Results in Chemistry 5 (2023) 100885

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Results in Chemistry
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Supercapacitor and electrochemical techniques: A brief review

Swati Sharma *, Prakash Chand *
Department of Physics, National Institute of Technology, Kurukshetra 136119, India

A R T I C L E I N F O A B S T R A C T

Keywords: Energy storage plays crucial role to complete global and economical requirements of human beings. Super­
Energy storage capacitor act as promising candidate for energy storage applications due to its astonishing properties like - high
Supercapacitor power density, remarkable crystallinity, large porosity, elongated life-cycle, exceptional chemical & thermal
Specific capacitance
stability, framework diversity and high specific surface area. The current review article embraces the history
Electrolytes
Electrochemical measurements
along with the difference of supercapacitors with fuel cells, capacitors, and batteries and detailed explanation of
fabrication of supercapacitors i.e. proper selection of electrode and electrolyte material, separator and current
collector. As a supercapacitor electrode material, several carbon-based materials, metal-oxides, and metal­
–organic frameworks have been briefly mentioned here. The current review article also discusses the super­
capacitor components and various types of electrolytes. Electrochemical characterization techniques such as
Cyclic Voltammetry (CV), Galvanostatic Charge Discharge (GCD) and Electrochemical Impedance Spectroscopy
(EIS) are also briefly discussed here. Furthermore, this article outlines the current issues as well as potential
solutions for upcoming time period.

1. Introduction These all can be distinguished on the basis of their energy density, power
density, efficiency, conductivity, voltage window [10] and current
Energy plays a key role for human development like we use elec­ density. Fig. 1 depicts the Ragone plot of various energy storage devices.
tricity 24 h a day. Without it, we can’t imagine even a single moment.
Modern society in 21st century demands low cost [1], environment
1.1. Historical background of various energy storage devices
friendly energy conversion devices. Energy conversion and storage both
[2] are crucial for coming generation. There are two types of energy
1.1.1. Fuel cell
sources namely non-renewable and renewable energy sources those can
First successful fuel cell was discovered in 1932. Fuel cells are not
be distinguished on the basis of their supply and recycling capability.
used for energy storage. It is a high efficiency device which directly
Fossil-fuels such as coal, wood, natural gas comes under category of non-
converts chemical energy into electrical energy. Fuel cell consists of
renewable energy sources. They can’t be reused and limited in supply.
cathode, anode, separator and electrolyte as shown in Fig. 2(a). These
Instead renewable sources namely solar energy from sun, wind energy,
are continuously supplied with fuels (e.g. propane, natural gas, diesel,
[3,4] hydroelectric power, biomass derived carbon, geothermal energy
hydrogen etc.) and oxygen so they provide us electrical energy [11,12]
and animal dung can be reused. These are also called non-conventional
for long period of time. For smooth operation of fuel cell, electrolyte
sources of energy [5]. They produce clean and environmental friendly
must be dense and leak tight, good ionic conductor at operating tem­
energy of unlimited supply. In today era, ozone depletion, global
perature, high thermal stability, high surface area and economically
warming and vehicular pollution has become big problem due to
processable. Electrodes (e.g. proton-conducting media, carbon sup­
increasing use of non-renewable or conventional sources of energy [6].
ported catalyst and electron conducting fibres) must have high electrical
We have diverse need of non-conventional energy sources [7,8] to
conductivity, [13,14] high surface area and compatible with electrolyte
complete our global demands and to solve our economical problems.
(and interconnect).
There are many devices those can convert one form of energy into
another like rechargeable or lithium-ion batteries, capacitors, film caps,
1.1.2. Capacitor
SMES [9], supercapacitor (also called ultra-capacitors) and fuel cells.
Leyden jar invented in 1746 leads [15] to the discovery of capacitor.

* Corresponding authors.
E-mail addresses: [email protected] (S. Sharma), [email protected] (P. Chand).

https://doi.org/10.1016/j.rechem.2023.100885
Received 28 November 2022; Accepted 6 March 2023
Available online 8 March 2023
2211-7156/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
S. Sharma and P. Chand Results in Chemistry 5 (2023) 100885

Capacitor consists of two conductors act as electrodes separated by an and Lithium Nickel-oxide (LiNiO2) [18, 19]. Lithium Primary batteries
insulating or dielectric medium. Depending upon the geometry, capac­ are used in heart pace maker, instrumentation and oil drilling. Li-ion
itors [16] are categorized into three parts: (i). Parallel plate capacitor in batteries are used in portable electronics, electric vehicles and
which two parallel plates are separated by a dielectric as shown in Fig. 2 aerospace.
(b). Capacitance of parallel plate capacitor is increased by introducing
conducting slab or dielectric. It is denoted by C and measured in 2. Supercapacitor
microfarad as depicted in equation (1).
Now a days, Supercapacitors gains attention of scientists due to their
A∈0
C = (1) improvement over batteries. Supercapacitors have large efficiency
d
instead batteries shows abrupt decrease in efficiency [20] due to fast
Where, A is area of plates, d is spacing between two parallel conducting charging cycles. Batteries have short life time and act as intermediate
plates,∈0 is electric permittivity of free space. between Supercapacitor and fuel cells as shown in Ragone plot. Super­
They have high power density, less capacitance value and low energy capacitors have high capacitance value, high power density, functions
density in comparison to supercapacitor [17]. (ii). Spherical capacitor, over large range of temperature and long term durability. Comparison of
one spherical conductor of radius r1 is surrounded by another concentric various energy storage devices is shown in Table 1. They show high
grounded sphere of radius r2 as shown in Fig. 2(c). Capacitance of capacitance value because in supercapacitors we use electrical double
spherical capacitor is calculated with the help of equation (2). layer capacitance and pseudocapacitance instead of solid dielectric
which was used in capacitors [21,22]. It depends on parameters like
4π∈0 r1 r2 thermal stability, ionic conductivity of materials used as electrodes and
C= (2)
r2 − r1 electrolytes etc. Overall performance of supercapacitor [23] depends on
(iii). Cylindrical capacitor is that whose geometry is like a coaxial careful selection of separator, electrodes and electrolyte material.
cable as shown in Fig. 2(d). Equation (3) describes the capacitance of Supercapacitor consists of two electrodes, an ion-permeable membrane
cylindrical capacitor with inner radius r1 and outer radius r2. known as separator and an electrolyte ionically connecting both elec­
trodes. Separator like polyolefin, cellulose allows transport of ions
2π∈0 L
C= (3) across electrodes during charging and discharging processes and prevent
loge rr21
device from short circuit. We have aqueous electrolyte (used at low
voltage window) and organic electrolyte (used at high voltage window).
1.1.3. Battery Aqueous electrolyte is preferable because their ionic conductivity is
Battery consists of two or more electrochemical cells which can higher that enhance power density of supercapacitors [24]. Another
convert chemical energy into electrical energy as shown in Fig. 2(e). reason of their usage over organic electrolytes [25] is that to prevent the
These are used as energy conversion and storage devices. It contains a chemical decomposition of electrolytes, operating voltage of super­
limited amount of fuel and oxidant so they provide electrical energy for capacitor cell should be kept low. To enhance electrochemical perfor­
short period of time. Electrodes (e.g. metals zinc, lead and lithium) must mance of supercapacitor, we can use a mixture of aqueous and organic
have good electrical conductivity, high surface area for maximum electrolyte [e.g. H2SO4, KOH] with some redox active species [e.g. K3Fe
capacitance value and compatible with electrolyte for smooth operation (CN)6, KI]. On basis of geometry, Supercapacitor divided into three
of battery. There are two types of batteries namely primary (e.g. Lithium categories namely thin film supercapacitors, flexible (mostly used) type
battery) and secondary (e.g. Lithium-ion battery). Former is non- and planar supercapacitors [26–29]. This review focuses on components
rechargeable (metallic) and later one is rechargeable. Li-ion batteries of supercapacitors and the various types of electrolytes. Electrochemical
hold less energy but supply high load current in comparison to non- characterization techniques such as cyclic voltammetry (CV), galvano­
rechargeable batteries. Both consist of anode, cathode, separator and static charge–discharge (GCD) and electrochemical impedance spec­
electrolyte. Nanostructured cathode materials for Li-ion batteries are troscopy (EIS) are also briefly introduced. Chhetri et al. reported [30]
Lithium Cobalt-oxide (LiCoO2), Lithium Manganese-oxide (LiMnO4), ZIF-8 derived nanoporous carbon composite enfolded with Co3O4-

