, he had before him the example of his
father’s character, in which a rare degree of gentleness and modesty of
disposition was joined to unflinching energy, and a determination to
overcome all difficulties.

NOTE A (p. 5).

The Bourbon Suspension Bridges.[24]
The suspension bridges designed by Sir Isambard Brunel for crossing rivers
in the Ile de Bourbon were two in number. One of them had two spans of
122 feet each in the clear, and 131 feet 9 inches between the points of
suspension of the chains. The second had but one span of the same
dimensions as those of the larger bridge. In the design of these bridges one
of the most important points to be attended to, was to render them secure
against hurricanes, which are both frequent and severe in the Ile de
Bourbon.
In the larger bridge there was a pier of masonry, built in the middle of
the river up to the level of the roadway of the bridge. The suspension chains
of the bridge were in three groups, 9 feet 8 inches apart, so as to leave room
for two roadways, each about 8 feet 9 inches wide. Each of these groups of
chains consisted of two chains side by side. Each chain was made with long
links like those of the chain cables used for moorings.
These links, which were made of iron 1·36 inch in diameter, were 4 feet
8 inches long, inside measure, and were each connected together by two
short coupling links, 8¾ inches long, inside measure, of iron 1·36 inch by 1
inch, and two pins, each two inches in diameter.
The two chains of each group were placed side by side, with the links
upright; one of the pins at each joint was made long enough to serve for
both chains, and, in the middle of its length between the two chains, was
passed through an eye at the upper end of one of the suspending rods of the
bridge. Thus to every joint in each group of the main chains, or at intervals
of about 5 feet, there was a suspending rod. These rods were 1¼ inch in
diameter.
The pins of the joints of the main chains had half heads at each end of
them. They could thus be easily inserted in erecting the bridge, but once in
place were quite secure. At every fourth joint in the main chains one of the
joint pins was made in two halves, with wedges inserted between them for
adjusting the length of the main chains.
Thus there were six chains, and as the links of these had each two parts
of iron 1·36 inch in diameter, the total sectional area of the six chains was
17·4 inches.
Each group of the main chains was supported at a height of 25 feet 6
inches above the roadway at the centre pier, and at a height of 5 feet 3
inches at each of the side piers, the lowest portion of the curve of the chain
being about 1 foot below the points of suspension of the side piers.
The upright standards, carrying the chains both at the centre pier and at
the side piers, consisted for each group of chains of a triangular framework
of cast iron, strengthened by long bolts of wrought iron. There were thus
three of these triangular frames parallel to each other at each of the piers,
and those at the centre pier were braced together over the carriage road. The
main chains were not bolted to the standards, but were slung from them by
a vertical suspension link, which thus allowed them to move a little
lengthways. This link, in fact, performed the function of the rollers now
generally put under the saddles of suspension bridges.
The ends of the main chains were held by back stays, formed of bars 3
inches broad by 1¼ inch thick, and 10 feet long, with joints made with short
links, and 2⅜ inch pins. The ends of those back stays were secured to
holding down plates 3 feet in diameter, sunk deep in the ground and well
loaded.
As there was a vertical suspension rod at each joint of the main chains,
there was a suspension rod hanging from each of the three groups of chains
at about every five feet of the length of the bridge. To each set of these rods
was attached a cross girder of cast iron of a T section, with a large rounded
bead at the lower edge of the upright web; and connecting these under each
of the main chains was a longitudinal timber beam about 8 inches square.
The cast-iron cross girders carried longitudinal teak planking, the planks
on which the carriage wheels ran being 12 inches wide and 4 inches thick,
protected at the top by wrought-iron plates running longitudinally. The
horse-path was protected by iron plates arranged crosswise.
Under each span of the bridge were four chains curved upwards and also
sideways. These chains were fastened at their ends into the piers, and were
connected to the roadway by ties drawn up tight and attached to the main
