SuperCap - Ref - J of Solid State Electrochem 23 (2019) 667-692 - Background+Fundamental Understanding+progress in Elecctrocchemiccal Capacitors

Journal of Solid State Electrochemistry (2019) 23:667–692
https://doi.org/10.1007/s10008-018-4160-3
REVIEW
Background, fundamental understanding and progress

in electrochemical capacitors
Yogesh Kumar 1 & Sangeeta Rawal 2 & Bhawana Joshi 2 & S. A. Hashmi 3
Received: 10 August 2018 / Revised: 15 November 2018 / Accepted: 19 November 2018 / Published online: 2 January 2019
# Springer-Verlag GmbH Germany, part of Springer Nature 2019
Abstract
Supercapacitors means electrochemical capacitors are being considered these days to be a good alternative for the conventional
power sources (fuel cells and batteries) in many applications because of their high power density, long cycle life and less charging
and discharging time. This review article presents an overview of different types of supercapacitors (electrical double-layer
capacitors (EDLCs), pseudocapacitors and hybrid supercapacitors. The device configurations (symmetric, asymmetric and
hybrid), the mechanism of charge storing at the surface (ion adsorption for EDLCs and fast surface redox reactions for
pseudocapacitors) and the effect of electrode material (activated carbon, carbon aerogels, carbon fabrics, carbide-derived carbons,
carbon nanotubes (CNTs), graphene, biomass, etc. for EDLCs and conducting polymers and insertion type compounds for
pseudocapacitors) and electrolytes are crucial. Electrolytes used in the supercapacitors also play important role to determine
its operating voltage range, energy density, power density, etc. Both the classes of electrolytes, liquid electrolytes (aqueous,
organic, ionic liquids) and solid electrolytes (polymer-based electrolytes) are also discussed in the last section of this review. The
voltage range, energy density and power density ultimately define their use for different applications namely heavy electric
vehicles and portable electronic devices.
Keywords Electrical double-layer capacitors . Bio-resource derived carbon . Graphene . Electrolytes . Metal oxides
Lithium ion capacitor
Introduction interest in developing new solutions for powering vehicles and

other appliances. In this context, there are numerous programs
The scarcity of fossil fuels due to continuously increasing con- worldwide, aiming at research and developing vehicles based on
sumption and the pollution resulting from their use, together with fuel cells or batteries coupled with supercapacitors [1, 2].
the needs of a secure diversification of sources, has increased Supercapacitors, electrochemical capacitors (ECs), electrical
double-layer capacitors (EDLCs), pseudocapacitors,
ultracapacitors or power caches have been considered from many
* Yogesh Kumar years for energy storage in many applications. The primary ad-
[email protected]
vantages of ECs are that they have provided high power density,
excellent reversibility and good cycle life.
Sangeeta Rawal
[email protected] The performance of an electrochemical energy storage system
can be estimated by plotting its Ragone diagram, which repre-
Bhawana Joshi
[email protected]
sents the relative power and energy densities. Such a diagram is
represented in Fig. 1 for the current generation of batteries, fuel
S. A. Hashmi cells and supercapacitors [3]. It shows clearly that the fuel cells
[email protected]
have the highest energy density, whereas supercapacitors com-
1
Department of Physics, ARSD College University of Delhi, New paratively show high power density but low energy density as
Delhi 110021, India compared to batteries and fuel cells. The two main factors which
2
Department of Applied Physics, Gautam Buddha University, Greater determine the overall capacitance, energy density and power
Noida, Uttar Pradesh 201308, India density of a supercapacitor are the types of the electrode and
3
Department of Physics & Astrophysics, University of Delhi, New electrolyte materials. The electrochemical capacitors are those
Delhi 110007, India energy-storage devices that include a variety of active materials
Content courtesy of Springer Nature, terms of use apply. Rights reserved.

668 J Solid State Electrochem (2019) 23:667–692
whereas in case of batteries it takes hours to charge it [7, 8].

The working principle of ECs is same as that of a conventional
capacitor (i.e. two parallel plates or conductors separated by a
dielectric material or non-conductive region). In a convention-
al parallel plate capacitor, the capacitance C (measured in
Farad) directly depends on the area of each electrodes and
the electrochemical capacitors have very high surface area
electrodes which give rise to a very high value of specific
capacitance (F g−1 or F cm−2 of electroactive electrode mate-
rials) [4, 5]. The charge stored in the electrochemical capaci-
tors is limited by the electrode microstructure, active surface
area, electrolyte type and the interface (electrode/electrolyte)
reactions while in batteries, the complete active mass, thermo-
dynamics and the entire electrode are responsible for it. The
Fig. 1 Ragone diagram for the current generation of capacitor, maximum voltage sustained by ECs is limited by the break-
supercapacitor, battery and fuel cell. Reprinted with permission from [3] down voltage of the electrolytes.
for electrodes (various forms of carbons, metal oxides,

conducting polymers, nitrides and their compounds) and electro- Fundamentals of supercapacitors and their
lytes. Different types of electrolytes which have been used in classifications
supercapacitors are aqueous and non-aqueous electrolytes, poly-
mer electrolytes and ionic liquids [4–6]. As discussed earlier, electrode microstructures and electrode/
Supercapacitors are related to batteries from practical point electrolyte interface play a vital role in the charge storage mech-
of view, and these days ‘high rate’ batteries have been discov- anism. Hence, on the basis of the electrodes materials and mode
ered that exhibit pseudocapacitance phenomena at nanoscale of energy storage, ECs are classified into three main categories
and in disordered forms [4–6]. It can be concluded from the (i) pseudocapacitor or redox EC (ii) electric double-layer capac-
Ragone plot shown in Fig. 1 that supercapacitors have higher itor or EDLC and (iii) hybrid. Figure 2 shows the classification
power density then other energy storing devices such as fuel of these types of supercapacitors. A conventional capacitor is a
cells and batteries but less than the conventional capacitors. passive two-terminal component consisting of two conductive
EDLCs having carbon nanotube–based electrode possess bet- parallel plates separated by a dielectric medium, and charge is
ter electrochemical properties than other electrochemical ca- stored on the plates, whereas in EDLCs, charge is stored by
pacitors. But the energy density of the supercapacitors is not means of ions adhesion onto the surface of the electrode. The
as good as that for batteries. The diversities in the electrode ion adhered on the electrode surface forms an electric double
material and design flexibility are the main features that illus- layer. So, in EDLCs, charge is stored by means of double layers
trate why supercapacitors cover a broad area on the Ragone formed at the electrode/electrolyte interface, while in
plot. In electrochemical capacitors only, the electrolyte ions
close to the surface of the active electrode material participate Capacitors
in the charge–discharge process whereas in batteries, the
whole active mass participates. Due to this dissimilarity, the
charge–discharge response of the ECs is very fast (few sec- Electrochemical Nonelectrolyc
Electrolyc
onds only) as compared to that of batteries (up to few hours). Capacitors
ECs show the symmetric charge–discharge profiles and good
efficiency. The cycle life of ECs is also found to be better (~ Electric Double Layer Hybrid
10 years) than batteries (~ 3 years) which have the cycle life Pseudocapacitors
capacitors (EDLCs) Supercapacitors
that is limited by the chemical reversibility.
Conducng Redox-metal
Polymers oxides
Electrochemical capacitors
Electrochemical capacitors are the electrochemical high- Baery/Capacitor

Redox-asymmetric Composite
combinaons
power energy-storage devices with very high value of capac-
itance. A supercapacitor can quickly release or uptake energy Fig. 2 Classification of the supercapacitors based on charge storage
and can be charged or discharged completely in few seconds mechanism, materials used and configuration

J Solid State Electrochem (2019) 23:667–692 669
conventional capacitors, a single layer of charges is formed. So, the charge storage mechanism in pseudocapacitors is
However, in the pseudocapacitors or redox supercapacitors, different from EDLCs but similar to the batteries (the faradic
charge storage occurs due to fast and reversible faradic processes mechanism). In a battery, the whole active material partici-
taking place at the electrode/electrolyte interface due to pates in the reaction, whereas a pseudocapacitor involves elec-
electroactive species. Furthermore, just like conventional capac- trode material for the reversible redox reactions.
itors, pseudocapacitors consist of two electrode plates separated
by an electrolyte but the charge storage mechanism is different; Conducting polymer–based redox supercapacitors
therefore, they are named as pseudocapacitors (pseudo means
not real). When these two mechanisms of charge storage, i.e. Generally, conducting polymer–based supercapacitors store
double-layer formation and redox reactions function simulta- and release charges through oxidation reduction process oc-
neously, they give rise to a new class of supercapacitors called curring at the electrode surface. During oxidation (or ‘dop-
hybrid supercapacitors in which asymmetric configuration of the ing’), electrolyte ions move to the electrode (or polymer back-
electrode material is considered. The electrolytes used in bone) and during reduction (or dedoping) electrolyte ions
supercapacitors are aqueous and non-aqueous, ionic liquids, move back into the electrolyte. If thin films of conducting
polymer-based electrolytes with organic solvents or ionic liquids. polymer are used for pseudocapacitor electrode, then charging
The device configurations are symmetric, asymmetric and hy- takes place all over the electrode material (or bulk of the film)
brid and hence exhibit a diverse class of electrochemical energy- and not only on the surface of the electrodes as is the case for
storage devices. EDLCs giving rise to high value of specific capacitance.
Conducting polymers contain mainly π–orbital conjugations
Pseudocapacitors or redox supercapacitors that are responsible for good electronic conductivity in poly-
mers. Hence conducting polymers can be reduced or oxidized
In pseudocapacitors, charge storage mechanism is different electrochemically just by injection or withdrawal of electrons,
from the conventional capacitors and EDLCs and this respectively [6–8]. Conducting polymer film capacitors have
pseudocapacitance occurs due to the reversible redox reactions been reported having energy density value up to 39 Wh kg−1
or fast oxidation reduction reactions taking place between the and power density value up to 35 kW kg−1 [9, 10]. There are
electrode surface and electrolyte. The amount of the two types of the conducting polymers namely p-doped and n-
pseudocapacitance will depend on the electrode material its doped conducting polymers. The mechanism of the electro-
surface area and electrolyte. The electroactive materials chemical doping and dedoping of a conducting polymer film
exhibiting redox behaviour such as transition metal oxides, in for p-doping (oxidation) and n-doping (reduction) is shown in
addition to conducting polymers are being used for the elec- Fig. 3a, b respectively [9].
trode material in pseudocapacitors. Transition metal oxides Rudge et al. [9] have proposed three schemes of configu-
doped with conductive electrode material such as carbon are ration of redox reactions of p-doped (oxidized) and n-doped
also used as electrode material. Many transition metal oxides (reduced) states in conducting that areshown in Fig. 4 and are
such as nickel oxide (NiO), iridium oxide (IrO2), manganese discussed below.
oxide (MnO2) and ruthenium oxide (RuO2) and sulphides of
certain noble metals like titanium sulphide (TiS2) offer high Type I capacitors: In the first case, two alike p-dopable
pseudocapacitance and can be used as pseudocapacitor elec- polymers are used as active electrodes. When the state is
trodes. The reversibility of these transition metal oxide and fully charged, one electrode will be fully positive (p-
sulphide is excellent and hence when used as pseudocapacitor doped) state and other will be in the discharged state. In
electrode they can offer good cycle life. this type, a potential difference of 0.8–1.0 V is obtained.
Various electron-conducting polymers such as polypyrrole, Type II capacitors: Type II capacitors consists of two dif-
polyacetylene, polythiophene polyaniline and ferent p-dopable polymers as electrodes. These have differ-
poly(phenylenevinylene) also offer low conducting resistance ent potential ranges of the l for oxidation state and reduction
and high value of pseudocapacitance. The cycle life of state. This type of system offers an extensive range of oper-
conducting polymers is not as good as of transition metal oxides ating voltage up to 1.5 V, which leads to twofold enhance-
because they have low reversibility value due to slow faradic ment of energy density with respect to type I.
charge transfer [4, 5]. In the pseudocapacitors, electrode surface Type III capacitors: In type III capacitors, p-doped and n-
generally, three types of Faradaic processes take place for the doped conducting polymers are considered for the elec-
charge storage namely (i) reversible surface adsorption of electrode materials. This type of system offers a wide range of
trolyte ions at the electrode surface, (ii) reversible doping–de operating voltage up to 3.1 V, which leads to ninefold
doping at the electrode surface of the conducting polymer and enhancement of energy density with respect to type I.
(iii) redox reactions occurring between the electrolyte ions and Although type III capacitors are attractive from the oper-
the transition metal oxide–based electrode surface (e.g. IrO2) [4]. ating voltage and energy density point of view, but it is