Fig. 1. Ragone plot of distinct energy storage devices.

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S. Sharma and P. Chand Results in Chemistry 5 (2023) 100885

polyaniline as supercapacitor electrode material, with 1407 Fg− 1 spe­ supercapacitor device is nearly 2.5 mg. Sunaina et al. reported the
cific capacitance at 1 Ag− 1 current density. Furthermore, an asymmetric electrochemical behaviour of α-MnO2. The hydrothermal approach was
supercapacitor with 52.81 WhKg− 1 energy density corresponds to used to create α-MnO2 at two distinct temperatures: 120 ◦ C (M1) and
751.51 WKg− 1 power density and excellent cyclic stability of 88.43 % 150 ◦ C (M2) [33]. The sample manufactured at 120 ◦ C yielded the
after 10,000 cycles at 10 Ag− 1 is constructed. Wan et al. showed [31] the specific capacitance C of 218.8F/g at current density of 0.5 A/g, and
synthesis of nitrogen-doped porous carbon/carbon nanotubes furthermore, the electrochemical analysis (CV and GCD). We have
(CNT@CZIF-2) with 324 Fg− 1 specific capacitance (surface area ~ 287 another three types of supercapacitors namely electric-double layer
m2g− 1) and outstanding capacitance persistence of 93.5 % after 1000 capacitors, pseudocapacitors and hybrid capacitors which can be
cycles. In the current study, [32] Zeolitic Imidazolate Framework-8 (ZIF- distinguished on basis of their charge storage mechanism as shown in
8) was made utilizing a straightforward solvothermal approach at Table 2.
ambient temperature. The newly created pure ZIF-8 exhibits battery-like
redox behaviour in a three-electrode system with redox additive elec­
2.1. Electric double layer supercapacitors (EDLCs)
trolyte (RAE), and at 10 A/g current density, ZIF-8 yields an extremely
high specific capacity (637.5C/g). Mass loading of active materials in
EDLCs have longer cyclic stability as comparison to rechargeable or
reported pristine ZIF-8 is 0.8 mg and for fabricated asymmetric
lithium-ion batteries. There is charge distribution at double layer in

Fig. 2. (a) Schematic diagram of fuel cell as energy storage devices, (b-d) Schematic diagram of parallel plate, spherical & cylindrical capacitor, (e) Schematic
diagram of battery.

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S. Sharma and P. Chand Results in Chemistry 5 (2023) 100885

Fig. 2. (continued).

Table 1 E = 1/2CV 2 (4)

Comparison of various energy storage devices.
S. Energy storage devices Energy density (Wh Power Where, E is energy stored by electrode material of supercapacitor that is
No. Kg− 1) density directly proportional to capacitance (C) and square of voltage (V) [35].
(W Kg− 1) Using coconut shells as a precursor, granular micro/mesoporous carbon
1 Film Caps 10− 2–10− 1 106–107 was produced by a single thermal process [36] with a 93% capacitance
2 Capacitor <0.1 104–106 retention at a high current density of 5 A/g. A straightforward, practical,
3 Supercapacitor 10− 1–101 102–104 and cost-effective method including hydrothermal treatment was used
4 Superconducting Magnetic Energy 101–102
<100
to create a hierarchical porous carbon with a high surface area that was
Storage (SMES)
5 Batteries 101–102 101–102 generated from peanut shells [37]. The carbon electrodes made from
6 Fuel Cells 102–103 <100 peanut shells were discovered to have high capacitance (340F/g),
excellent rate performance (54.7% capacitance retention from 0.25 A/g
to 50 A/g), and exceptional cycle stability (capacitance decay of 4.7%
Table 2 after 10,000 cycles at 1 A/g). For potential energy storage application in
Difference between EDLC, Pseudo-capacitors and hybrid supercapacitors based supercapacitors, watermelon rind (WR) has been proposed as a nitrogen-
on charge storage mechanism. rich precursor of nitrogen-doped activated carbon (WRAC) [38]. In 6 M
Types Electric double Pseudocapacitor Hybrid
KOH at a current density of 1 A/g, the nitrogen-doped WRAC electrode
layer supercapacitor exhibits high gravimetric specific capacitance (333.42F/g), with
supercapacitor 96.82% of capacitance remaining after 10,000 cycles. Using simple and
Sub types • Redox • Asymmetric hygienic pre-carbonization, acid washing, and KOH activation pro­
• Underpotential • Battery type cesses, we effectively created extremely porous carbon with tube-like
deposition • Composite structures from tea waste in the current study [39]. The porous carbon
• Intercalation based
is shown to have large specific capacitances, measuring 332F/g at 1 A/g
Charge Electrostatic Electrochemical Electrostatic and
storage Electrochemical
and 222F/g at 100 A/g. In this paper, we describe an effective one-step
mechanism pyrolysis and activation procedure at various temperatures for the
Process Non-Faradic Faradic Faradic and non- synthesis of hierarchical porous carbon microrods. This demonstrates a
faradic pretty high specific capacitance in a 6 M KOH electrolyte of 406F/g at
Materials • Activated • Transition Metal • CNT//MnO2
0.5 A/g and 335F/g at 10 A/g [40]. One of the nitrogen-rich biomass
Carbon Oxides (MnO2, • PbO2//
• rGO WO3) Graphene wastes used in the process was the soybean pod, which showed superior
• CNTs • Conducting • TiO2@rGO// areal capacitance of 4.70F/cm2 at 10 mA/cm2, and the value could still
• Carbon aerogel Polymer (PANI, CNT be maintained after 10,000 cycles [41] as shown in Table 6.
PEDOT:PSS)
Electrode material is chosen such that they have large surface area
and interconnected mesopores. Careful selection of porosity and surface
terfaces of electrode/electrolyte in which charges are separated by few area of electrodes materials (e.g. activated carbon (AC), carbon nano­
Angstrom and they are static in nature as shown in Fig. 3(a). Overall tubes (CNT) and graphene) plays important role [42–44] in electro­
EDLCs are supercapacitor that store charge electrostatically. During chemical performance of electric double layer supercapacitors. AC have
charging/discharging of battery there is swelling at electrodes. Instead large surface area and low cost [45,46] Range of pore diameter is 1–20
EDLC prevent swelling as there is no faradic reaction at electrodes. We nm. Mesopores have size above 1 nm favours ionic motion between
can use aqueous electrolyte and organic electrolyte for ionic transport electrodes leads to increase in conductivity and capacitance value. Mi­
between two electrodes [34]. But in EDLCs we mainly use organic cropores have size <2 nm prevent ionic motion [47,48]. Micropores are
electrolytes because they store more charge using adsorption of ions due not preferable because too small pore size restricts the mobility of ions.
to their large voltage window between 2 and 3 V. The energy density of For mesoporous carbon, Capacitance per unit area is given below in
supercapacitors is determined as per equation (4) by its operating equation (5).
voltage (V) and capacitance (C).