longitudinal bearers of the platform; the object being to stiffen the platform.
These under tie chains were made each of a set of rods 1¼ inch in
diameter with eyes at their ends, the ends being connected by short joint
links and 1¼ inch pins; and to these joint links were attached the tie rods
which connect these inverted chains with the platform of the bridge, and so
prevented its being lifted or blown sideways by the force of the wind.
In the smaller bridge, which, as has been said, consisted of one span of
131 feet 9 inches between the points of suspension, these points were 15
feet 5 inches above the roadway, and the lowest part of the chain was 9 feet
7 inches below the points of suspension. The details of this bridge were
similar to those of the larger one.
 NOTE B (p. 5).
Experiments with Carbonic Acid Gas.
In 1823 Mr. Faraday made the important discovery that under certain
conditions of temperature and pressure many gases could be liquefied, and
that these liquids exerted great expansive force by slight additions of
temperature, returning quickly with regularity and certainty to their original
state upon the application of cold.
The discovery of this new force appeared of such importance, that Mr.
Faraday lost no time in publishing it to the world; and Sir Isambard Brunel
very soon afterwards commenced a series of experiments to determine the
value of the liquid gas as a mechanical agent.
The first experiments were made at Chelsea; but the prosecution of them
was soon transferred to the care of Mr. Brunel at Rotherhithe, where he
devoted all his spare time to the construction of his father’s proposed
‘Differential Power Engine.’
That the progress of this discovery, and of the experiments made with a
view to the application of the liquid gas, as a motive power, may be
understood, it is necessary to state that in March 1823 Mr. Faraday
communicated to the Royal Society the results of his first experiments on
the liquefaction of gases.
The fluid was then produced by the decomposition of the hydrate of
chlorine by heat in a closed tube, the amount of gas evolved being so great
as to produce a pressure in the tube sufficient to condense the gas into a
fluid of the same volume.
This interesting experiment was followed by others with that rapidity
and success so remarkable in everything undertaken at that time in the
laboratory of the Royal Institution; and within a month another paper was
read before the Royal Society, in which the degrees of pressure and
temperature at which several gases could be liquefied were recorded, and
the means employed to produce and liquefy each gas accurately described.
On April 17 a third paper was communicated by Mr. Faraday, ‘On the
Application of Liquids produced by the Condensation of Gases as
Mechanical Agents.’
The question is thus stated: ‘The ratio of the elastic force dependent
upon pressure is to be combined with that of the expansive force dependent
on temperature; and the development of latent heat on compression and the
necessity of its reabsorption in expansion must awaken doubts as to the
economical results to be obtained by employing the steam of water under
very great pressures and very elevated temperatures.
No such doubt can arise respecting liquids, which require for their
existence even a compression equal to thirty or forty atmospheres, and
where slight elevations of temperature are sufficient to produce an immense
elastic force, and where the principal question arising is whether the effort
of mechanical motion is to be most easily produced by an increase or
diminution of heat by artificial means.’
Difficulties were suggested by Mr. Faraday as to the possibility of
obtaining sufficient strength in the apparatus, but the small difference of
temperature required to produce an elastic force of many atmospheres, he
considered would render the risk of explosion small.
To construct the machinery whereby this new force could be practically
applied as a substitute for steam, occupied the time of Sir Isambard Brunel
and his son at intervals for several years; for although Mr. Brunel was
satisfied at an early period of the enquiry that the liquefied gases could only
be advantageously employed where the cost of motive force was secondary
to economy of space and to the avoidance of the cumbrous apparatus
required for the use of steam, still he was so impressed with the importance
of the subject, if the difficulties he foresaw in its application could be
overcome, that he continued his experiments for a long period with
unflagging energy and perseverance.
