Journal of Energy Storage 50 (2022) 104222

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Journal of Energy Storage

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Review Article

Recent trends in electrolytes for supercapacitors

T.S. Bhat a, b, P.S. Patil b, *, R.B. Rakhi c, d, *
a
School of Nanoscience and Biotechnology, Shivaji University, Kolhapur 416 004, M.S., India
b
Thin Film Materials Laboratory, Department of Physics, Shivaji University, Kolhapur 416 004, M.S., India
c
Department of Physics, University of Kerala, Kariavattom, Thiruvananthapuram 695581, India
d
Materials Science and Technology Division, CSIR-National Institute of Interdisciplinary Science and Technology (CSIR-NIIST), Thiruvananthapuram, Kerala 695019,
India

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

Keywords: Supercapacitors (SCs) emerge as effective energy storage technologies with a short charge / discharge time, long
Supercapacitors life cycle, and good temperature behavior, yet still have a low energy density compared to batteries. In elec­
Hybrid electrolytes trochemical supercapacitors (ESCs), due to its physical and chemical properties, the electrolyte is the influencing
Smart and wearable electronics
element that determines the performance of the devices in terms of capacity, power density, energy density,
Energy density
Power density
speed performance, stability and safety. The current state of understanding of the electrode-electrolyte inter­
action in ESCs is at the core of this topic. There are numerous types of electrolytes, including aqueous, organic,
ionic liquids, solid or quasi-solid electrolytes, and redox active electrolytes. The latest types of electrolytes for SCs
are discussed here. This study also suggests a greater understanding of the unborn evolution of this field.

LiTFSI Lithium bis(trifluoromethanesulfonyl)imide

Abbreviations 1. Introduction
Temp temperature
RT room temperature The growing demand for energy and the scarcity of non-renewable
CNT carbon nanotube energy sources have led to a focus on renewable energy sources such
HFIP 1,1,1,3,3,3-hexafluoropropan-2-ol as wind, solar and tidal energy, among others. When using renewable
AC activated carbon energy sources, energy storage systems are required [1–4]. Batteries are
ADN adiponitrile known for devices with high energy density, while capacitors are known
TEMABF4 triethylmethylammonium tetrafluoroborate for devices with high energy density. Researchers are currently working
PS 1,3-propylene sulfite on an energy storage device that bridges the gap between the battery
EC ethylene carbonate and capacitor i. e. Supercapacitor with high power density, quick
DMC dimethyl carbonate charge-discharge rate, extended life cycle, wide temperature operating
EA ethyl acetate range, and low maintenance costs [5–7]. Fig. 1(a) shows the diagram of
PANI polyaniline energy storage systems, i. e. Power versus energy density, also known as
PVA Polyvinyl alcohol Ragone plot [8].
PAA peracetic acid According to the energy storage mechanism, SCs are divided into
PEO polyethylene oxide three classes: electrochemical double-layer capacitors (EDLC), pseudo-
PMMA Polymethyl methacrylate capacitors (PC), and hybrid SCs, as can be seen in Fig. 1(b) [9]. EDLCs
PVDF-HFP Polyvinylidene fluoride-co hexafluoropropene can store charges electrostatically, which does not involve any charge
PC propylene carbonate transfer between the electrode and electrolyte ions [10 - 12]. Charge
DMF dimethyl formamide storage in EDLCs is the electrochemical double layer, while
EC ethylene carbonate pseudo-capacitors store charges through the faradic process, in which
SN succinonitrile

* Corresponding authors.
E-mail addresses: [email protected] (P.S. Patil), [email protected], [email protected] (R.B. Rakhi).

https://doi.org/10.1016/j.est.2022.104222
Received 16 November 2021; Received in revised form 28 January 2022; Accepted 11 February 2022
Available online 20 February 2022
2352-152X/© 2022 Elsevier Ltd. All rights reserved.
T.S. Bhat et al. Journal of Energy Storage 50 (2022) 104222

charge is transferred between the electrode and the electrolyte, as shown range, stability and safety.
in Fig. 1 (c and d) [12,13]. EDLCs offer excellent cycle and performance This review gives an overall insight of various gel polymer electro­
stability, while pseudocapacitors have a high energy density [14]. lytes (GPEs) and the factors influencing their performance, the criteria of
Carbonaceous materials such as carbon nanofibers, carbon nanotubes an ideal GPEs, and the performance of supercapacitors based on
(CNTs), activated carbon (AC), and graphene are EDLC electrode ma­ different GPEs. Key research results are summarized in tabular form
terials [15,16]. On the other hand, metal oxides, conducting polymers highlighting the electrochemical properties. Thus, the first section will
and their composites are pseudocapacitive materials due to their redox give the types of supercapacitors and traditional electrolytes and the
charge storage mechanism [17–20]. In the case of the hybrid system, parameters for evaluating the electrochemical performance. The second
there is the advantage that the battery-like electrode power source is section is devoted to consideration of hybrid electrolytes alongwith the
combined with a capacitor-like electrode power source in a single device parameters for evaluating the electrochemical performance, proton-
as shown in Fig. 1 (e and f). By choosing a suitable combination of conducting mechanisms and recent progress in different GPEs and the
electrode materials and a suitable electrolyte, the window of working ongoing efforts to improve their ionic conductivity and electrochemical
potential can be widened, which in turn leads to increased power and performance. In the final section, applications of flexible solid-state SCs
energy densities [21]. and several possible strategies are given to overcome the challenges for
The electrolyte is the essential ionic conductor between the two the development of ideal GPEs.
electrodes in SCs and supplies ionic current to allow cellular processes The graph in Fig. 2(a) shows the number of articles published so far
with a significant influence on the electrochemical properties of the (source: Scopus). Research on this has always been sluggish. (As seen in
devices, in particular their voltage window, speed capacity, and cycle Fig. 2(a)) More and more research is being done to change electrode
stability [22]. The properties that characterize electrolytes are mainly materials, and not many electrolyte studies are published every year.
their ionic conductivity, electrochemical window, working temperature The literature on electrolytes has grown modestly in recent years,