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S. Sharma and P. Chand Results in Chemistry 5 (2023) 100885

Fig. 3. Classification of supercapacitor. Electric double layer capacitors, Pseudo capacitors, Hybrid supercapacitors.

C ∈r ∈0
= (5) C ∈r ∈0
A r2 ln(r2−r2r ) = (6)
1 A r2 ln ar20

Where, R2 is pore radius, R1 is distance between ion and carbon surface,

Where, A is specific surface area , a0 is effective size of ion.
∈r is relative permittivity of the medium and ∈0 is permittivity of free
Macropores have pore diameter greater than 50 nm. Very wide pores
space or air.
consists of free space prevent electrolyte wetting and rapid ionic motion
For micropores, Capacitance per unit area is described by equation
between current collector electrodes. There is less coordination among
(6).
pore and ion size (for too small < 2 nm and too large greater than 50 nm
pore diameter) leads to decrease in specific capacitance Cs [49].
Overall, pore diameter increases in following order-.

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S. Sharma and P. Chand Results in Chemistry 5 (2023) 100885

Fig. 3. (continued).

Micropore (2 nm) < Mesopores (2–50 nm) < Macropores < (50 nm). properties, selected material for our research work should be of low cost,
Mesopores are preferably used to enhance electrochemical perfor­ environment friendly and work over wide temperature range.
mance of supercapacitor by utilizing the specific surface area (SSA)
more efficiently. They allow easy flow of electrolyte ions across double 2.3. Hybrid supercapacitor
layer of EDLC.
This is most important category of charge storage. Hybrid word in its
name implies that it is a combination of EDLC and pseudocapacitive
2.2. Pseudocapacitor materials as shown in Fig. 3(c). EDLC electrode materials are activated
carbon (AC), carbon nanotubes (CNT), graphene and pseudocapacitive
In this category of charge storage there is faradic transfer of charge electrode materials are conducting polymer [52] and metal-oxides.
between electrodes and electrolytes. Redox charge transfer plays sig­ Hybrid supercapacitor is constructed by using conducting polymer as
nificant role in pseudocapacitors as shown in Fig. 3(b). It is known that positive electrode known as anode and activated carbon as negative
pseudocapacitive electrodes, which rely on transfer of electrical charges electrode known as cathode. Electrode materials are chosen in such a
through redox reactions and intercalation/de-intercalation processes of way that they complete the kinetics so that there is no imbalance in
electrode materials beyond electrostatic adsorption, typically RuO2 and charge/discharge rate. On the basis of chosen material for electrodes,
MnO2. Their capacitance values are relatively constant within the po­ hybrid supercapacitors are further divided into three categories namely
tential window. Redox reaction is that in which oxidation and reduction asymmetric hybrids [53–55], battery type hybrid and composites hy­
takes place simultaneously. Charge stored Q is directly proportional to brids (e.g.Fe3O4/graphene, rGO-f/PANI).Cathode store charges by sur­
voltage Vas described in equation (7). face adsorption/desorption called non-faradic process and anode store
Q = CV (7) charges by intercalation called faradic process [56]. In battery-type
electrodes, in which charge storage is faradaic in nature, their specific
The differentiation of charge (Q) with respect to time (t) gives cur­ capacity values vary with the voltage window and their specific capacity
rent (I) as described in equation (8). is better expressed in Cg− 1 or mAhg− 1. Overall they store charges by
dV both faradic and non-faradic processes thereby remove disadvantages of
I=C (8) EDLC and pseudocapacitor. They are of low cost, provide better per­
dt
formance characteristics, works over wide temperature range, high en­
Where, C is proportionality constant, known as specific capacitance ergy density, power density, mechanical strength, cyclic stability and
measured in Fg− 1 or Fcm− 2 . Pseudocapacitor electrochemical perfor­ low resistance. Hybrid supercapacitor mostly used in vehicles as power
mance lies between batteries and EDLCs. They have high capacitance sources [57].
and low power density than EDLCs. With redox charge transfer there is
transfer of charge by under-potential deposition (deposition of lead on 3. Synthesis strategies for electrode materials
gold) and intercalation process also [50]. Bulk lattice of taken electrode
is inserted by cations is called intercalation. Conducting polymers (e.g. Various synthesis [58] techniques differ from each other in initiating
PANI, rGO-f/PANI), Metal-oxides (e.g. RuO2, IrO2, V2O5). They have materials (e.g. Solvents, inorganic salts) and synthesis condition (e.g.
good electrical conductivity, long cycle life, low current density, high temperature, pressure, PH composition, solute and solution concentra­
power density and high capacitance value [51]. With all these tion). Some synthesis approaches are as follows:

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S. Sharma and P. Chand Results in Chemistry 5 (2023) 100885