The facts relating to the liquefaction of the gases, their elastic force
when liquefied under different temperatures, the rapidity with which they
could be alternately expanded and condensed, and the best mode of
producing each gas, were determined by Mr. Faraday; and as Mr. Brunel
was at that time attending the morning chemical lectures at the Royal
Institution, he was in constant communication with him, and thoroughly
conversant with his experiments.
After Mr. Brunel had made a few preliminary experiments, Sir Isambard
determined to employ liquefied carbonic acid gas for the motive power of
the proposed new engine, the facility and cheapness of its production, its
great expansive force, and its neutral character distinguishing it from any
other gas; but it was long before vessels were constructed, in which gas
could be produced in sufficient quantity and purity to exert the force
required to liquefy it in its own volume, for it was soon found to be
impossible to obtain the required pressure with pumps.
Carbonate of ammonia and sulphuric acid were the elements used, and
the generator was so arranged that it could be charged, emptied of
atmospheric air, and the joints made perfect, before the commencement of
the formation of the gas which was to be liquefied.
To the generator was attached a receiver, which could be surrounded
with a freezing mixture, so that the temperature of the gas in the cylinder
might be below that in the generator.
The gradual formation of the liquid, the development of its elastic force,
and the regularity and rapidity with which it increased or diminished by
each degree of heat or cold, were carefully watched through a glass gauge,
and the receiver when filled with liquid could be disconnected from the
generator.
The mechanical difficulties as they arose, one after the other, in the
construction and arrangement of the various parts of the generator and
receiver were at length overcome; and the receiver was not only filled with
liquid gas, but found to be capable of retaining it, whether exerting an
elastic force of 30 atmospheres at ordinary temperatures, or of 100
atmospheres when subjected to a slight degree of heat.
The receiver being satisfactorily completed, the next object of attention
was the design and construction of a working cylinder capable of resisting
at least 1,400 lbs. pressure on the square inch; a task which was one of great
anxiety, as any weakness might have caused a serious accident.
It was only after the trial of every known method of making joints to
resist high pressures had failed, that an arrangement was devised, requiring
the most perfect workmanship, by which packing of any kind was
dispensed with, and the cylinder fitted for use.
With the improved tools of the present day it is not easy to realise the
difficulties, delays, and disappointments which forty-five years ago
occurred from the failure, first of one part of a joint, and then of another;
but the construction of vessels capable of producing and also of retaining
the gas in its liquid state, with the means of alternately expanding and
condensing it from thirty or forty to eighty or one hundred atmospheres,
having been accomplished, the object of the expenditure of so much labour
and inventive power appeared to be within reach.
The construction of the machinery to utilise the elastic force contained in
the cylinder was now proceeded with. Day by day new difficulties arose,
and each as it was successfully met seemed but to leave another of greater
importance to be surmounted.
It is not necessary in this Note to describe the various arrangements
which were devised for transferring the great elastic force in the cylinder of
small diameter to a piston in another cylinder of much larger dimensions; it
is sufficient to say, that after the devotion of much valuable time extending
over several years, and a very large expenditure of money, and after
carefully considering the cost of the liquid carbonic acid gas, the difficulty
of preventing waste, and the necessarily very expensive character of the
machinery, Mr. Brunel was satisfied ‘that no sufficient advantage in the
sense of economy of fuel can be obtained by the application of liquefied
carbonic acid gas as a motive power’; but so thoroughly did he exhaust the
subject before he committed himself to this opinion, that no one has since
renewed the enquiry or attempted to make a machine to be moved by the
elastic force of liquefied gases, the construction of which, it was well
known, had baffled the inventive genius of Sir Isambard Brunel and his son.
 CHAPTER II.