Fig. 3 A schematic
representation of the charging and
discharging process at conducting
polymer electrode associated with
a p-doping and b n-doping.
Reprinted with permission from
[9]
seldom reported in literature as the preparation of n-type consequence of morphology on the capacitive performance.
polymer is difficult and chemical–electrochemical insta- It was found that all the three nanostructures, nanospheres,
bility at the ambient conditions. nanorod and nanofibres, show different values of capacitance,
i.e. 71, 133 and 192 F g−1 respectively. Nanofibres show
higher capacitance as compared to other two structures due
Polyaniline is the most studied conducting polymer in to its good structural ordering and high aspect ratio [12]. Chen
supercapacitor applications for type I devices, and a very high et al. also studied the electrochemical performance of different
value of energy density and power density can be obtained shapes of polyaniline nanostructures synthesized by template
with polyaniline electrodes. W. Chen et al. synthesized method and measured a very high value of capacitance for
polyaniline nanotubes by in situ chemical polymerization by polyaniline nanotubes (896 F g−1) which can be attributed to
using MnO2 nanotubes as templates. Polyaniline nanotubes their high surface area [13].
shows better performance with energy density value of Polypyrrole has also been considered as a good electrode
84 W h kg−1 in ionic medium then in acidic medium [11]. In material for type I and type II capacitor devices. Polypyrrole
polyaniline, the aspect ratio or the morphology of the nano- generally gives less specific capacitance value as compared to
structures directly affects the capacitance value because the polyaniline due to its dense morphology. But it shows good
protonation level or the oxidation of the conducting polymers electroactivity for aqueous, nonaqueous and aprotic electro-
varies directly with the aspect ratio. Park et al. synthesized lytes and shows highest specific capacitance values for aque-
three different forms of polyaniline, i.e. nanospheres, nanorod ous electrolytes as compared to non-aqueous electrolytes as
and nanofibres, and performed the electrochemical studies in aqueous electrolytes have high ionic conductivity and these
an acidic medium under the same conditions to study the ions may get easy access in the dense structures of the
Fig. 4 Schematic representation

of charge and discharge operation
of different electrochemical
supercapacitor a Type I, b Type II,
and c Type III. Reprinted with
permission from [4, 5, 9]

polypyrrole [14]. J Zhao et al. synthesized polypyrrole nano- maximum capacitance up to 243 F g−1 for 54.3 wt% of ruthe-
wires (120 nm in width) for supercapacitor electrode. The nium in mesoporous carbon. It is also observed that if more
polypyrrole nanowire–based electrode showed quite high spe- ruthenium is loaded in carbon, the capacitance value start de-
cific capacitance value (420 F g−1) and good cycle life at creasing because of increase in the internal resistance due to
1.5 A g −1 [15]. The electrochemical performance of hindrance in the motion of the ions in the pores of the carbon
polypyrrole-based electrodes can be improved by making by ruthenium ions [22]. Composite material made up of metal
the composite of polypyrrole with transition metal oxide and oxide and carbon nanotube also offer good electrochemical
different forms of carbon. Nanocomposite of polypyrrole and performance such as X. Qin et al. used the template grown
graphene as supercapacitor electrode gives good results and CNTs to make its composite RuO2. xH2O/CNTs with RuO2
specific capacitance values of 277 F g−1 can be obtained with and performed the electrochemical studies on this composite
these nanocomposites along with good cycle life [16, 17]. R. material in aqueous medium and found approximately ten times
K. Shama et al. synthesized MnO2–polypyrrole nanocompos- increment in the capacitance values. The capacitance values
ite material–based films to study its electrochemical perfor- obtained from and CNTs and RuO2. xH2O/CNTs electrode
mance and noticed quite high increment in the specific capac- were 27 and 295 F g−1, respectively [23]. A brief list conducting
itance value for the nanocomposite films (620 F g−1) as com- polymers based redox capacitors is given in the Table 1.
pared to the specific capacitance values of MnO2 (225 F g−1)
and polypyrrole (250 F g−1 [18]. Polythiophene conducting Transition metal oxide based redox supercapacitor
polymer–based electrodes are used in type III devices, i.e. it
can be used for both n-dopable and p-dopable. However, As discussed above, numerous transition metal oxides and
polythiophene shows less specific capacitance and poor con- sulphides, such as TiO2, RuO2, MnO2, Co3O4, NiO, Fe2O3,
ductivity for n-doped in comparison to p-doped [19] and to Ir2O3 and SnO2, are also used as pseudocapacitor electrode
enhance its performance, derivatives of polythiophene are pre- material for the supercapacitor applications with their
pared with low band gap materials. pseudocapacitance mechanisms of charge storage. Amongst
Conductive polymers are also being used as conductive these metal oxides for supercapacitor electrodes, amorphous
polymer gels for the synthesis of carbon framework as they hydrous ruthenium oxide (RuO2·xH2O) is considered as a
can provide an electrically conductive network for the easy very good electrode material because of its high specific
transportation of ions. Electrochemical performances of pseudocapacitance (owing to fast faradic reaction), high re-
conducting polymers can be enhanced by doping as dopants versibility and good cycle life [4, 24–26]. Powdered RuO2·
improve the conductivity of the conducting polymers. xH2O synthesized by various methods such as colloidal, solid
Hybridization of the conducting polymers with other materials state and sol–gel method and used as redox supercapacitor
such as transition metal oxide [20], carbon nanotube [21] and electrode gives high power density and specific energy [27].
activated carbon [22] also improves the electrical and electro- But, RuO2 is expensive, naturally less abundant and toxic and
chemical properties. Metal oxides and activated carbon com- which has restricted their commercial use. Also, RuO2 needs
posite materials also shows good capacitive behaviour. J. H. strong acidic electrolyte (e.g. sulphuric acid), which when
Jang et al. prepared ruthenium/carbon composite material with used for many cycles can dissolve the metal oxide and subse-
ruthenium nanoparticle and porous carbon and found quently cause the fading of the specific capacitance with cycle
Table 1 Specific capacitance,

energy density and power density Capacitor cells Capacitance Energy Power Ref.
of some conducting polymer– (Wh kg−1) (kW kg−1)
based redox supercapacitors (F g−1) (mF cm−2)
PFPT|TEMATf + CAN|PFPT| 86 – 39 35 [9]

PANI|HClO4 + NaClO4|PANI 1300 – – 0.5 [10]
PEDT-RuO2|H2SO4|PANI-RuO2 420 – 27.2 – [20]
pDAAQ|PMMA-EC-PC-(C2H5)4NClO4|pDAAQ 184 5.4 135 – [4]
pPy|PVA-H3PO4|pPy 84 5 12 – [4]
PANI-AC|1 M H2SO4|PANI-AC 160 – – – [21]
pPy|PEO9·LiCF3SO3 + PEG|pPy 13.0 2.0 1.8 – [24]
pMeT|PEO8·LiCF3SO3 + PEG|pMeT 42.0 3.7 2.1 – [24]
pPy|PEO8·LiCF3SO3 + PEG|pMeT 30.0 3.5 12 – [24]
pDTT|PEO-TEABF4-PC|pDTT 11 50 8 0.22 [25]
P3MT|PEO-Et4NBF4-EC-PCnanoclay|AC 18.5 – 10.2 0.096 [26]