3.1. Chemical vapour deposition (CVD) specific capacitance of 2157 Fg− 1 and excellent cyclic stability with
capacitance retention of 96.5% after 10,000 charge/discharge cycles.
This synthesis method is mainly used for preparation of Mxenes,
transition metal oxide (TMO) and 3-D porous surfaces namely metal 3.7. Electrodeposition
oxide frameworks (e.g. ZIFs from precursors and templates). MOFs have
high specific surface area and porosity. High SSA and porosity plays an This is facile method for synthesis of different morphological mate­
important role in CVD synthesis [59]. Take material in vapour form then rials on the basis of careful selection of deposition (no toxic), PH of
put it in high temperature limit leads to the formation of even solution. Conducting polymer (CP), MTMO and mesoporous asymmetric
morphological structures. For instance-Synthesis of graphene by CVD supercapacitor (e.g. PANI) electrode materials are generally synthesized
have high mobility in cell. by electrodeposition. Take a precursor solution in which nanoparticles
are co-electrodeposited [65] then these nanoparticles starts to decom­
3.2. Physical vapour deposition (PVD)/Physical vapour transport (PVT) pose under suitable thermal conditions. By using the electrodeposition
approach, Kaur et al. create a NiCo2O4 electrode for supercapacitors at
Take material in solid or liquid form, convert it into gaseous form by deposition time of 6 min (NC6) and 10 min (NC10). The outcomes
evaporation and finally come back to solid phase by deposition. PVT is demonstrated that at a scan rate of 1.0 mV/s, the NC6 sample exhibited a
generally used to produce thin films [16] (e.g. thin film solar panels). very high specific capacitance value of 1472F/g. The NC6 sample had a
PVD is also used to create coating for instance put a ceramic powder flower-like arrangement, according to scanning electron microscopy
(solid form) in plasma. It ionizes ceramic solid because plasma exists at (SEM) research, while the NC10 sample had the morphology of a sea
very high temperature (7000–10,000 K) and lastly we get ceramic coral. For instance-electrodeposition of CoO-PPY on 3D Ni foam in
coating by condensation. aqueous (KOH, NaOH) electrolyte have specific capacitance Cs of 2223
Fg− 1 with retention of 99.8% after 2000 charge/discharge cycles.
3.3. Hydrothermal synthesis Electrode materials for supercapacitor applications prepared by this
approach have high specific capacitance, high energy and power density
This synthesis approach is widely used as it involves preparation of and excellent cyclic stability.
electrode materials with high homogeneity and purity under controlled
physical and chemical attribute. Hydrothermal [60] is a combination of
two words hydro (means water) and thermal (means temperature). In 3.8. Chemical precipitation synthesis
this synthesis of material, take water [61] as solvent in a closed vessel at
temperature above 100 ◦ C and pressure above 1 bar. This technique is used for large scale production of micro/nano­
particles [66]. Dissolve a highly concentrated solute into supersaturated
3.4. Solvothermal method solution at high temperature. We get precipitates after filtration. It is
difficult to determine morphology of materials because this process have
In this method water is replaced by organic solvent (e.g. ethanol, high reaction rate.
methanol, amines) or carbon containing inorganic solvent (e.g. carbides,
carbon dioxide). Dielectric constant and solubility of solvent changes 3.9. Metal organic framework (MOF)/porous polymers
drastically in saturated phase [58]. Many materials as [61] super­
capacitor electrode have been prepared by this method (e.g. hexagonal MOF [67] [e.g. zeolitic imidazolate framework (ZIF)] as templates or
NiCo2O4 nanoparticles). Both hydrothermal/solvothermal synthesis precursors are widely used for synthesis of porous carbon materials and
provide information about morphology of materials by careful selection mixed transition metal oxides (MTMO). They can produce one (1D), two
of temperature, pH and concentration of solvent. (2D), three (3D) dimensions nanocomposites [68]. Instead of bare MOF,
its composites with activated carbon, metal oxides, graphitic carbon are
3.5. Direct coating preferably used as supercapacitor electrode material to enhance capac­
itance, specific surface area (SSA), energy density and power density of
As its name implies it involves direct enforcement [62] of active supercapacitor. They have unique structural properties with high spe­
material (e.g. carbon black, PTFE) with maximum adhesion onto cific surface area. Most of bare MOFs have poor conductivity that resists
substrate. ionic motion between electrodes. This limitation of MOFs as precursor or
template is removed by producing their composites with activated car­
3.6. Sol-gel technique bon, transition metal oxide, composite polymer, graphitic carbon and so
on. For instance, when we use bare ZIF-67 as precursor in 6 M KOH
The word sol in its name implies that micro/nanoparticles agglom­ electrolyte at 0.5 Ag− 1 current density having 1723 m2g− 1 specific
erate in solution, and then these sol links together to form long chain surface area, 190 Fg− 1 capacitance. Instead its composite symmetric
called gel [53]. This technique is mainly used for preparation of tran­ supercapacitor device The two-electrode symmetrical supercapacitor
sition metal oxides (TMO) at STP by two methods namely colloidal device, that is, “ZIF-67/rGO//ZIF-67/rGO” was first studied for its
method and polymeric method. S. Saini et al. used a hydrothermal working potential window. The ZIF-67/rGO [69] in presence of redox
method for synthesis of h-WO3 at room temperature and reported the additive electrolyte (RAE) has high specific capacitance (326 Fg− 1) at 3
nanorods morphology of h-WO3. The as-prepared electrode showed Ag− 1 current density with energy density (25.5 KWKg− 1) and power
outstanding specific capacitance (432.5F/g at 1 A/g) in 6 M KOH elec­ density (2.7 KWKg− 1). This composite have excellent cyclic stability
trolyte and excellent cyclic stability [63]. These two methods [64] can with 88% retention after 1000 charge/discharge cycles. The values of
be distinguished on the basis of precursors used. Precursor is mixed in specific capacitance with ZIF-67/rGO and ZIF-67 electrodes (at a current
water for colloidal and with organic solvent (e.g. alcohol) in polymeric density of 4.5 A g− 1) have been estimated as 1453 and 1014F g− 1,
method. Synthesized MTMO from this approach is of low cost, highly respectively. A higher specific capacitance by ZIF-67/rGO is explained
homogeneous, better electrochemical performance, high specific surface by the incorporation of rGO nanosheets which facilitated faster electron
area and pure. We get different morphological materials from this transport and more efficient diffusion of ions into the redox sites of the
technique depends on temperature, pressure, solvent under consider­ composite material. Further, the ZIF-67/rGO electrode has also shown a
ation, type of surfactants fabrication and reaction time. Liu et al. have good long-term cyclic stability as it retained almost 90% of its capacity
reported NiO/LaNiO3 composite fabricated by sol gel technique with after 1000 continuous charge–discharge cycles.