THE CLIFTON SUSPENSION BRIDGE.

A.D. 1829—1853. ÆTATIS 24—48.

ORIGIN OF THE UNDERTAKING—THE FIRST COMPETITION,

NOVEMBER 1829—DESCRIPTION OF MR. BRUNEL’S PLANS—
MR. TELFORD’S DECISION AS UMPIRE—MR. TELFORD’S
DESIGN—THE SECOND COMPETITION—MR. BRUNEL
APPOINTED ENGINEER, MARCH 1831—COMMENCEMENT OF
THE WORKS, AUGUST 1836—DESCRIPTION OF THE DESIGN—
ABANDONMENT OF THE WORKS, 1853—FORMATION OF A
NEW COMPANY AND COMPLETION OF THE BRIDGE, 1864.
NOTE: THE HUNGERFORD SUSPENSION BRIDGE.

AFTER Mr. Brunel had recovered from his accident in the Thames Tunnel,
he went for a trip to Plymouth, where he examined with great interest the
Breakwater and other engineering works in the neighbourhood. He notes in
his diary that he went to Saltash, and that he thought the river there ‘much
too wide to be worth having a bridge.’ This remark was no doubt made in
consequence of his father having some years before been consulted as to the
construction of a suspension bridge at this place, which Mr. Brunel himself,
eighteen years afterwards, selected for the crossing of the Tamar by the
Cornwall Railway, and built there the largest and most remarkable of his
bridges.
For the remainder of the year 1828, and during the greater part of 1829,
Mr. Brunel kept himself fully employed in scientific researches, and in
intercourse with Mr. Babbage, Mr. Faraday, and other friends; but he was
without any regular occupation, until, in the autumn of 1829, he heard that
designs were required for a suspension bridge over the Avon at Bristol, and
he determined to compete.
This project originated in a bequest made in 1753, by Alderman William
Vick, of the sum of 1,000l. to be placed in the hands of the Society of
Merchant Venturers of Bristol, with directions that it should accumulate at
compound interest until it reached 10,000l., when it was to be expended in
the erection of a stone bridge over the river Avon, from Clifton Down to
Leigh Down. Alderman Vick stated that he had heard and believed that the
building of such a bridge was practicable, and might be completed for less
than 10,000l.

The legacy was duly paid to the Society of Merchant Venturers, and
invested by them. The interest accumulated; and in 1829, when the fund
amounted to nearly 8,000l., a committee was appointed to consider in what
way it would be possible to carry out Alderman Vick’s intentions.
An estimate for a stone bridge was procured, but as it gave the cost at
90,000l., it was evident that this scheme must be abandoned.

The committee then advertised for designs for a suspension bridge. Mr.
Brunel, on hearing through a friend of the proposed competition, went to
Bristol; and, after examining the locality, he selected four different points
within the limits prescribed by the instructions of the committee, and made
a separate design for each of them. His plans were sent in on the day
appointed, Nov. 19, 1829, with a long statement, from which the following
description of them is taken.
The first design was for a bridge of 760 feet span between the points of
suspension, the length of the suspended floor being 720 feet. In order to
obtain a height of 215 feet above high-water mark (which was the least that
the levels allowed of), towers 70 feet high would have had to be built on the
cliffs to carry the chains. The total length of chain, including the land-ties,
was about 1,620 feet. Mr. Brunel did not approve of this design, as the
situation was not favourable to architectural effect, a point to which the
committee attached great importance; but he suggested it from its being
somewhat more economical in construction than his other plans.
In another design, the situation being some way farther down the river
than that of the design last mentioned, towers would also have been
necessary. The distance between the points of suspension was 1,180 feet,
with a suspended floor of over 900 feet. It is probable that Mr. Brunel only
proposed this plan because the site came within the limits of deviation, as
he does not say anything in favour of it in his report.
 The two remaining plans are the most interesting of the series, as there
can be no doubt that, if Mr. Brunel had had his own way, he would have
adopted one of them for execution; and it appears from a little sketch on the
top of one of his earliest letters from Bristol, that his first idea for the bridge
was that which is carried out in these two designs. The site selected was one
where the rocks rise perpendicularly for a considerable height above the
proposed level of the bridge, and therefore piers and land-ties were
dispensed with, the chains being hung directly from the rock. No masonry
was required except for architectural effect.[25]

Plate I.
CLIFTON SUSPENSION BRIDGE.
Elevation of Drawing Nº 3 of Mr. Brunel’s Designs in the first
competition. AD. 1829

Elevation of the Bridge according to the Design on which the works were
commenced. AD. 1836.
[Larger view]
[Largest view]