life. If non-corrosive electrolytes can be used in place of con- (453 F g−1). Electrochemical performances also get enhanced
centrated acidic electrolyte for RuO2, then they can certainly by doping with other metal and non-metal atoms. Yoo et al.
be used in various applications. [75] used vanadium and iron for doping manganese oxide thin
Many other doped and undoped metal oxides and their films by the hydrothermal method and found that the electro-
composites than those discussed above have also been tried chemical performance of the metal oxide films enhanced the
for supercapacitor applications [28–30]. These include IrO2 or properties and Fe dopant has more positive effect on the elec-
CoO2 [30] but just like RuO2, they are also expensive and trochemical properties. Luo et al. [48] stated that Mn–Ni–Co
operate in strong alkaline or acidic electrolytes. Furthermore, oxide composite supercapacitor electrode gives very high ca-
the potential window for these metal oxides is significantly pacitance values (1260 F g−1) in aqueous electrolyte (6 M
smaller than that for RuO2. In place of the above discussed KOH). A number of oxide-based electrodes are in develop-
expansive metal oxides, some low-cost metal oxides have also mental stage and need a serious study to establish them in
been tried for supercapacitor devices such as molybdenum supercapacitor technology.
oxides. Hence, MoO3 [31] and MnO2 [32, 33] are being used
these days in many supercapacitor applications owing to their
lower cost. A. Kumar et al. used the sputtering method to EDLCs
synthesize the MnO2 nanorods for supercapacitor applications
and obtained a good value of specific capacitance from binder An electric double-layer capacitor (EDLC) offers relatively
free electrodes made up of MnO2 nanorods [34–36]. higher capacitance and energy density value than an electro-
Table 2 shows the specific capacitance values, energy den- lyte capacitor. They are called double-layer capacitors because
sity and power density values exhibited by different metal in EDLCs, charge is stored by forming a double layer of elec-
oxides and their composites with the different electrolyte sys- trolyte ions at the electrode surface. EDLCs employ different
tems used. The manganese oxide has been recently introduced forms of carbon (activated carbons, carbide-derived carbons,
as a capable active material for supercapacitor electrodes [33]. templated carbons, CNTs, carbon fabrics, carbon xerogels/
Manganese exits in different oxidation states, and all of these aerogels, carbon blacks, graphene, etc.) as electrode material
different structural properties and crystalline phases and used [4, 5]. Charges are stored electrostatically in EDLCs in the
for several applications. MnO2 phase is found to be used in form of polarized electric double layers formed between an
various energy storage devices such as batteries and ionically conducting electrolyte and carbon electrode under
supercapacitors [66]. Manganese oxide materials can be syn- the application of an electric potential. Hence, the charge stor-
thesized by many methods, for instance the sol–gel method age mechanism of EDLC is similar to that of a conventional
[67], solution-based chemical routes [68], electrochemical de- capacitor. Hence, the two-charge layers at the electrodes (both
position [69], hydrothermal method [70] and sputtering meth- negative and positive electrodes) are analogous to two capac-
od [71]. Those synthesis methods are preferred which gives itors connected in series. In EDLCs, the positive and negative
rise to enhanced electrochemical performance, such as a high charge layers, separated by a very a short distance (10 Å), are
specific capacitance, good cycling life, and fast charging/ formed at both the contact boundary of the electrolyte and two
discharging rates. Broughton and Brett [71] reported the solid carbon electrodes. The excess ions in the solution bal-
highest capacitance of 700 F g−1 for MnO2 films prepared ance the extra charge at the surface of the electrodes material.
by sputtering method. According to some recent reports, The concept of a ‘double layer’ in the electrochemical cell
mixed oxide composites and their compounds have good elec- was first given by Helmholtz in 1879; therefore, it is also
trochemical performance as compared to solo transition metal called as Helmholtz layer [76]. According to Helmholtz mod-
oxide as electrode. Li et al. [72] reported capacitive perfor- el, in electric double-layer capacitors, two opposite charge
mances of chromium doped MnO2 nanostructured material layers separated by very small distance (an atomic distance)
synthesized by hydrothermal method. Prasad et al. [53] report- are formed at the interface are of electrode and electrolyte and
ed the electrochemical performances of nickel–manganese ox- the amount of charge stored in EDLC varies with the electrode
ide thin films, synthesized by electrochemical method. The potential [77–79]. If the capacitances of the two double layers
supercapacitor electrodes made from these thin films shows (one with positive and another with negative polarity) are
good specific capacitance values (621 F g−1) and good cycle represented by C1 and C2 respectively, then the overall capac-
life. In addition, the nanostructured electrodes show better rate itance (CT) of the supercapacitor cell can be stated as [56].
capabilities as compared to traditional materials as discussed
by Cao et al. [73]. Capacitance values gets enhanced when the 1 1 1
two or more metal oxides are used as supercapacitor elec- ¼ þ ð1Þ
CT C1 C2
trodes such as what Liu et al. [74] showed that NiO/MnO2
mixed oxide prepared by sol–gel method when used for Gouy and Chapman modified the Helmholtz model
supercapacitor electrodes gives specific capacitance value [80–82] and proposed a new model known as diffuse model

Table 2 Specific capacitance,

energy and power density of some Electrode Electrolyte Specific capacitance Specific energy Specific power Ref.
important metal oxide–based materials (F g−1) (Wh kg−1) (kW kg−1)
electrode materials in aqueous
and ionic liquid electrolytes for RuO2 1.0 M 954 33 – [37]
supercapacitor applications H2SO4
Pb-RuO2 0.5 M 160 – – [38]
H2SO4
RuO2–TiO2 1.0 M KOH 46 6 1.2 [39]
RuO2–SnO2 0.1 M 690 – – [40]
H2SO4
LixRuO2 + xH2O 1.0 M 391 66 – [41]
Li2SO4
RuO2-C 1.0 M 250 – – [42]
H2SO4
RuO2–SnO2 0.5 M 88 – – [43]
H2SO4
NiO 2.0 M KOH 167 – – [44]
Ni(OH)2 2.0 M KOH 350 – – [45]
Ni–Co-oxide 1.0 M KOH 569 – – [46]
NiO-C BMIM-PF6 357 50 0.5 [47]
Mn–Ni–Co-oxide 6.0 M KOH 1260 – – [48]
NiO-RuO2 1.0 M KOH 210 – – [49]
RuO2− TiO2 0.5 M 686 – – [50]
H2SO4
Co(OH)2 1.0 M KOH 860 – – [51]
Co3O4 6.0 M KOH 746 – – [52]
Co–MnO2 1.0 M 498 – – [53]
Na2SO4
Co(OH)2/TiO2 6.0 M KOH 229 – – [54]
V2O5 0.1 M 170 – – [55]
K2SO4
V2O5-C 2.0 M 33 – – [56]
NaNO3
Fe2O3 0.25 M 210 – – [57]
Na2SO3
Fe3O4-C 6.0 M KOH 38 – – [58]
MoO2-C 0.1 M 597 – – [59]
Na2SO4
MoO2 1.0 M 140 – – [60]
H2SO4
Bi-oxide 1.0 M 98 – – [61]
NaOH
Bi Fe oxide 1.0 M 81 – – [62]
NaOH
SnO2 0.1 M 101 – – [53]
Na2SO4
CuO 1.0 M 43 – – [63]
Na2SO4
In2O3 1.0 M 190 – – [64]
Na2SO3
IrO2–MnO2 0.5 M 550 – – [65]
H2SO4
of the electrical double-layer according to which the electro- it was further modified by Stern [83] who combined the two
lyte ions are continuously distributed in the electrolyte solu- models (Helmholtz model and diffuse model). According to
tion. According to diffuse model, it is found that there is an Stern model electric double layer consists of two regions for
exponential decay in electric double-layer potential from the ion distribution namely (i) Stern layer or compact layer also
electrode surface to the bulk of the solution. However, this called the inner region and (ii) the diffuse layer. In the compact
model leads to an over estimation of the capacitance; hence, layer, ions from the electrolyte are strongly adsorbed at the

electrode surface. The adsorbed ions in the compact layer formation [89]. According to some theoretical reports, the
generally consist of anions and their counterions which are specific capacitance values of carbon-based electrodes should
distinguished by inner Helmholtz plane or IHP and outer rise with increase in surface area. But, Shi along with his co-
Helmholtz plane OHP respectively as shown in Fig. 5. worker [90, 91] studied the correlation between pore size, pore
Thus, according to Stern model total double-layer capaci- volume and specific surface area and for numerous activated
tance (Cdl) is contributed by the capacitance of both regions carbon materials and stated that the theoretical hypothesis is
(compact layer and the diffuse layer). If CH is the compact not certainly true for practical cases. The compatibility be-
double layer or Stern capacitance and Cdiff the diffusion region tween the electrode material pore size and electrolyte ions
capacitance the total double-layer capacitance can be influences greatly the double-layer capacitance. If the pore
expressed as follows: size is too big, it may not hold the electrolyte ions and if the
pores are too small then the electrolyte ions do not get the easy
1 1 1
¼ þ ð2Þ access to get adsorbed on the electrode surface. Another factor
C dl C H C diff
affecting the electrochemical performance is the mobility ion-
ic as ionic mobility in the electrolytic solution is totally differ-
The factors such as the electric field across the electrode sur- ent than within the pores [92]. Hence the electrolyte solution
face, the kinds of electrolyte ions and the solvent containing the should be wisely chosen to suit the pore size of the material
electrolyte ions, affect the double-layer behaviour at a planar elec- and the pore size distribution should be optimal as per the
trode surface. One more important factor that affects this behav- ionic sizes [92]. Various important EDLC cells with different
iour is the chemical affinity and compatibility of the adsorbed ions kinds of electrolytes including liquid electrolytes, ionic liquids
and the microstructure of the electrode material [77]. and polymer-based electrolytes (solvent-free and gels), and
Different forms of carbon materials and its derivatives have various forms of carbons are listed in Table 3.
been intensively studied for supercapacitor applications [4, 5]. Mobility of the ions inside the pores is also related to the ionic
Carbon materials particularly activated carbons generally have conductivity, and Frackowiak et al. [92] stated that the ionic
high surface area, 1000–2500 m2 g−1 and are available in conductivity is affected by the texture of the electrode material.
different forms, e.g. powder, fabric and fibre. High surface The other forms of the carbons, which are used as supercapacitor
area and good porosity in carbon materials can be obtained electrodes, are carbon xerogels/aerogels. Carbon xerogels are the
by carbonization, activation [84–86], phase separation [87], monolithic 3D network of carbon nanoparticles. Carbon xerogels
gelation [87], emulsification [88] and aerogel-xerogel are generally obtained from the pyrolysis method of organic
Fig. 5 Models showing electrical double-layer formed at a positively layer starts from OHP and its thickness lies in the range 10–100 nm. After
charged electrode in aqueous electrolyte: a Helmholtz, b Gouy– the diffuse layer, the bulk electrolyte starts. Reprinted with permission
Chapman and c Stern models. IHP refers to the distance of the closest from [77]
ion sheath and OHP to the non-specifically adsorbed ions. The diffuse

Table 3 Specific capacitance, energy and power density values of some important EDLCs based on various forms of carbon electrodes for different
kinds of electrolytes (i.e. organic, aqueous, ionic and polymer-based electrolytes)
Capacitor cells Capacitance Specific energy Specific power Ref.