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S. Sharma and P. Chand Results in Chemistry 5 (2023) 100885

3.10. Other synthesis approaches functioning voltage window and resistance. The energy density is
related to the square of the voltage window, but the ionic resistivity is
SC electrode materials can also be fabricated by pulsed layer depo­ inversely proportional to the power capability of the cell. As a result,
sition method, dealloying method, In-situ polymerization and vacuum proper choice of the best electrolyte is essential [72] in the fabrication of
filtration technique [70]. high performance supercapacitors. Electrolytes with superior chemical
and electrochemical stabilities offer wider potential windows without
4. Components of supercapacitor compromising performance. Electrolyte materials should have minimal
volatility, flammability, and corrosion potential to facilitate the safe
Proper selection of electrode material, electrolyte, separator and functioning of ESs. The electrolyte nature includes [73]:
current collector plays important role in overall performance of super­
capacitor [71].The following section discusses each component of • Size and type of ion
supercapacitor in detail. • Concentration of ion
• Type of solvent
4.1. Electrode materials and electrode fabrication • Interaction between the ions and solvent
• Interaction between electrode material and electrolyte
Commonly used electrode materials are activated carbon, graphene, • Voltage window
carbon nanotubes, conducting polymers and transition metal oxides.
Working electrode was fabricated by mixing active material for instance, These all factors have major impact on the capacitance, power
ZIF-8, acetylene black and polyvinylidene difluoride (PVDF) in the ratio density, energy density and cycle life of the supercapacitors. Each
8:1:1. PVDF act as binder material produced by polymerization of electrolyte type is thoroughly discussed in the following section.
vinylidene difluoride. Mix all the three compounds properly using
mortar and pestle. Then add 3–4 drops of N-methyl-2-pyrrolidone 4.2.1. Aqueous electrolyte
(NMP) solvent dropwise to mixture under constant stirring for over­ Aqueous electrolytes have been widely employed in research and
night. This prepared homogeneous slurry was then glued on nickel mesh development because they are easier to handle in the laboratory than
with 1*1 cm2 area and dried for 12hrs in oven at 80 ◦ C as shown in Fig. 4 organic electrolytes and ionic liquids, which need purifying processes.
(a). Aqueous electrolytes [74,75] typically have high conductivity, such as
0.8 S/cm2 for 1 M H2SO4, which is atleast one order of magnitude
4.2. Electrolyte greater than organic and ionic liquid electrolytes. High conductivity is
useful for decreasing the equivalent series resistance (ESR) and leads to
The electrolyte means the salt of electrolyte plus solvent, act as key better power density. The widely popular aqueous electrolytes include
components for electrochemical supercapacitors. They have significant H2SO4, KOH, and potassium chloride (KCl), which have the advantage of
impact on the formation of the double-layer and availability of pores to being easy to handle [76,77] in an open environment and having low
electrolyte ions. Electrolytes have a direct impact on the cell’s ionic resistance. The downsides of aqueous electrolytes include

Fig. 4. (a-c) Schematic diagram for electrode fabrication and three electrodes set up.

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S. Sharma and P. Chand Results in Chemistry 5 (2023) 100885

Fig. 4. (continued).

corrosion and poor stability-window (ΔV) concerns, which limit cell tetrafluoroborate, tetraethylphosphonium tetra-fluoroborate, and trie­
performance and stability. Acidic or basic pH values in a system can thylmethylammonium tetrafluoroborate are among the salts used inor­
include corrosion of packaging materials and collectors. Corrosive re­ ganic electrolytes. Salts with lesser uniform structures have lower crystal
actions degrade system performance and diminish cycle lifetimes. Due lattice energy and hence higher solubility. Furthermore, there are also
to water breakdown at 1.23 V, aqueous electrolytes [78] often restrict more challenges to consider when employing organic electrolytes in
their cell voltage to 1 V. The low voltage stability of aqueous electrolytes supercapacitors [81]. Organic electrolytes are often more expensive
severely limits the energy and power density that may be achieved in an than aqueous electrolytes, have a lower specific capacitance, poorer
ES. While Tomiyasu et al. reported [79] the widest voltage window of conductivity, and safety problems related to flammability, toxicity, and
3.2 V for aqueous electrolytes by using saturated aqueous solution of volatility.
sodium perchlorate (SSPAS). Based on this result, it can conclude that
SSPAS could replace non-aqueous electrolyte for attaining superior 4.2.3. Redox additive electrolyte (RAE)
electrochemical properties. Supercapacitor performance showed enormous increment when
electrode is assembled with RAE due to increment in redox active sites
4.2.2. Organic electrolyte on both electrode surface and electrolyte in comparison of aqueous
Organic electrolytes presently lead the commercial electrochemical electrolytes. Its large voltage window leads to enhancement in energy
supercapacitors industry due to its potential operating window of 2.2 to density that is usable in many applications. S. et al. reported the syn­
2.7 V [80]. Acetonitrile (ACN) and propylenecarbonate (PC) are the thesis of ZIF-67/rGO [69] composite in presence of RAE, thereby
most often utilized organic electrolyte solvents. ACN may dissolve more showed improvement in conductivity, surface area, high retentivity
salts but is hazardous, whereas PC-based electrolytes are more ecolog­ after 1000 charge–discharge cycles.
ically safe, with a broad working voltage, high working temperature,
and lower but reasonably strong conductivity. Tetraethylammonium

9
S. Sharma and P. Chand Results in Chemistry 5 (2023) 100885

4.2.4. Ionic liquids molecular contact, which improves performance by reducing interfacial
Ionic liquids (ILs) are beginning to address organic solvent safety resistance between active layers and current collectors. The connection
concerns and enhance crucial properties for usage in electrochemical between the electrode and the metal collector might weaken over time
supercapacitors. Ionic liquids [82] are also recognized as room tem­ owing to shrinkage and electrode material loss to the electrolyte. These
perature/low temperature molten salts and are described as salts that losses result in increased resistance, decreased capacitance, and
are entirely constituted of ions and have a melting point of <100 ◦ C. decreased device cycle life. Like a situation may be avoided by using
Room temperature ionic liquids are appealing to supercapacitors polymeric binding agents [87] such as nafion and polytetrafluoro­
because they are non-volatile, poorly flammable, and heat-resistant, all ethylene, which prevent the separation of active material from the
of which are unusual and impossible to achieve with standard solvents current collectors. Binders strengthen the collector-electrode interface’s
[83]. ILs has the broadest operating voltage window (0 to 3–5 V) and can endurance and prevent it from deteriorating over time. Another effective
be heated up to 300 ◦ C without vaporization. Ionic liquids have sparked technique to deal with this scenario is to guarantee good contact and
considerable attention as alternative electrolytes owing to their unique operations involving collector surface treatment, such as imparting an
structures and characteristics. Ionic liquids used for supercapacitors extra conducting coating with the binding chemicals. Nickel mesh,
includes sulfonium, ammonium, pyrrolidinium, imidazolium, and nickel foam, and aluminium sheets have been employed as current
phosphonium cations as well as tetrafluoroborate (BF4), hexa­ collectors in recent years. The active electrode materials are directly
fluorophosphate (PF6), bis(fluorosulfonyl)imide (FSI), bis(tri- placed on these conducting materials. A polymer serving as a binder is
fluoromethanesulfonyl)imide (TFSI), and dicyanamide (DCA) anions. utilized in some circumstances to improve the adherence of active ma­
However, in comparison to aqueous and organic electrolytes, ionic liq­ terial to current collectors. However, it is critical to select an appropriate
uids have a constraint of limited ionic conductivity. In the system, the binding material that has no effect on the performance of the active
electrolyte serves two functions. It not only participates in conductance, material. Using conducting polymers as binders might improve
but it also serves as a pathway for dissociation. performance.