The principal difference between these two designs is that in the second
a short tunnel is avoided at one end. The style of architecture selected for
the tunnel-front and the face of the rock, as shown on the drawings sent in
to the committee, is Norman. There are also extant many beautiful sketches
made by Mr. Brunel for different parts of the design.[26]
In determining upon the mode of construction, which was the same in
the four designs, Mr. Brunel acted upon the principle which guided him in
all his subsequent undertakings, which was, as he states in his report, ‘to
make use of all that has been found good in similar works, and to avail
himself of the experience gained in them, and to combine with all their
advantages the precautions which time and experience had pointed out.’
He dismissed in a few words the plan of breaking the span into two or
three lengths. This was in his opinion unnecessary, and he computed that
the cost of a pier built up from the water’s edge to sufficient height above
the bridge to carry the chains, would be at least 10,000l. For this reason he
recommended the adoption of spans, the smallest of which far exceeded any
up to that time constructed.
In designing the chains, he dispensed with the short connecting links,
which had been previously adopted in suspension bridges, introducing
instead the method now universally used, of connecting each set of links
directly with the adjoining one by means of a pin passed through the holes
of both. The number of joints and pins was thus reduced one half, and a
considerable saving of expense, as well as diminution of weight, effected.
Another improvement, which diminished still further the weight of the
chains, was making the links in lengths of 16 feet, or nearly double that of
the longest links at the Menai bridge. The chief reason for this alteration
was to ensure a near approximation to equality in the strains on the different
links, should all the distances between the holes not be exactly equal. This
improvement was afterwards carried still further in the Hungerford
Suspension Bridge, the links of which were 24 feet long.[27]
Mr. Brunel also intended to introduce equalising beams in the supports
of the floor, so that each chain should bear an equal share of the load. By
this arrangement, there would have been comparatively few points of
suspension, and ‘the view of the scenery would not be impeded from the
observer being surrounded by a forest of suspension rods.’
The disturbance of the strains on the links arising from the greater
expansion of the metal of the outer links by the direct heat of the sun, he
proposed to obviate by sheet-iron plates placed on each side of the chains,
but separated from them by a small interval, and thus screening them from
the heat. He did not, however, use this protecting covering at the
Hungerford bridge.
All the designs show a camber or rise in the centre of the platform of the
bridge, to the extent of two or three feet; and the main chains are brought
down almost to the level of the platform. To this last arrangement, as
tending to prevent undulation, Mr. Brunel attached some importance; and
he further intended to stiffen the bridge against the action of high winds by
a system of transverse bracing, and by the addition of inverted chains,
similar to those used with success by his father in the Bourbon bridges.[28]
Such, then, were the main features of the bold and carefully matured
designs placed by Mr. Brunel before the committee. Out of twenty-two
plans submitted, only those of Mr. Brunel and four other competitors were
deemed worthy of consideration. He and his friends were naturally much
gratified at this, and were full of hope for his ultimate victory. But now,
when he seemed to have a fair chance of success in a contest which he
justly deemed would have a most important bearing upon his future
professional career, an obstacle presented itself, which for the time seemed
almost insurmountable; for he met with an unexpected opponent in Mr.
Telford, the foremost engineer of the day, and the designer of the famous
suspension bridge over the Menai Straits.
The committee of the Society of Merchants had, not unnaturally, found
themselves unable to decide upon the merits of designs for a suspension
bridge, and had asked Mr. Telford to act as their adviser in the matter.
Unfortunately for Mr. Brunel, Mr. Telford was of opinion that the maximum
span admissible was that of the Menai bridge, i.e. under 600 feet, and that
Mr. Brunel’s proposed bridge, though very pretty and ingenious, would
most certainly tumble down in a high wind.
This decision was, of course, fatal to the success of any design which
substituted one large span for two or more smaller ones, and dispensed with
pillars. Mr. Brunel therefore obtained permission to withdraw his plans
from the competition.
Mr. Telford then reported to the committee that none of the remaining
designs were suitable for adoption without the introduction of such material
alterations as would, in fact, constitute a new design. Whereupon the
committee took the only course which, under the circumstances, was open
to them, and requested Mr. Telford to prepare a design himself.
 Mr. Brunel was not a little disappointed at the turn matters had taken;
but, having, as he said,‘smoked away his anger,’ he took leave of his friends
at Bristol, and went for a visit to some of the principal manufacturing towns
in the north.
Meanwhile Mr. Telford prepared his design, and it was exhibited in