(Wh kg−1) (kW kg−1)
(F g−1) (mF cm−2)
(a) For organic and aqueous liquid electrolyte

HD-ACF|KCl|HD-ACF 28 – – – [93]
C|KOH|C:(C:aerogel) 40 – – – [5]
PAN-MF|5 M KOH|PAN-MF – – 3 – [5]
PAN-MF|0.5 M LiClO4 + CH3CN|PAN-MF – – 5 5.0 [5]
AC-CNT|TEABF4 + CH3CN|AC-CNT 95 – – – [94]
AC|H2 SO4|AC 180 – – – [95]
C|ACN-TEABF4|C 100 – – – [96]
ACF|PC-TEABF4|ACF 169 – – – [97]
C|KCl|C; (C: rice husk) 210 – – – [98]
C|H2 SO4|C; (C: aerogel) 104 – – – [99]
AC|KOH|AC 412 – – – [90]
ACF|KCl(aq.)|ACF 28 – – – [93]
CB|KOH|CB 108 – – – [100]
CF|H2 SO4|CF 170 – – – [101]
AC|PC-TEABF4|AC 58.7 – – – [102]
Ni-ACF|PC-LiClO4|Ni-ACF 95 – – – [103]
ACFC|KOH|ACFC 106 – – – [104]
ACC|LiClO4-PC|ACC 82 – – – [105]
AC|1 M LiClO4-EC-DEC|AC 132 – – – [106]
Nano-C|polycarbonates|nano-C 75 – 76 506 [107]
AC|TEABF4-ACN|AC 100 – 17 44 [108]
AC|1 M Et4NBF4-PC|AC 38 48 10.9 – [109]
CB-AC|EC-DEC-LiClO4|CB-AC 104 – – – [110]
VGCFs-AC|EC-DEC-LiClO4|VGCFs-AC 106 – – – [110]
Y-AN|1 M H2 SO4|Y-AN 340 – – – [111]
Y-AC|1 M H2 SO4|Y-AC 240 – – – [111]
AC|1 M H2 SO4|AC 120 – – – [111]
NE-AC|4 M H2 SO4|NE-AC 191 – – – [112]
NE-AC|7 M KOH|NE-AC 200 – 8.1 10 [112]
SOMCs|6 M KOH|SOMCs 165 – 8 1.25 [113]
LOMCs|6 M KOH|LOMCs 143 0.010 – – [113]
CDC|1.2 M Et4NBF4 ACN|CDC 122 87 5.2 4.99 [114]
CNF|1 M LiClO4-ACN|CNF 3.5 5.5 – – [115]
(b) For ionic liquid electrolyte
AC|EMIBF4|AC – – 20 2.3 [116]
AC|EMICF3SO3|AC – – 10 2.1 [116]
AC|EMITFSI|AC – – 28 2.3 [116]
AC|BMIPF6|AC 160 0.0061 – – [117]
AC|EMI(Tf2)N|AC 180 0.0069 – – [117]
AC|BMP(Tf2)N|AC 167 0.0064 – – [118]
AC|1 M DEMEBF6-PC|AC 44 – – – [118]
AC|[(C6H13)3P(C14H29)](Tf2)N|AC < 15 – – – [119]
AC|[(C6H13)3P(C14H29)](CN)2 N|AC < 15 – – – [119]
AC|[(C6H13)3P(C14H29)](Tf2 N-ACN)|AC 100 – – – [119]
AC|[(C6H13)3P(C14H29)](CN)2 N-ACN|AC 40 – – – [119]

Table 3 (continued)

(F g−1) (mF cm−2)
C-xerogel|EMITFSI|C-xerogel 128 – – 9.5 [120]

C-xerogel|PYR14TFSI|C-xerogel 120 – 30 11.4 [120]
CDC|EMITFSI|CDC 160 85 F cm−3 – – [121]
CDC|EMITFSI|CDC 91 45 F cm−3 – – [121]
AC|DEMEBF4|AC 25.4 – – – [122]
AC|EMITaF6|AC – 14 F cm−3 – – [123]
AC|EMINbF6|AC – 13 F cm−3 – – [122]
AC|EMIF-2.3HF|AC 178 31 F cm−3 63 J cm−3 – [123]
AC-FC|EC-2 M EMIPF6|AC-FC 123 – – – [124]
AC-FC|PC-2 M EMIPF6|AC-FC 127 – – – [124]
AC-FC|DMC-2 M EMIPF6|AC-FC 126 – – – [124]
AC-FC|EMC-2 M EMIPF6|AC-FC 123 – – – [124]
AC-FC|EC-DMC-2 M EMIPF6|AC-FC 129 – – – [124]
AC-FC|PC-EMC-2 M EMIPF6|AC-FC 129 – – – [124]
AC-FC|EC-DMC-2 M EMIBF6|AC-FC 135 – – – [124]
AC|PYR14TFSI|AC 90 – 31 8.6 [125]
AC|EMITFSI|AC 100 0.007 – – [126]
GCP|BMIMBF4|GCP – 210 – – [127]
GCP|EMIMPF6|GCP – 250 – – [127]
(c) For polymer-based electrolyte
ACP|PEO-BMIm|ACP 35 0.0042 – – [128]
Nano-CB|PEO-NPPP-LiClO4|nano-CB 17 9.22 8 0.096 [129]
AC|PEO-KOH-H2O|AC 93 – – – [130]
ACC|PEO-PPO-LiClO4-PC|ACC 86 – – – [105]
CB|PEO-PEG-LiClO4-|CB 60 – 20 kJ L−1 300 W L−1 [131]
ACF|PMMA-PEO-TEABF4-PC|ACF – 400 – – [5]
CE|PEO-PEG-LiClO4|CE 60 – 6.2 0.3 [5]
ACF|PEO-PEG-LiCF3SO3-|ACF 4 20 – – [5]
ACF|PMMA-PEO-(C2H5)4NBF4-PC|ACF 20 570 16.2 – [132]
EG|PEO-PE-PC LiClO4|EG – 0.98 – – [133]
ACP|PAN-EMIBF4|ACP 200 0.0077 – – [128]
AC|PTFE-EMITFSI|AC – – 6 2.842 [116]
AC|PVDF-HFP-EMITFSI-Zeolite|AC – – 7 2.727 [116]
AC|PVDF-EMITf-TMS|AC 239 – 38 kJ kg−1 80 [134]
AC|PVDF-EMITf|AC 130 – – – [134]
ACF|Nylon6-10-H3PO4||ACF 70 – 1.4 – [135]
ACF|PAN-(C2H5)4NBF4-PC||ACF 16 370 – – [136]
ACF|PVA-H3PO4||ACF 90 470 14–18 – [137]
AC|PVdF-HFP-EC-PC-(C2H5)4NBF4|AC 123 – – – [138]
AB|PVdF-HFP-TEABF4-EC-PC|AB 4.1 – – – [139]
ACP|PVA-HClO4|ACP 44 – – – [140]
ACF|PVP-PVAc-TEABF4-PC|ACF 38 – – – [141]
AC|PVA-KOH|AC 123 – 10.00 29.61 [142]
AC|PP/PE separator|AC 61 – 5.6 7.86 [142]
ACFC|S-PP + KOH + H2O|ACFC 110 – – – [104]
AC|PMMA-LiClO4--EC-PC|AC 46 84 6.4 0.21 [143]
AC|PMMA-NaClO4--EC-PC|AC 78 151 10.8 0.19 [143]

Table 3 (continued)

(F g−1) (mF cm−2)
AC|PMMA-TEAClO4--EC-PC|AC 38 68 5.3 0.22 [143]

CB|polyurethane-LiClO4|CB 8.4 4 – – [144]
AC|PVdF-HFP--EC-PC LiClO4|AC 4.3 100 – – [78]
BP|Nafion|BP; (BP: Black Pearls) 13.5 175 – – [79]
ACFC|PVA + GA+ H2SO4|ACFC 115 – – – [145]
aerogels. The organic aerogels used for the synthesis of carbon the carbon surface with metal oxides and conducting polymers
xerogels are obtained by the sol–gel process from resorcinol causes an increase in capacitance due to pseudofaradaic reac-
formaldehyde [147, 148]. These aerogels show high surface area tions. Varying the pore sizes in the electrode material also
value, good electrical conductivity, low density and tuneable pore affects the capacitance value because it affects the electrode
size. Hence, they are considered as excellent material for making surface area available to electrolyte ions. Chimola et al. [121,
EDLC electrodes [89]. 151] systematically studied the effect of pore size distribution
Various new techniques are being used these days to syn- on the double-layer capacitance of carbide derived carbon in
thesize carbon nanostructured which possess high available an organic electrolyte for pore sizes ranging from 0.6 to
surface area electrodes for EDLCs [149]. Supersonic cluster 2.25 nm. The variation of normalized capacitance with aver-
beam deposition method is one such method which is used for age pore size is divided into three regions region I for pore size
growing nanostructured carbon films. The carbon films grown greater than double the size of electrolyte ions, region II for
by supersonic cluster beam deposition method shows grain pore size less than twice the electrolyte ion size but greater
size of approximately few tens of nanometres that is good than the ion size and region III when the pore size is less than
for supercapacitor applications and shows 75 F g −1 , the electrolyte ion size. The results are shown in Fig. 6, and
76 Wh kg−1 and 506 kW kg−1 values for specific capacitance, conclusions are explained below [121, 151].
energy density and power density respectively [149].
Various functional groups can also be introduced into the Region I: When the size of the carbon pores is larger than
carbon materials to improve the capacitance values. Chu et al. size of the solvated ions (approximately twice), there was a
[150] studied the effects of functional groups on surface mod- positive effect on the normalized capacitance due to the for-
ification on EDLC values of various carbon electrodes mation of compact layers of ions on both adjacent pore walls.
through various chemical and electrochemical techniques (ox- Region II: If the pore size is reduced to less than twice
idation/reduction) and. Another parameter which affects the the ion sizes, the capacitance decreases due to the de-
power density of the supercapacitors is the conductivity of the crease in available surface area as compact ion layers
electrodes as conductivity varies inversely with the particle formed from adjacent pore walls impinge. This decrease
size. Hence, a material having good surface area but in capacitance value with pore size continues for pore
possessing smaller particles develops decreased resistance sizes more than 1 nm.
and thus power density can be improved by using activated Region III: The trend (decrease in capacitance with pore
carbons having larger pores. size) does not continue further when the pore size de-
Sometimes, binders are mixed with the carbon material for creases to less than that of the electrolyte ionic size.
making electrodes such as polyvinylidene fluoride-co- Decreasing the pore size towards crystallographic diam-
hexafluoropropylene (PVdF-HFP) and the use of these bind- eter of the ion leads to a 100% increase in capacitance.
ing materials affects the conductivity. Hence, power perfor-
mance of such materials can be improved by using less
amount of binder [92]. The double-layer effects of charge Such anomalous result is still under the active consider-
storage mechanism occur mainly on the surface of the elec- ation by theoretical physicists and chemists.
trodes. Hence, double-layer effects can be enhanced by the
treatment of the activated carbon with metal oxides to increase Carbon nanotubes based EDLCs
the surface functionality. Frackowiak [92] studied the effect of
oxidized metal particles and conducting polymers deposited Carbon nanotubes (CNTs) are the nanostructures having large
on the various forms of carbon and stated that by modifying length/diameter ratio and having tubular shapes [152]. CNTs