4.3. Separator 5. Basics of electrochemical (EC) workstation

Separators [84] prohibit contact and electron transfer between two 5.1. Cyclic Voltammetry (CV)
electrodes. A separator should be mechanically strong in order to offer
device reliability and avoid active materials migration over time. CV is a powerful and ubiquitous electrochemical technique used to
Inadequate quality separators can reduce overall cell performance by understand the complete behaviour of a system, both thermodynami­
introducing extra resistance. In the worst-case scenario, the entire cell cally and kinetically [88,89]. It is a useful method for measuring the
may be short-circuited. As a result, selecting a separator [85] is a critical current response of a redox active solution and recording the current
step prior to cell formation. The separators must comply with the versus potential. CV is hallmark of electrochemical analysis. It is a so­
following requirements: phisticated potentiometric and voltammetric method. Potentiometry is a
method of measuring electric potential of an electrochemical cell under
• Separators must be non-conductive static conditions and in voltammetry [90,91] current is measured while
• Separators must be chemically resistant to corrosion from electro­ potential between two electrodes is varied. CV measurements carried
lytes and by-products of electrode deterioration. out at different scan rates in unit of mVs− 1 with constant current density
• The material should possess electronic insulating properties and in Ag− 1. The derivative of charge Q with respect to potential V is dif­
excellent ion conductance. ferential capacitance C, which gives relevant information about process.
• The electrolyte should be able to wet the separators easily. By 3-electrodes set up, we get a characteristics duck-shaped plot known
as a cyclic voltammogram as shown in Fig. 4(b, c) [92]. Requirements of
Material like glass, paper, and ceramics are used as separators. 3-electrode electrochemical cells:
Polymer-based separators like polyvinylidene difluoride, poly­
propylene, polypropylene-carbonate, and polyethylene have been • Working electrode (WE), where compound of interest is reduced or
widely employed in supercapacitors owing to their reasonable cost, oxidised. As its name suggests, this is the electrode where electro­
porous nature, and flexibility. Polypropylene is the most extensively chemical reaction takes place. WE must be conductive so that
utilized of these polymers due to its ease of wettability. Paper-based charges can move to and from the solution. WE made up of
separators are also employed; however they have low mechanical unreactive material to achieve inertness and they must not have any
strength and endurance in high-temperature operation conditions. The redox properties on its own. For instance- platinum, gold, graphite
existence of a separator in a supercapacitor guarantees that ions are electrodes etc. The electrolyte, solvent and nature of the WE all in­
transported smoothly without undergoing any chemical changes. fluence the potential window that can be used for a CV experiment.
Type of WE can be varied from experiment to experiment. Electrode
4.4. Current collector surface must be clean and its surface area well defined. Cleaning of
electrode surface is done by mechanical polishing followed by son­
The current collector [86] transports current from the current source ication in ultrapure water.
to the electrode and from the electrode to the external load while also • Reference electrode (RE)-It is a stable and non-polarisable electrode.
performing the secondary function of heat dispersion developed within It is used as a reference point against which potential of other elec­
the cell. As a result, they must be electronically conducting as well as trodes can be measured in an electrochemical cell. The most common
durable in the cell environment, able to endure chemical degradation RE is saturated calomel electrode, AgCl/Ag electrode. In non-
from electrolytes. In most circumstances, charge conduction through an aqueous solvents, reference electrodes based on Ag+/Ag couple are
electrode’s active material is inadequate, resulting in greater resistance usually used.
that might degrade the performance characteristics of an otherwise • Counter electrode (CE)-Current flows between WE and CE when
excellent electrochemical supercapacitor material. Efficient and effec­ potential is applied to WE. That current is recorded by CE in order to
tive contacts and additives are required to successfully carry charge complete the electrical circuit in an electrochemical cell. For
current and deliver sufficient power to a system. Aluminium, steel, iron, instance, large area Pt electrode, Mesh type Pt electrode.
copper, and alloys are examples of current collectors. Furthermore, • Supporting Electrolyte-Chosen electrolyte can be aqueous or organic
directly coated active materials onto current collectors can offer strong depending on which electrode materials are used. Electrolyte must

10
S. Sharma and P. Chand Results in Chemistry 5 (2023) 100885

be highly soluble in solvent chosen. It is chemically and electro­

∫v+
chemically inert in conditions of experiment. It can be purified. A Where, IdV = Integral area of CV curve, (v+ − v− ) = operational poten­
v−
solvent must be chosen which dissolves both compound of interest
tial window.
and electrolyte. Concentrations of redox species at electrode surface
or simply, it can be written as,
is determined by Nernst equation [93] which is defined in equation
(9). 1
∫V
Cs = I(V)dV
RT Cred 2 × m × v × ΔV Vo
ET = E 0 − ln (9)
nF Cox
Where m = mass of active material on electrode in gram, v = scan rate,
∫V
where, ET = Reversible cell voltage at an arbitrary temperature T, E0 = ΔV = potential window and Vo I(V)dV = area under the curve.
Standard-state reversible cell voltage, F=Faraday’s constant, R = Gas There are many applications of CV like, it provide electrochemical
constant, Cred =Concentration of reductive species, Cox = Concentration synthesis of conducting polymers, nanoparticles films on electrodes,
of oxidative species. determining the reversibility and electron transfer kinetics of a reaction,
The peak current of the reversible redox reaction is described by the study of corrosion phenomena of metals. CV provides useful applications
Randles-Sevcik equation. Relation between concentration and peak in energy conversion and storage for lithium-ion batteries, super­
current [94] is given by Randles-Sevcik equation which is defined in capacitor [99], fuel cells, SMES and capacitor. It is highly useful in other
equation (10). fields like materials science, photonics, cell biology, neuroscience,
electrical engineering and condensed-phase physics.
(10)
3 1 1
ip = 2.69*105 AC0 n2 D2 v2