Bristol in January 1830. It consisted of a suspension bridge of three spans
(the centre span 360 feet, and the side ones 180 feet each), the chains being
supported at the intermediate points by tall stone piers rising from the
river’s banks at just sufficient distance apart to avoid interfering with the
roadways on either side of the stream. The style of architecture was a florid
Gothic; and, in order to display the peculiar features of that style, the faces
of the piers were covered with elaborate panelling, and the chains
ornamented with fret-work.
This design was received with a flourish of trumpets; numerous
engravings were published, exhibiting the bridge from various points of
view, and ‘thousands of copies were disposed of;’ but, after a time, it would
appear that the captivating effect of the Gothic belfries wore off, and that
the more the citizens of Bristol looked at Mr. Telford’s plan, the less they
were satisfied with it; for, although it was deposited in the Private Bill
Office, on application being made for an Act of Parliament, the trustees who
were appointed under the Act determined to invite a second competition.
On this occasion, Mr. Telford appeared as a competitor and not as a
referee, that office being filled by Mr. Davies Gilbert, sometime President
of the Royal Society.
The site of the bridge was fixed, being that selected by Mr. Telford; but
the trustees expressly left it to the judgment of the competitors to decide
whether there should be intermediate piers or one unbroken span.
Of the thirteen designs sent in, five, including those submitted by Mr.
Telford and Mr. Brunel, were reserved for further examination. On March
17, 1831, Mr. Davies Gilbert (who had been assisted by Mr. Seward) made
his report. Mr. Telford’s design was put aside, ‘on account of the
inadequacy of the funds requisite for meeting the cost of such high and
massive towers as were essential to the plan which that distinguished
individual had proposed.’
Mr. Brunel’s design was placed second.[29] Although Mr. Gilbert
reported that it presented every desirable strength and security, he saw
objections to many of the details, and therefore did not recommend it for
adoption. However, on the following day, March 18, he stated to the
trustees that he had seen Mr. Brunel, and that it gave him much pleasure to
state that the explanations made by Mr. Brunel had materially altered his
views as to the details of the plans, which he (Mr. Gilbert) was now
satisfied were quite equal to those which he had placed first, and that,
considering the superiority of Mr. Brunel’s design in the essential particular
of strength, he should judge it preferable to any of the others.
Thereupon the trustees, ‘having considered Mr. Davies Gilbert’s report,
and referred to all the plans, including Mr. Telford’s, unanimously gave the
preference to Mr. Brunel’s,’ and appointed him their engineer.
Subscriptions came in but slowly, and it was not till 1836 that the works
were commenced.
The first stone of the abutment on the Leigh woods or Somersetshire
side of the river was laid on August 27 by the Marquis of Northampton,
President of the British Association, which was then holding its meeting in
Bristol.[30]
The span of the bridge is greater than that of Mr. Brunel’s design for the
second competition, but much less than the spans of the earlier designs, to
which he had given the preference.[31] On this point, as well as on the
question of site, he had to conform to the wishes of the trustees.[32] The
span approved of by them necessitated the building of a very large abutment
on the Leigh woods side, the height of which, from the surface of the rock
to the level of the roadway, is 110 feet. Above the roadway, the tower to
carry the chains is built to a height of 86 feet. On the Clifton side, the base
of the tower is formed by one of the boldest of the range of St. Vincent’s
rocks, which here rise almost perpendicularly to a height of 230 feet above
high water, and consequently a very small abutment was required. The
tower on this side is 3 feet higher than that on the Leigh woods side, and the
roadway has a general inclination of about 1 in 233. Mr. Brunel thought that
if the roadway were level, it would have the appearance of falling towards
Clifton, owing to the ground there being precipitous, while on the Leigh
woods side it is sloping.
He intended, in the construction of the bridge, to have followed out the
ideas embodied in his report of 1829, and would have preferred to have had
only one chain on each side of the bridge, and that much stronger than was
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knowledge seekers. We believe that every book holds a new world,
offering opportunities for learning, discovery, and personal growth.
That’s why we are dedicated to bringing you a diverse collection of
books, ranging from classic literature and specialized publications to
self-development guides and children's books.

More than just a book-buying platform, we strive to be a bridge

connecting you with timeless cultural and intellectual values. With an
elegant, user-friendly interface and a smart search system, you can
quickly find the books that best suit your interests. Additionally,
our special promotions and home delivery services help you save time
and fully enjoy the joy of reading.

Join us on a journey of knowledge exploration, passion nurturing, and

personal growth every day!

ebookbell.com