Fig. 6 a Plot of specific

capacitance normalized by
Brunauer–Emmett–Teller specific
surface area (BET SSA) for the
carbons with identical
electrolytes. The normalized
capacitance decreased with
decreasing pore size until a
critical value was reached, unlike
the traditional view which
assumed that capacitance
continually decreased. It would be
expected that as the pore size
becomes large enough to
accommodate diffuse charge
layers, the capacitance would
approach a constant value. b–d
Drawings of solvated ions
residing in pores with distance
between adjacent pore walls b
greater than 2 nm, c between 1
and 2 nm and d less than 1 nm
illustrate anomalous behaviour
schematically. Reprinted with
permission from [151]
possess unique physical properties like good corrosion resis- equivalent series resistance or ESR, resulting in high power
tance, chemical stability, surface area, good electrical conduc- density and rate capability. Various forms of CNTs such as
tivity, low mass density and good mechanical strength, be- directly grown, aligned CNTs, porous tablets and entangled
cause of which they have applications in various fields CNTs have been tested as electrode materials. Directly grown
[153–157]. Even CNT/polymer (polyaniline, polypyrrole, de- CNTs on graphite foil can show a specific capacitance value
rivatives of polythiophene) composites are also considered as of 115.7 F g−1 [161] as directly grown CNTs in general de-
good alternative materials for various applications, electronic crease the contact resistance between the active electrode sur-
paper and antistatic coatings, including flexible electrodes in face and current collector [161]. However, recent studies have
displays, protective clothing, bulletproof vests, automotive in- shown that the electrodes fabricated with aligned CNTs show
dustries and composites for aircraft [19, 158–160]. These higher capacitance than the electrodes fabricated with
days, CNTs are used as electrode materials in electrochemical entangled CNTs as aligned CNTs provides rapid ion transpor-
energy conversion and storage devices for example batteries tation than entangled CNTs. Entangled CNTs also shows the
and supercapacitors [161]. The concentric cylinders of closed high entanglement of the structure and irregular pore struc-
rolled-up graphene sheets are termed as CNTs. There are two tures [161–165]. Thus, due to larger pore sizes, lower ESR,
types of CNTs according to number of concentric cylinders of conductive path of the electrodes, more regular pore structures
rolled sheets, i.e. single-walled carbon nanotubes or SWCNTs and better reaction rate capability aligned CNTs as electrodes
consisting of one rolled graphene sheet and multi-walled car- are advantageous for high-power performances [164].
bon nanotubes or MWCNTs consisting of two or more rolled CNTs can be synthesized by various techniques including
graphene sheets. The interlayer distance in MWCNTs is ~ arc discharge [162, 166] laser-ablation [164], chemical vapour
0.33 nm. The typical diameter of SWCNTs lies in the range decomposition (catalytic growth) [165] and high-pressure CO
from 1.2 to 5 nm, whereas that of MWCNTs is found in the disproportionation (HiPCO) [166]. The specific surface area
range 10–50 nm. Iijima [316] was the first who observed of SWCNTs has been reported in the range from 240 to
(MWNTs). 1250 m2 g−1 [161]. The specific capacitance of the CNTs,
In contrast to other forms of carbon electrodes, the pores reported in the literature, ranges from 20 F g −1 to >
(mesopores) in CNTs are interconnected, which helps to uti- 300 F g − 1 . Niu et al. [167] first time reported the
lize almost all of the available surface area for the continuous supercapacitor application MWNT based electrodes with spe-
charge distribution and easy access of electrolyte ions. This cific capacitance of 113 F g−1 and energy density value as
makes CNT electrodes based EDLCs to have lesser value of 0.56 Wh kg−1with a power density of 8 kW kg−1 in aqueous

electrolyte (H2SO4). SWCNT electrode–based cells have been different electrolytes (1 M H 2SO4 , 6 M KOH, or 1 M
reported to exhibit a good specific capacitance, large power tetraethylammonium tetrafluoroborate (TEABF4) in acetoni-
density and an energy density of 180 F g−1, 20 kW kg−1 and trile [181]. SWNT/(PANI) composite–based electrodes syn-
7–6.5 Wh kg−1 respectively [161]. Whereas for MWCNT thesized by in situ electrochemical polymerization shows spe-
electrodes, a specific surface area of 430 m2 g−1 offering a cific capacitance values 310 F g−1 which is more than that of
specific capacitance, power density and an energy density of pure PANI, due to the existence of more active sites in com-
values of 113 F g−1, 8 kW kg−1 and 0.56 Wh kg−1 has been posite [182]. SWNT/polyvinylidene chloride composite–
reported in the literature [167, 168]. based electrodes evaluated in aqueous electrolytes (7.5 M
As discussed in the previous section, physical and chemical KOH) gives specific capacitance, good power density and
activations are very simple and low-cost methods of produc- energy density values of 180 F g −1 , 20 kW kg −1 and
ing high specific surface area activated carbons (up to 7 Wh kg−1 respectively [183]. Graphene oxide exhibits higher
3000 m2 g−1). Activation method has also been used for the capacitance than graphene because in graphene oxide oxygen
treatment of CNT-based electrodes to enhance the specific containing functional groups provides additional
surface area. It was reported that physically activated [169] pseudocapacitance [184].
and chemically activated [170] carbon nanotube–based elec-
trodes show higher specific surface area and specific capaci- Graphene-based EDLCs
tance values. The wetting ability of the electrodes is also a
main factor that affects the capacitance behaviour of the car- Recently, graphene oxide (GO) has emerged as a distinct ma-
bon electrodes. For this reason, hot nitric acid [80, 170], fluo- terial in view of its use as electrodes due to its fascinating
rine [175] or ammonia plasma [173], functionalized CNT- properties, such as (i) unlike CNTs, production route of GO,
based electrodes have been tested for electrochemical perfor- which gives high yield, is easy and cost-effective because it
mance. Generally, by surface functionalization of CNTs using can be prepared from the precursor graphite powder, (ii) it is a
carboxyl and hydroxyl groups, the CNTs get converted into very low-cost material and can be used for large scale produc-
hydrophilic from hydrophobic and this increased hydrophilic- tion of graphene [185, 186] and (iii) the high surface area GO
ity results in wettability of the electrodes and hence larger containing oxygen functional groups is a better choice as elec-
capacitance values are expected [161]. A very high value of trode material than graphene to give enhanced capacitance
specific capacitance (350 F g−1) is reported in the literature for and hence verifying the significance of surface functional
pyrrole treated functionalized SWCNTs [171]. The modifica- groups [80, 187]. Furthermore, GO needs no deliberate
tion of carbon nanotubes by conducting polymers is another functionalization just as we do in case of CNTs so that they
effective approach to improve the specific capacitance values may disperse uniformly in any solvent and hence avoid ag-
due to redox process of the conducting polymers [174]. In the glomeration [188].
CNT and conducting polymer composite, conducting poly- A single layer (or few layers) of graphene with oxygen rich
mers serve as the electron donors while CNTs are electron groups is referred as graphene oxide. Graphite oxide is also
acceptors and a charge transfer occurs between conducting considered as a compound of carbon, hydrogen and oxygen in
polymers and CNTs in their ground state [175]. The capaci- variable ratios. The presence of these oxygen groups in graph-
tance value up to 163 F g−1 can be obtained with CNT/ ite oxide increases the interlayer distance and makes the layers
conducting polymer composite [179]. SWNT and polypyrrole hydrophilic [185, 187]. As shown in following scheme, the
composite showed good capacitance value up to 260 F g−1 graphite powder is first oxidized in the presence of oxidants
[183]. Many studies have been done for MWNT and and strong acids and (H2SO4, NaNO3 and KMnO4) using
conducting polymer composites, and it was found that Hummer’s method or modified Hummer’s method to give
unoriented MWNT and polypyrrole composite show at least graphite oxide. This graphite powder after exfoliation (peeling
two times higher capacitance values than that of the individual the layers) gives graphene oxide [185–190].
component [178]. Electrodes made from aligned arrays of
CNTs coated with polypyrrole also show good supercapacitor
behaviour that has also been stated in [179]. Negatively oxidation exfoliation
Graphite powder → graphite oxide → graphene oxide
charged MWNTs and polypyrrole layers deposited by co-
deposition method (by means of electrochemical oxidation Lerf and Klinowski proposed the most accepted model of
process of pyrrole) were also studied for supercapacitor elec- GO. According to this model the GO can be regarded as a
trodes. A MWNT and poly (3-methylthylthiophene) compos- sheet of carbon atoms having hydroxyl (C–OH) group sand
ite shows specific capacitance about 80 F g−1 in 1 M LiClO4 epoxide (C–O–C) groups on its basal planes and carboxyl
acetonitrile solution [180]. A MWNT/poly (C=O, O=C–OH) group on its edges [185, 191]. The carbon
(3,4ethylenedioxythiophene) composite exhibited capacitance to oxygen ratio (i.e. C/O ratio) in GO relies on the preparation
values from 60 to 160 F g−1 and good cycling performance for method. The C/O ratio ranging from 2:1 to 4:1 is generally

produced; however, this ratio on reduction may reach to ~ and can be derived from all kinds of plants and animals. These
12:1 or even higher [185]. resources are available in different forms like wood animal
Graphene is a single atom layer or sheet of carbon atoms wastes different types of plants, parts of plants, etc. Before
with sp2 hybridization and arranged in a 2D honeycomb kind being considered as a precursor for supercapacitors, energy
of lattice [195]. Electrochemical reduction or chemical meth- from biomass has been used for heating and cooking. But
od used for the synthesis of graphene comprises oxygen com- these days, the use of biomass resources in electrochemical
prising functional groups in the final product; henceforth, capacitors for the synthesis of activated carbon has increased
graphene synthesized by this way is known as reduced as these resources are very cheap, readily available and can be
graphene oxide (R-GO) [196, 197]. R-GO is known some obtained by using very simple methods. The usage of biomass
other names also such as functionalized grapheme, chemically derived resources in the production of activated carbon to be
modified graphene and chemically converted graphene [185]. used for supercapacitor electrodes is also considered as a con-
In order to avoid any confusion with pristine graphene, we vincing way of battling waste disposal problem in various
shall refer it as reduced graphene oxide (R-GO) in the rest of sectors such as agricultural industries. Carbon, nitrogen, oxy-
the text. As shown in Fig. 7, the graphene, depending on the gen, hydrogen and traces of chlorine and sulphur are the key
number of layers present can be termed as single-layer or constitutes of the biomass resources. Biomass resources gen-
monolayer graphene sheet (Fig. 7a), double-layer or bi-layer erally show not as much of energy storage complications as
graphene sheet (Fig. 7b), few-layer graphene (3 to 10 other renewable sources [85, 86].
graphene layers) (Fig. 7c), graphene nanoplatelets or To obtain high performance from these sources, a good
nanographene platelets (10–100 graphene layers or approxi- conversion method should be chosen because the morphology
mately 3–30 nm thick) (Fig. 7d). Further, if the number of and the pore structure of the carbon material can be tuned by
layers is greater than 100 then it is known as graphite [198]. varying the parameter during the conversion process. Various
Unlike CNTs and other electrode materials, the large specific methods and techniques can be used to obtain energy from
surface area of highly conducting, thermally and mechanically biomass products like pyrolysis combustion, fermentation and
robust graphene is not dependent on the distribution of pores gasification etc. Biomass products can be converted to acti-
rather it depends on the number of layers such as single or few vated carbon by physical activation, chemical activation and
layered graphene and CNTs with less agglomeration exhibiting hydrothermal method, and these methods are discussed in the
high specific surface area and hence resulting in improved next sections.
supercapacitor performance [188]. Further, as the charge in
EDLCs is stored at the electrode surface of the material between Physical activation method Physical activation method is a
two layers (which can adjust themselves according to the elec- very simple process used for making activated carbon. This
trolyte used), the graphene is an ideal electrode material for high process consists of two steps pyrolysis or carbonization
rate performance of supercapacitors [198, 199]. followed by activation. Activation can be done along with
carbonization in a single step process or done in two-stage
Biomass-derived carbon materials for EDLCs process. Carbonization is done at relatively low temperature
(below 850 °C), and this process takes place in the absence
Biomass materials, including biologically formed materials, oxygen. In the carbonaceous process, the raw material is heat-
usually specify the living matters in various forms on earth. ed at a temperature below 850 °C in an inert atmosphere. A
These biomass materials are the renewable organic materials disordered form of carbon with low specific area is obtained
Fig. 7 Classification of graphene