Where, ip = peak current A = Area of electrode, D = Diffusion coefficient 5.2. Galvanostatic Charging-Discharging (GCD)/Chronopotentiometry
(cm2 /s), C0 = Concentration, v = Scan rate, n is the number of electrons. (CP)
Dunn et al. gives another general relationship between peak current i
and sweep rate v as described in equation (11). Along with CV, GCD data is also used to evaluate specific capacitance
CCD , energy and power densities. These measurements carried out at
i(V) = av b
(11) different charge densities, for example, 1Ag− 1, 2 Ag− 1 and so on that
Diffusion controlled contribution and capacitive contribution is records potential variation with time. Cyclic stability is determined by
determined by calculating the value of b. Kinetic performance of various GCD curve by measuring its charging-discharging time. Current density
nano-electrode materials is calculated by this equation. We can distin­ and specific capacitance [100] have inversely proportional relationship.
guish EDLC, pseudocapacitance and battery type materials by value of b For EDLC [101] materials, GCD curve is linear and value of b is always
and by shape of CV curve as shown in Table 3. For EDLC materials, CV equal to 1, indicating good electrochemical capacitive nature. For
curve is rectangular [95,96] and value of b is always equal to 1. If CV pseudocapacitive [102] materials, charging-discharging profiles have
curve retain a ideal rectangular shape with increment of scan rate non-linear variation due to quasi reversible faradic reactions as shown in
without shifting of anodic peaks positively and cathodic peaks nega­ Table 3. Charge/voltage ratio of these faradic reactions no longer re­
tively, indicating superior capacitive nature. For pseudocapacitive [97] mains constant and varies with time, give non-symmetric curve. For
materials, CV curve is approximately rectangular with some inflection battery type materials, GCD curve has plateaus as shown in Fig. 5(c)
points and b value is close to 1. Unit of capacitance is farad denoted by F [98]. Specific capacitance of fabricated electrode from GCD data is
give charge storage capability. For battery-type materials, CV curve has calculated using equation (13).
redox peaks shows a quasi-reversible electron transfer process with 0.5
∫V +
value of b as shown in Fig. 5(a). Sweep rate for all materials is low 2Im
CCD = Vdt (13)
because at high sweep rate, ohmic contribution plays significant role. V2
We get four configurations of asymmetric and hybrid supercapacitor as
V−

shown in Table 4 and Table 5. Different ways of combining these EDLC, Where, CCD = charging-discharging capacitance, V = operational
pseudo and battery type electrodes to get asymmetric and hybrid V
∫+
supercapacitor is shown in Fig. 5(b) [98]. voltage window, Im is current density in Ag− 1 , Vdt is current integral
V−
We can evaluate specific capacitance Cs [20], energy density and
area.
power density of fabricated electrodes by using CV data. Cs value is high
Or simply, it can also be written as,
at lower scan rate due to attainability of large time for electrolyte ions to
undergo adsorption/desorption at electrode surface. Specific capaci­ I × Δt
tance (C, Fg− 1) of fabricated electrodes can be calculated from CV curve
Cs =
ΔV × m
with the help of equation (12) given below-
Where I, Δt, ΔV, m corresponds to discharge current (A), discharge time
∫v+
IdV (s), potential window (V) and the mass of active materials (g), respec­
Cs = (12) tively.
mv(v+ − v− )
v− For better electrochemical performance of supercapacitor [103]
rapid charge–discharge and negligible voltage drop (low internal resis­
Table 3 tance) is required. With increase in current density, power density de­
Distinguish EDLC, Pseudo-capacitors and hybrid supercapacitors based on CV creases and energy density, [10] on contrary increases. The specific
curve shape (b value). energy density E in unit of watt-hours per kilogram is shown in equation
Materials EDLC Pseudo-capacitive Battery type (14).

CV shape Rectangular Nearly Rectangular Redox peaks 1

E = Cs (ΔV)2 (14)
Formula i = avb i = avb i = avb 2
Value of b 1 ̴1 0.5
Unit F F C or mAh Where,ΔV is operational voltage window, Cs = Specific capacitance of
GCD profile linear Almost linear plateau fabricated electrode. The specific power density P in unit of watt per
Sweep rate low low low
kilogram is described in equation (15).

11
S. Sharma and P. Chand Results in Chemistry 5 (2023) 100885

Fig. 5. (a) Distinct shape of CV for EDLC, pseudo capacitive and battery type material. (b) Asymmetric and hybrid different configurations of distinct CV by
combining materials A and B. (c) GCD profile to distinguish EDLC, pseudo capacitive and battery type material [Reprinted with permission from Ref. [98] © John
Wiley and Sons (2019)]. (d) General circuit diagram for electrochemical impedance spectroscopy (EIS).

12
S. Sharma and P. Chand Results in Chemistry 5 (2023) 100885

Table 4 (I*(ΔV))
Configuration for fabrication of asymmetric supercapacitor devices.
P= (15)
m
S. Device configurations for asymmetric supercapacitors
No. Where, I = Applied constant current, m = Total mass of supercapacitor
in grams. Similarly, from GCD [104,105] data we can calculate specific
1 EDLC positive electrode Pseudocapacitive negative
electrode
capacitance, energy and power density of two electrode symmetrical
2 Pseudocapacitive positive electrode EDLC negative electrode supercapacitor. This series combination of two supercapacitors illumi­
3 EDLC positive electrode L EDLC negative electrode K nates a white LED [69]. Comparison of various carbon-based, metal-
4 Pseudocapacitive positive electrode Pseudocapacitive negative oxides, metal-sulphides, metal–organic frameworks (MOFs) as super­
M electrode N
capacitor electrode material are shown in Table 6.

Table 5 5.3. Electrochemical impedance spectroscopy (EIS)

Configuration for fabrication of hybrid supercapacitor devices.
S. No. Device configurations for hybrid supercapacitors Electrochemical impedance spectroscopy (EIS) is a powerful test that
1 EDLC positive electrode Battery-type negative electrode provide information regarding series resistance Rs , charge transfer
2 Battery-type positive electrode EDLC negative electrode resistance Rct , double layer capacitance Cdl and warburg impedance Zw
3 Battery-type positive electrode Pseudocapacitive negative created by diffusion [106,107] as shown in Fig. 5(d). Impedance Z equal
electrode
to 1010 Ω is limit of measurement capability of most EIS instruments.
4 Pseudocapacitive positive Battery-type negative electrode
electrode The common electrical circuit elements are resistor (Z = R), inductor
1
(Zl = iwL) and capacitor (Zc = iwC ). EIS [108,109] provide super­
capacitors with an alternating current in frequency range 0.01 Hz to 1
mHz These electrical circuits have Nyquist and bode plot. In Nyquist
[110] plot, real part of impedance Z(w) = Z0 (cosθ + isinθ)is plotted on X-