sheets. Reprinted with permission
from [198]. a Mono layer, b Bi-
layer. c Few layers. d Graphene
nanoplatelets

after the carbonization process which is not suitable for Chemical activation gives carbon material with high spe-
supercapacitor application; hence for getting good pore struc- cific area and good porous structure. NaOH, KOH and ZnCl2
ture with high surface area, carbonization process is followed are the activating agents commonly used for the chemical
by a subsequent activation process. Physical activation uses activation. Washing of the material is required after the acti-
CO2, H2O or a mixture of these as an activation gas. High vation to remove the residuals of reactants (such as chloride
surface area, good pore size distribution and chemical polarity ions and zinc compounds) and inorganic residue (ash).
of the activated carbon can be obtained by choosing suitable Chemical activation process is time-consuming, energy-con-
activating agent [85, 86]. Coffee, corncob, bagasse bottom suming, tedious and expensive as compared to physical acti-
ash, almond shells and macadamia nutshell have been used vation process but has superior merits also like low conversion
as biomass resources to produce activated carbon by physical temperature, higher carbon yield, good porosity and larger
activation method [200–203]. specific surface area and [85, 86]. Various raw materials in-
Taer et al. [204] used rubber wood sawdust to make porous cluding coal, peat, pitches, cokes to renewable biomass pre-
activated carbon monoliths with a highest BET surface area cursors and diverse agricultural wastes and forestry wastes
(194 m2 g−1) and a specific capacitance of 10.55 F g−1. Nabais (e.g. corncob, rice straw, rice husks, saw dust, barks, nut shells
et al. [200] synthesized activated from coffee endocarp by phys- and wood) have been extensively used for producing activated
ical activation method using carbon dioxide as the activating carbon by chemical activation method used for the energy
agent to make activated carbon exhibiting a high specific surface conversion and storage applications [207, 223–232]. The ac-
area of 1050 m2 g−1 and pore volume of 0.5 cm3 g−1 with a tivation mechanism for the chemical activation is still not fully
specific capacitance value of 176 F g−1 (Table 4). To design understood due to the involvement of numerous experimental
electrode material from activated carbon derived from biomass variables and many precursors.
products, it is necessary to understand the relationship of micro- In EDLCs, the increase in the surface area of the electrode
structure, conductivity and porosity as these are the critical pa- material and porosity can lead to more charge stored but there
rameters for designing supercapacitor electrode materials. exists no direct relation between the surface area and the
charge stored. Another important factor in EDLCs which af-
Chemical activation method Many authors have reported high fects its overall performance is the pore size distribution. The
specific area and good specific capacitance values for the macropores (pore size > 50 nm) do not help in the adsorption
electrodes made from the biomass derived porous carbon by of ions/charges and mesopores (2 nm < pore size < 50 nm)
chemical activation process [86] (Table 5). For example, a provide a path for the charge and ions. It is actually the mi-
honeycomb-like carbon foam derived from the natural flour cropores which adsorb the electrolyte ions during charging
by KOH activation showed specific surface area process. Hence, the carbon material having good pore size
(1313 m2 g−1) and a good specific capacitance (473 F g−1) distribution have optimum number of macro, meso and mi-
[86]. Wang et al. [209] studied the relationship of microstruc- cropores so that maximum developed area can be utilized in
ture, porosity, conductivity and performance, of celtuce leave- the double-layer formation but controlling the pore size distri-
derived porous carbon to design advanced electrode materials bution is not very easy. As discussed earlier also, activated
of 102 Wh kg−1 (48 Wh L−1), along with good cycling life carbon powder should be mixed with binders before being
stability [222]. Chemical activation process is one step process used as an electrode in supercapacitors which further de-
combining the carbonization and activation. Chemical activa- creases the performance of the device [233].
tion process is mixed with activating different activating Although activated carbon fabrics do not require binder
agents for example KOH, H3PO4, ZnCl2, FeCl3, NaOH and addition for its electrode applications and can have high sur-
K2CO3 and is mixed with precursor materials and heated at a face area as high as activated carbon powder [234], the high
temperature from 300 to 950 °C. cost of activated carbon fabrics causes a hindrance in their
Table 4 Specific surface area and pore volume values of carbon electrodes derived from numerous biomass resources by physical activation methods
and their specific capacitance values in aqueous electrolytes
Biomass resources Electrolyte Specific capacitance Specific surface area Pore volume Ref.
(F g−1) (cm2 g−1) (cm3 g−1)
Rubber wood sawdust H2SO4 (1 M) 138 913 0.61 [204]

Carbon residue from biomass gasification – – 590 0.335 [205]
Coffee endocarp H2SO4 (1 M) 176 1050 0.5 [200]
Firewoods NaNO3 (1 M) 105 1016 0.747 [95]
Pistachio shell NaNO3 (1 M) 80 1009 0.667 [95]

Table 5 The pore volume and specific surface area of few important carbon electrode materials derived from various biomass-derived resources by
chemical activation method and their specific capacitance values (in aqueous, liquid ionic and organic electrolytes)
Biomass resources Electrolyte Specific capacitance Specific surface Pore volume Ref.
(F g−1) area (cm2 g−1) (cm3 g−1)
Pine cone Organic 198 3950 2.395 [206]

Pig bone KOH (7 M) 185 2157 0.77 [207]
Willow catkins KOH (7 M) 253 1586 0.78 [208]
Celtuce leaves KOH (2 M) 421 3404 1.88 [209]
Waste tea leaves KOH (2 M) 330 2841 1.366 [210]
Sunflower seed 30 wt% KOH 311 2585 1.41 [211]
Ginkgo shells KOH (6 M) 178 1775 – [212]
Cow dung Organic 124 1984 0.91 [213]
Silk Liquid ionic 242 2494 2.28 [214]
Human hair KOH (6 M) 340 1306 0.9 [215]
Sewage sludge Na2SO4 (1 M) 379 2839 2.65 [216]
Fallen leaves KOH (6 M) 242 2869 1.598 [217]
Argan seed shells H2SO4(1 M) 355 2062 – [218]
Saccharum bengalense leaves ZnCl2 102.6 2090 – [219]
Oil palm H2SO4(1 M) 149 1704 – [220]
Waste coffee beans H2SO4 (1 M) 368 1019 – [221]
application for supercapacitor electrodes. Carbon nanotubes supercapacitors, the concept of the hybrid/asymmetric capac-
also have the high electrical conductivity and good surface itors has been adopted from the last decade. Primarily, three
area which are the good properties for EDLCs but CNT- important approaches have been adopted to fabricate the ca-
based supercapacitors generally do not show notable specific pacitors with hybrid or asymmetric configuration to replace
capacitance due to less volume of micropores. Surface the conventional symmetric configurations of EDLCs/redox
functionalization and activation of CNTs lead to significant supercapacitors.
improvement in the capacitance value but affects the cycle life These three approaches are briefly described as follows:
[170] adversely. Template synthesis method has been proven a
good method for the controlled and uniform porosity [235]. I. Type I: First type of a hybrid supercapacitor is fabricated
There are many other factors such as the desolvations of the with one electrode purely with materials showing
electrolyte ions, porosity saturation, ions trapping in pores and pseudocapacitance such as conducting polymers/metal ox-
intercalation/insertion of ions which affect the overall perfor- ides and another electrode with material which has the
mance of EDLCs [236]. double-layer effect of charge storage, i.e. any form of car-
bon materials. It is found that the energy density of these
Hybrid supercapacitors hybrid devices is significantly higher than that of pure
pseudocapacitors or EDLCs. Such hybrid configuration
To make the supercapacitor practical for use as power source was first time reported by Laforgue et al. [237].
to the electronic circuits and other applications, higher volt- Thereafter, various hybrid capacitors of these types have
ages are needed. Higher voltages can be obtained by been reported [6, 26].
connecting the cells in series, but if more than three or four II. Type II: Another type of hybrid capacitor configuration
capacitors are connected in series, then the problem of over- has been reported by Evans [238] in which RuO2 is used
voltage occurs which can be avoided by prevented by proper as a capacitive electrode (cathode) conjugated to a Ta2O5
voltage balancing. Further, the typical gravimetric energy den- electrolytic capacitor anode. This combination of anode
sity of supercapacitors is 1 to 10 Wh kg−1. Like any other and cathode gives rise to improved charge capacity and
energy storing devices, supercapacitor has its merit and de- energy density.
merits. The use of novel electrolytes, such as polymer electro- III. Type III: The third, most effective and most studied
lyte and ionic liquids (with high breakdown voltage) in place hybrid configuration of supercapacitor involves hybrid-
of conventional aqueous electrolytes, may lead to the en- ization of a faradically rechargeable battery electrode
hancement in the low energy density of EDLCs. In order to such as Ni(OH)2-NiOOH or Pb/PbO 2 with a non-
improve upon, particularly the specific energy of the faradically rechargeable supercapacitor electrode [6,

239]. The battery electrode–electrolyte interface ensures reported in terms of improved cyclability and safety.
higher specific energy, whereas the supercapacitive in- Figure 9 shows initial charge capacity versus the cycle number
terface ensures high power density. of some of these lithium-based capacitors [242]. Besides
Li4Ti5O12, several other oxide materials in nanoform are being
Important point to note is that in such hybrid systems, en- used in hybrid supercapacitors with high operating voltage
ergy density improvements are usually achieved at the cost of range and excellent cyclability [242].
long-term cycle life. These configurations have been shown
by Ragone plot in Fig. 8.
Lithium ion capacitor is a high-energy hybrid capacitor Electrolytes
which consists of activated carbon as the positive electrode
and negative electrode is made up of graphite material pre- As mentioned earlier, electrolyte is considered as an important
doped with lithium ions. Hence, lithium ion capacitor can be parameter of supercapacitors that determines its operating
considered as a combination of lithium ion battery (as nega- voltage range, energy density, power density, etc. [77, 80,
tive electrode) and EDLC (as positive electrode). These ca- 243]. An electrolyte, employed in supercapacitors, should
pacitors have high working voltage (3.8 to 4.0 V) which aids have the following requirements [80, 243].
to high-energy density (up to 30 kW kg−1) along with high
power density (up to 30 Wh kg−1) [233]. i. High electrochemical stability
Like lithium ion capacitor, nanohybrid capacitor is another ii. High concentration of free/dissociated ions along with
type of hybrid capacitor in which the negative electrode is high mobility and least ion pairing
made up of a composite material of carbon and lithium titanate iii. Availability at high purity
(Li4Ti5O12) and positive electrode is made from activated car- iv. Low volatility
bon. Lithium titanate is a safe and stable electrode material v. Wide voltage window
possessing good redox properties which enhances the energy vi. Low solvated ionic radius
density without affecting the interfacial characteristics [233]. vii. High conductivity giving high power delivery
Lithium titanate possesses several essential properties suitable viii. Low viscosity
for electrochemical capacitors such as it shows very high cou- ix. Low cost
lombic efficiency (~ 100%) and displays only small volumet- x. Low toxicity
ric changes. It may be concluded from the above discussion
that the nanohybrid capacitor exhibits excellent performance Primarily, following two classes of electrolytes are used as
at low temperatures. The Li4Ti5O12/electrolyte/AC system has separators in supercapacitors:
recently been proposed by Amatucci and co-workers and re-
ported more than 10 Wh kg−1 energy density (at 3.2 V) with i. Liquid electrolytes (such as aqueous, ionic liquids,
high power capability [240, 241]. Fuji Heavy Industry recent- organic)
ly announced a lithium ion capacitor with the same configu- ii. Solid electrolytes primarily polymer-based electrolytes
rations. Recently, the use of nanostructures of Li4Ti5O12 as
supercapacitor electrode in the hybrid capacitor has been These two types of electrolytes are discussed in the follow-
ing section.
Liquid electrolytes
Aqueous electrolytes are considered as strong electrolytes,

which exhibit high value of dissociation constant, ά, and gen-
erally have higher ionic concentration and least ion pairing
owing to high dielectric constant value, high conductivity val-
ue (∼ 1 S cm−1), smaller solvated ions having access even to
very small pores. Hence, aqueous electrolyte–based
supercapacitors exhibit higher capacitance and higher power
compared to organic electrolytes [80, 243]. The aqueous so-
lutions of NH4Cl, KOH, Na2SO4 and H2SO4 are generally
used in supercapacitors. However, aqueous electrolytes offer
relatively small voltage window (as low as ~ 1.2 V) than that
Fig. 8 Ragone plot of various proposed asymmetric/hybrid capacitors. for organic electrolytes [164, 243]. Hence, the energy density
Reprinted with permission from [239] and power density, which directly depends on the

Fig. 9 Cycling performance of a

hybrid capacitor. Reprinted with
permission from [242]
electrochemical window of the capacitors using aqueous elec- attractive properties like non-flammability, high thermal sta-
trolytes, are lower. Therefore, the performance of the devices bility, low vapour pressure high electrochemical stability for a
with aqueous electrolytes in terms of energy densities along varied potential window, non-toxicity and high ionic conduc-
with the power densities is poor due to their narrow voltage tivity at elevated temperature etc. [77, 80, 243]. But, due to
stability window. Hence, to increase the performance of their low conductivity and moderately high viscosity, IL-
supercapacitors to meet the high energy and power densities based EDLCs exhibit substantially higher value of ESR as
requirements, organic electrolytes are preferred as they have compared to conventional electrolytes but this high value of
higher operating voltages (from 2.5 to 3.0 V) [164]. One mo- ESR can be compensated by larger potential widow to give an
lar of Et4NBF4 (tetraethylammonium tetrafluoroborate) added acceptable value of power density [244].
to propylene carbonate (PC) or acetonitrile has been demon- Main cations, in general, used to synthesize ILs include
strated as the best candidate of this category [80]. The lower imidazolium and asymmetric aliphatic quaternary ammonium
value of specific capacitance value for supercapacitors using pyrrolidinium ions, and the anions involved are tetrafluorobo-
organic electrolyte is observed due to larger size of solvated rate (BF 4 − ), trifluoromethanesulfonate (CF 3 O 3 S − ), bis
ion. In this perspective, the controlled pore size distribution is (trifluoromethanesulfonyl) imide (TFSI−), bis
an important parameter to achieve good capacitance values (fluorosulfonyl) imide (FSI−) or hexafluorophosphate (PF6−)
[164]. Further, the low conductivity of organic electrolytes [245–247]. The nature of anions and cations determine the
as compared to aqueous electrolyte results in power deterio- properties of the ILs, e.g. pyrrolidinium and aliphatic quater-
ration. Organic electrolytes suffer from many other problems nary ammonium and salts offer a wider potential window (>
also including complex purification procedure, toxicity and 5 V) and lower conductivity in comparison to 1-ethyl-3-
safety concerns due to the flammability, e.g. lithium- methylimidazolium-based ionic liquids that offer high con-
containing electrolytes are hygroscopic that results in explo- ductivity (10−2 S cm−1) at room temperature [246]. The main
sion and flammability when exposed to air [77, 164]. challenge is to design ILs exhibiting wider potential window
Ionic liquids (ILs) or room temperature (RT) molten salts and higher conductivity over a larger range of temperature.
that consist of salts in the liquid state are the recently discov- As mentioned above, the liquid electrolytes exhibit good
ered environment friendly and safe class of the liquid electro- electrochemical performance, however, they suffer from nu-
lytes [80]. These electrolytes are liquids at room temperature merous problems such as leakage, corrosion, bulky size and
(known as room temperature ionic liquids or RTILs) and at self-discharge etc. [4, 248–250] which restrict their use in
low temperatures. Ionic liquids consist of poorly coordinated various electrochemical devices including supercapacitors
ions making them an attractive candidate for various applica- and rechargeable batteries. Hence, the development of high
tions such as solvents and ‘green electrolytes’ or electrically ion conducting, mechanically and electrochemically stable
conducting fluids [77]. Ionic liquids have attracted global re- polymer–based electrolytes is being considered in place of
searchers for the supercapacitors owing to their several liquid electrolytes [251–260].

Polymer-based electrolytes ionic salts into different polymer hosts viz. poly propylene
oxide (PPO) and poly ethylene oxide [263, 270].
Polymer-based electrolytes are the solid polymeric mem- II. Plasticized polymer electrolytes: These types of electro-
branes which can be used as ion or electron conductors by lytes are prepared by mixing liquid plasticizers such as by
adding suitable salts such as potassium or sodium. Due to their mixing ethylene carbonate (EC) and propylene carbonate
good ion transport properties, they find their applications in (PC) or polyethylene glycol (PEG) etc. with the dry solid
supercapacitors. Polymer-based electrolytes have good me- polymer electrolytes [263–265].
chanical and ionic properties like good ionic conductivity III. Rubbery electrolytes: These are also referred as ‘poly-
(10−3 S cm−1) at ambient conditions, ease of fabrication and mer-in-salt’ materials and are prepared by mixing salts with
flexibility which make them superior than other solid electro- the small amount of polymers viz. PEO and PPO [271].
lytes. The detailed description including their historical back- IV. Solvent-swollen polymers: In these electrolytes, some
ground and classifications is given in following sections. solvents swell the polymer hosts. Both the aqueous and
In solid polymer electrolytes (SPEs), an appropriate salt is non-aqueous types of solvents are used to swell the poly-
dissolved in a solvating polymer medium (matrix). SPEs have mers for instance polyvinyl pyrrolidone (PVP) and polyvi-
fast ion transport mainly due to the presence of amorphous nyl alcohol (PVA), and the dopant ionic solutes like H3PO4
phase in the polymeric matrix and the conductivity in polymer and H2SO4 are accommodated in swollen lattice [272].
electrolytes increases with the amorphous nature of the host V. Polyelectrolytes: Such electrolytes are also termed as
medium [261]. Thus, the major research efforts in the past in poly-ions or ionomers. In polyelectrolytes, repeating units
SPEs were focused mainly on producing an amorphous phase stand an electrolyte (salt) group or a self-ion-generating
for the polymeric host medium which is with good stability group attached with the main chain of the polymers [273,
and low value of glass transition temperatures (Tg) for good 274]. The self-generating group in polyelectrolytes is re-
elasticity of the polymer chains to have faster ionic transport. sponsible for the ionic conductivity.
However, this concept that amorphous phase of polymeric VI. GPEs: Gel polymer electrolytes (GPEs) are obtained by
matrix is responsible for the ion transport is recently upturned mixing a large quantity of the salt solution in liquid plasticiz-
by Gadjourava and co-workers [262]. Gadjourava et al. exper- er to a polymer matrix. Hence, gel polymer electrolytes are
imentally verified that the stable and ordered crystalline kind the polymer network inflamed with appropriate solvents
of environments of the polymer host medium also adds to the and, henceforth, own the properties of both solids as well
high ionic conduction for SPEs. If polymer electrolytes are to asofliquids.Thepolymermatrixusedshouldform stablegel
be used in electrochemical devices, then they should have [254, 264, 265]. GPEs have high ambient conductivities but
below mentioned properties [263–275]: low mechanical stability. It was Fenullade and Perche [275]
who first time in 1975 established that polymers can be plas-
i. Ionic transference number should be one (‘tion’ ~ 1) ticizedwithanaproticsolution(comprisingofanalkalimetal
ii. High value of ion conductivity (≥ 10−4 S m−1) salt). The alkali metal salt stuck within polymer matrix form
iii. Good mechanical strength gels, and these gels have high ionic conduction values. Since
iv. High thermal, chemical and electrochemical stabilities then, many polymer hosts viz. PEO [276], poly(vinylidene
v. High compatibility with the electrode fluoride) (PVdF) [277, 278], poly(acrylonitrile) (PAN) [279,
280], poly(methyl methacrylate) (PMMA) [281, 282],
poly(vinylidene fluoride-hexafluoropropylene) (PVdF-co-
Classification of polymer-based electrolytes HFP) [11, 195] and cellulose acetate (CA) [283] have been
used for gel polymer electrolytes which exhibited the con-
Peter V. Wright in 1973 first time showed that poly ethylene ductivity values ranging between 10−4 and 10−3 S cm−1 at
oxide or PEO (an ion conducting polymer) with sodium and ambient conditions. Usually, low-evaporation solvents viz.
potassium salt can be used as a solid electrical conductor dimethyl carbonate (DMC), EC, PC, diethyl carbonate
[266]. After that, several polymer-based electrolytes (with dif- (DEC)anddimethyl formamide(DMF)canbeusedas‘plas-
ferent ions viz. Mg++, H+, Na+, Li+) have been investigated for ticizers’ [266]. It has been observed that in some polymer
their physico-chemical properties and their applicability in hosts having low glass transition temperature (as low as −
many devices [263–265]. Various preparation routes such as 40 °C), the immobilization of liquid electrolyte increases the
solution-cast technique and hot-press method are used for amorphous character and this increase in amorphous char-
polymer electrolytes. Polymer electrolytes are mainly divided actercausesanincreaseinthemobilityofthe gel electrolytes.
into the following categories [268, 269]: Henceforth,thetotalincreaseintheconductivityoftheGPEs
is mainly due to substantial enhancement of the ionic mobil-
I. Polymer–salt complexes: Polymer–salt complexes are ityattheexpensesofdiffusivetransportpropertyoftheliquid
solvent free SPEs and are formed by mixing a variety of phase [284, 285].