Table 6
Comparison of various carbon-based, metal-oxides, and metal–organic frameworks (MOFs) as supercapacitor electrode material.
S. Electrode Morphology Surface area Specific Electrolyte Cycle stability Reference
No. (m2g− 1) capacitance/
capacity

1 Activated carbon from Rougher and irregular 1532 228 at 5 6 M KOH 93% after 3000 [36]
Coconut shell mVs− 1 cycles
2 ZIF-8 Hexagonal 877 637.5C/g at 10 0.35 M [K4(Fe 75% after 1500 [32]
Ag− 1 (CN)6)].3H2O in 6 M cycles
NaOH
3 Activated carbon from Blocky structure 1549 340 at 1 1 M H2SO4 95.3% after [37]
Peanut shell Ag− 1 10,000 cycles
4 ZIF-8 (Calcined at 300 ◦ C) Agglomerated granules – 77.5C/g at 10 mV/s 6 M KOH 80% after 1500 [58]
cycles
5 Activated carbon from Porous structure 2277 333.4 at 1 6 M KOH 96.8% after [38]
Watermelon rind Ag− 1 10,000 cycles
6 ZIF-8 Rectangular plates – 42.22F/g at 10 6 M KOH – [61]
mV/s
7 Activated carbon from Rod-like 1610 332 at 1 6 M KOH 97.8% afer [39]
Tea waste buds Ag− 1 100,000 cycles
8 CNT@CZIF-2 necklace 287 324F/g at 0.5 6 M KOH 93.5% after [31]
Ag− 1 1000 cycles
− 2
9 Nanoporous NiCo2O4 Porous 40.6 mFcm 2157F/g at 0.133 2 M KOH 96.5% after [64]
thin film mAcm− 2 10,000 cycles
10 Activated carbon from Rod-like 2757.6 406 at 0.5 6 M KOH 97% after 5000 [40]
Albizia flowers Ag− 1 cycles
11 Co3O4-PANI@ZIF-8NPC rhombic dodecahedron 52.29 1407F/g at 1 3 M KOH 87.7% after [30]
nanocomposite Ag− 1 10,000 cycles
12 NiCo2O4 Porous flower-like – 1462.8F/g at 1 2 M KOH 83% after 2500 [65]
Ag− 1 cycles
13 NiCo2O4 Sea-coral – 756.71F/g at 1 2 M KOH 81% after 2500 [65]
Ag− 1 cycles
14 ZIF-67 3D polyhedral shape 947 1014F/g at 4.5 0.2 M K3[Fe(CN)6] in1M – [69]
Ag− 1 Na2SO4
15 ZIF-67/rGO composite Uniform growth of the MOF crystals 571 1453F/g at 4.5 0.2 M K3[Fe(CN)6] in1M 90.5% after [69]
over the sheet-like surface of rGO Ag− 1 Na2SO4 1000 cycles
16 Activated carbon from Tube-like 2612 352.6 at 0.5 1 M Na2SO4 94.2% after [41]
Soyabean pods Ag− 1 50,000 cycles
17 α-MnO2 Nanorods-assembled micospheres – 218.8F/g at 0.5 1 M KNO3 92% after 5000 [33]
Ag− 1 cycles
18 α-MnO2 Nanofibres – 199 at 0.5 1 M KNO3 69% after 5000 [33]
Ag− 1 cycles
19 h-WO3 Nanorods – 741 at 1 0.5 M H2SO4 46% after 5000 [63]
Ag− 1 cycles
20 h-WO3 Nanorods – 290.9 at 1 1 M KNO3 65% after 5000 [63]
Ag− 1 cycles
21 h-WO3 Nanorods – 432.5 at 1 6 M KOH 80% after 5000 [63]
Ag− 1 cycles

13
S. Sharma and P. Chand Results in Chemistry 5 (2023) 100885

axis and imaginary part is plotted on Y-axis. Phase angle is θ = arg.Z. density simultaneously.
These plots contain semicircles in high frequency region which is a
characteristic of faradic redox reactions or electronic conduction of 7. Conclusions
electrode, 45◦ straight line at medium frequencies related to molecular
diffusion known as Warburg region and 90◦ straight line at low fre­ In summary, the present review summarizes the historical back­
quency indicates formation of double layer on electrode surface. Charge ground of various energy storage devices for instance, fuel cell, capac­
transfer phenomena between electrode–electrolyte interfaces are itor, battery and supercapacitor. Proper selection of electrode &
possible when there is extension of semicircle from high to medium electrolyte material, separator and current collector plays important role
frequencies region. Equivalent series resistance Rs is represented by in overall performance of supercapacitor is also discussed in this review.
intercept of semicircle [111] on real axis. Charge transfer resistance Rct Many carbon-based materials, metal-oxides, and metal–organic frame­
is estimated by analyzing low-frequency regions. Its low value provides works have been briefly addressed here as potential supercapacitor
fast charge transfer mechanism. Bode plot is plotted between w along X- electrode materials. The present study also provides detailed explana­
axis and phase shift θ or logZ along Y-axis. Faradic impedance Rf for tion of Cyclic Voltammetry (CV), Galvanostatic Charging-Discharging
charge transfer and diffusional processes is determined by using equa­ (GCD)/Chronopotentiometry (CP), Electrochemical Impedance Spec­
tion (16). troscopy (EIS) techniques. The resulting energy conversion/storage
equipments will be economically feasible soon, beneficial to overpower
Rf = Rct + Rw (16)
worldwide energy trouble.
1
Where, Rw = σ with Warburg coefficient σ in units of Ω rad2 s− 1 .
w2
1
CRediT authorship contribution statement
And warburg impedance Zf is calculated using equation (17).
Swati Sharma: Conceptualization, Methodology, Writing – original
2 1
Zf = ( )2 σ (17) draft. Prakash Chand: Conceptualization, Resources, Supervision,
w
Validation, Writing – review & editing.
Theoretically, Phase angle for bode plot is determined by using
equation (18) as described below.
Declaration of Competing Interest
σ
1
θ = tan [ − 1 w2
σ ] (18) The authors declare that they have no known competing financial
Rct + 1
w2
interests or personal relationships that could have appeared to influence
For reversible process,Rct = 0 < = 45◦ . For quasi-reversible the work reported in this paper.
process,Rct > 0 < 45◦
And the capacitance of Electrical double layer that is Cdl is deter­ Data availability
mined by using equation (19).
Data will be made available on request.
1
Cdl = 1 (19)
σ w2
Acknowledgements
Where, w = angular frequency in units of rad s− 1 .
On Nyquist plot, Warburg impedance appears as diagonal line with a The authors are also grateful to the Director, NIT Kurukshetra for
slope of 45◦ On bode plot, Zf exhibits a phase shift of 45◦ Values of Rw providing the facilities in Physics Department.
and Rct must be low for negligible IR drop that provide large output
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