Polyethylene oxide–based gel electrolytes, comprising of lith- enhanced. The ionic conductivity of the polymer electrolytes
ium salts and propylene carbonate and/or EC as plasticizers such such as PEO can be enhanced by mixing room temperature
as LiClO4, LiCF3SO3 and LiN(SO2CF3)2, form soft solids and ILs but the selection of a suitable room temperature ionic
possess very high conductivity at room temperature (~ liquid (RTIL), e.g. 1-ethyl-3-methylimidazolium (EMI+) cat-
10−3 S cm−1) [276, 286]. But PEO-based gels have poor mechan- ion and BMP+ for electrochemical devices. These RTILs have
ical strength because PEO becomes soluble in the solvents [286]. many desirable properties such as high ionic conductivity,
The mechanical strength of these PEO-based gels can be en- wider electrochemical stability window and low viscosity in
hanced by cross-linking of PE and polymer hosts by various GPEs for supercapacitors application [294].
methods such as by exposing them to different types of radiations
viz. UV [287], thermal [288], photo [289] and electron beam VII. Composite polymer electrolytes or composite gel
[290]. These radiations help in the trapping of the liquid electro- polymer electrolytes: They are basically two-phase
lyte in the polymer host matrix. In the PAN polymers dispersed polymer/gel electrolytes. These electrolytes are pre-
salts and plasticizers, because of the lacking of oxygen atoms, a pared by dispersing small amount of micro- or
greater dissociation, i.e. greater conductivity of lithium salts nanosized inorganic particles such as ceramic into solid
could be attained [291]. Croce et al. [292] studied PAN-based polymer or gel electrolyte [298]. The mechanical
electrolytes comprising distinct lithium salts viz. LiAsF6, LiClO4 strength, interfacial activity and ionic conductivity of
and Li(CF3SO2)2. In these GPEs, the Li+ ion transference num- GPEs improve by these dispersed particles, and their
ber and the ionic conductivity were very high. However, these size plays significant role in enhancing the physical
GPEs are not frequently used in the lithium batteries as lithium properties [299].
electrode surface are not very stable. VIII. Plastic crystal gel polymer electrolytes: It has been
Polyvinylidene difluoride or PVdF-based gel is also being reported that the solid electrolytes such as polymer-based
used as electrolyte in supercapacitors. PVdF has electron- electrolytes containing plastic crystalline materials (e.g.
withdrawing functional group (–C–F) that is responsible for succinonitrile or SN) are also being used in the
Li–salt dissociation and possess high dielectric constant (up to supercapacitors [300–305]. In these electrolytes, plastic
8.4) due to which it has been used as a polymer host for the crystalline material acts as solid-state solvent. SN-based
GPEs. Though, the electrolytes consisting of PVdF-based gel gel/polymer electrolytes doped with several salts such as
show good electrochemical performances, but due to the poor sodium or lithium shows increase in ionic conductivity
interfacial properties between fluorine (from fluorinated poly- (from 10−4 to 10−3 S cm−1) at room temperature
mer host) and lithium (from PVdF-based gel electrolytes) [300–307]. The succinonitrile is a nitrile consisting of
electrolytes based on PVdF, gels do not show good stability two C2H4(CN)2 molecules per unit cell in crystalline
for lithium and its salts. Co-polymerizing PVdF with phase. The plastic phase of succinonitrile is stable for a
hexafluoropropylene (HFP) can substantially enhance its particular temperature from − 40 to 58 °C [303–305].
(PVdF) electrolyte properties. The PVdF-HFP showed lower Below − 40 °C, SN molecules occur only in gauche con-
crystallinity, reduced glass transition temperature and better formation. Gauche conformation has complete rigid
solubility for organic solvents than pure PVdF [293]. monoclinic kind of structure with all the rotatory motions
Plasticized GPEs exhibit high conductivity values due to being seized, whereas the plastic phase of succinonitrile
the presence of organic solvents, however, they have other at room temperature shows orientational disorder owing
disadvantages such as volatility, flammability and thermal to the co-occurrence of gauche and trans isomers. The
and electrochemical instabilities [293]. Hence, it is of the trans isomers present in SN act as impurity as they are
prime consideration to form gel or polymer electrolytes made responsible for the improvement of the lattice defects and
up of non-volatile solvents which shows better electrochemi- decrease in the activation energy for fast ionic transport
cal and thermal stabilities and wider potential window. [308–310]. The mechanism of ion transport for plastic
Recently, gel polymer electrolytes or ionic liquid–based poly- crystal was first reported for Li2SO4, the rotator motions
mer electrolytes are being used in place of molecular plasti- of the anion back the motion of the lithium ion from one
cizers such as EC–PC as promising electrolytes for batteries cation site to another in the lattice in a fashion that has
[294, 295], supercapacitors [294, 296], fuel cells [294, 297], been likened to a revolving door or paddle-wheel
etc. However, in the ionic liquid–based polymer electrolytes, mechanism.
the role of target ion to the total ion transport is relatively low,
which affects their performance in batteries but it does not As compared to the conventional organic solvents, SN has
affect the performance of supercapacitors. Ionic liquids have high ionic conductivity due to its high dielectric constant (~
high ionic concentration and hence do not encounter the elec- 55 at ambient conditions) and polarity [300, 308–314]. The
trolyte depletion problem as faced by the conventional elec- electrolyte based on SN shows the ability of accommodating
trolytes, and therefore, the capacitor performances are more mechanical stress due to their plastic character. Due to

this mechanical stress ability, these electrolytes offer better and can store a lot of charge in spite of being light in weight.
electrode–electrolyte contacts during electrochemical opera- Unlike lithium ion batteries, supercapacitors are safer, have low
tions due to ion switching at the interfaces of electrode and value of internal resistance and do not heat much in the case of a
electrolytes [315]. SN-like plastic crystalline materials show short circuit. Another advantage of supercapacitors in compari-
less loss of electrolyte by evaporation due to their small va- son to battery is that they do not degrade as rapidly as the batte-
pour pressure and are safe to use as they have minimal flam- ries and shows good tolerance at high temperatures. However,
mability. But, pure SN-based electrolytes are not suitable for supercapacitors show rapid discharge (supercapacitors voltage
ionic devices applications as flexible electrolyte shapes cannot decreases linearly with stored charge, whereas batteries generally
be obtained due to poor mechanical properties. So as to pro- supply constant voltage till they are entirely washed out) and
vide a definite shape such as a flexible film polymer hosts, e.g. though they can be charged in just few seconds but for that they
PAN and PVdF-HFP PEO should be used for the entrapment require large power supply. Hence, in supercapacitors, additional
of the electrolytes [301–304]. circuit is required to maintain the constant voltage but this addi-
tional circuit consumes some energy so, to get desirable voltage
and to deliver high energy. For that, the supercapacitors should
Summary and future perspective be coupled in series which increases the size, weight and cost of
the product. It is proposed that in the near future, the develop-
Supercapacitors have been considered as high power density ment of graphene or CNT based hybrid material for
storage devices that store charge at the interface between po- supercapacitor applications may increase the energy density
rous carbon electrodes and electrolyte solution. along with fast charging time and high cycle life at a low cost.
Supercapacitors are classically governed by the same funda- Lithium ion capacitors can be a good source of energy in coming
mental equations as conventional capacitors, in addition days. They may replace lithium-ion batteries in hybrid BatCaps
higher surface area electrodes and thinner imaginary dielec- hybrid system. Moreover, the hybrid supercapacitors/lithium
trics which distinguish them from conventional capacitors and ion-capacitors may take space in the portable electronic device
provide greater capacitances. These devices may complement as well as in hybrid electrical vehicles. Environmentalists would
batteries for a sustainable future. On the basis of the energy be happy with supercapacitors because they are less hazardous.
storage mechanisms, types of the electrodes used and their Supercapacitors could also be used in growing market of
configuration and classification of supercapcitors are microhybrid cars in the future where a supercapacitor could pro-
discussed. The capacitance comes from the pure electrostatic vide the power during the stop and for the restart and will be
charges accumulated at the electrode/electrolyte interface in recharged while the car is running.
EDLCs. Therefore, it is strongly dependent on the surface area
of the electrode (mainly various forms of carbon) that is ac- Funding information The authors acknowledge the financial support re-
ceived from the Science and Engineering Research Board (SERB),
cessible to the electrolyte ions. The fast and reversible faradic
Department of Science and Technology, Government of India (sanction
processes take place due to electroactive species in redox ca- no. ECR/2016/001871) under the scheme Early Career Research Award.
pacitors. The combination of EDLCs, redox capacitors and
battery-type electrode based symmetric and asymmetric con- Publisher’s note Springer Nature remains neutral with regard to jurisdic-
tional claims in published maps and institutional affiliations.
figuration is still in considerations to improve energy density.
Nevertheless, biomass/waste has been proposed as a good
precursor for the production of activated carbon because it is References
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Journal of Solid State Electrochemistry (2019) 23:667–692

Background, fundamental understanding and progress

Introduction interest in developing new solutions for powering vehicles and

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whereas in case of batteries it takes hours to charge it [7, 8].

for electrodes (various forms of carbons, metal oxides,

Electrochemical capacitors are the electrochemical high- Baery/Capacitor

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Fig. 4 Schematic representation

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Table 1 Specific capacitance,

PFPT|TEMATf + CAN|PFPT| 86 – 39 35 [9]

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Table 2 Specific capacitance,

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Capacitor cells Capacitance Specific energy Specific power Ref.

(a) For organic and aqueous liquid electrolyte

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Capacitor cells Capacitance Specific energy Specific power Ref.

C-xerogel|EMITFSI|C-xerogel 128 – – 9.5 [120]

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Capacitor cells Capacitance Specific energy Specific power Ref.

AC|PMMA-TEAClO4--EC-PC|AC 38 68 5.3 0.22 [143]

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Fig. 6 a Plot of specific

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Fig. 7 Classification of graphene

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Rubber wood sawdust H2SO4 (1 M) 138 913 0.61 [204]

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Pine cone Organic 198 3950 2.395 [206]

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Aqueous electrolytes are considered as strong electrolytes,

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Fig. 9 Cycling performance of a

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