Fig. 1. (a) Ragone plot shows the demand for high power/energy electrochemical energy storage devices relative to present day technology. Reprinted with
permission from ref. [8], Copyright 2014 American Chemical Society. Schematic illustration of a supercapacitor classified by capacitive type. (b) Schematic illus­
tration of EDLC, which has cations and anions that are physically layered from electrodes. The schematic cyclic voltmeter has the same shape as a capacitor. (c)
Schematic illustration of redox pseudocapacitor, which stores and releases energy through chemical adsorption reactions at the surface of the electrode. The
schematic cyclic voltmeter is not the same as a capacitor but has a similar shape. (d) Schematic illustration of intercalation pseudocapacitor, which stores and releases
energy through chemically transform reactions based on the faradaic charge storage mechanism. The schematic cyclic voltmeter shows the characteristics between
the capacitor and the battery. (e) Schematic illustration of hybrid capacitor integrated both electrode types, which is EDLC and redox pseudocapacitive material. (f)
Schematic illustration of hybrid capacitor integrated with both electrode types, which are EDLC and intercalation pseudocapacitive material. Reprinted with
permission from ref. [11], Copyright 2020 MDPI.

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T.S. Bhat et al. Journal of Energy Storage 50 (2022) 104222

Fig. 2. (a) Total number of reported literatures related to SCs from 1992 to 2022. Search formulation for “Electrolytes for supercapacitors” in title, search from
Scopus; search time: 10, January 2022. (b) Effects of the electrolyte on the ESCs performance.

particularly in relation to novel electrolytes, which have caught our The main disadvantages of aqueous electrolytes are their volatility and
attention and have led to the original aim of this work. Many factors can their small window of electrochemical potential, which creates a
influence the electrochemical performance of SCs [22] as can be seen in bottleneck for energy density.
Fig. 2(b). Although the criteria differ by electrode, the basic design goals A SC operating voltage of 0.9 V to 2.7 V may be increased by
of an ideal electrolyte remain the same across technologies: to produce substituting organic electrolytes for aqueous electrolytes [35]. A system
desirable intermediate stages in the central stage, as well as safety, speed of organic electrolytes contains a supporting electrolyte and an organic
performance, electrochemical stability, and affordability. Only until all solvent [36]. Solvents made from organic compounds are attracted by
these conditions are met can any electrolyte system be considered their low volatility, high electrochemistry stability, and large dielectric
commercially viable [23]. constant. An overview of organic electrolytes-based SCs is given in
Table 2. Research on organic electrolytes consists of finding the best
2. Electrolytes for ESCs organic solvent ratio for a given electrolyte and electrode. Organic
electrolytes ought to be free from water so that capacitor performance
2.1. Traditional electrolytes will be improved and self-discharge will be reduced [37]. Overcharging
a capacitor can also result in hazardous volatile compounds being
Conventional electrolytes are divided into aqueous, organic, IL, and released and a substantial loss or reduction in power storage capacity
solid or quasi-solid (Fig. 3(a)) [26,27]. Aqueous electrolytes, the type [38].
originally used in SCs, have strong ionic conductivity, low internal An innovative green electrolyte has emerged in recent years i.e. Ionic
resistance, and a small molecule diameter, allowing them to easily liquid (IL) has been widely employed in SCs, particularly in the field of
penetrate through micropores. Aqueous electrolytes are mainly used in EDLCs [44,45]. ILs has a relatively good conductivity and ion mobility, a
electrochemical processes in PC’s and EDLC’s. Research on aqueous wide electrochemical window, almost no volatilization, and low
electrolytes is mainly focused on acidic, neutral and alkaline aqueous toxicity. Fig. 4 shows some of the most commonly used cations, anions of
solutions, being the aqueous solutions of H2SO4 and KOH the most used ILs for SCs. This form of SC is, however, limited by the excessive vis­
[26]. The performance of aqueous electrolyte SCs is shown in Table 1. cosity of IL. Also, IL-based SCs have a much lower specific capacitance

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T.S. Bhat et al. Journal of Energy Storage 50 (2022) 104222

Fig. 3. (a) The classification tree of electrolytes for supercapacitor. Reprinted with permission from ref. [24], Copyright 2021 IntechOpen. (b) Classification of new
types of hybrid electrolytes for electrochemical SCs. Reprinted with permission from ref. [25], Copyright 2021 Elsevier.

than aqueous electrolytes. With solid electrolytes, miniaturized and 2.2. Hybrid electrolytes
ultra-fine SCs are possible thanks to their reliability, high specific energy
and absence of electrolyte leakage. However, due to the low conduc­ Given the foregoing, the new forms of hybrid electrolytes are mostly
tivity of most polymeric electrolytes at room temperature, poor contact based on the combination of classic electrolytes of various types, such as
between electrodes and electrolytes, and the comparatively limited aqueous and organic, aqueous and gel polymer, IL and organic, IL and
solubility of electrolyte salts in the polymer, the practical application of gel polymer as illustrated in Fig. 3(b). Table 3 shows the comparison of
solid electrolytes in SCs it is associated with difficulties [27]. various hybrid electrolytes. The hybridization of several electrolytes
In conclusion, each form of electrolyte has benefits and limitations, results in unique reaction mechanisms, applications, and future pros­
and it is impossible for a single type of electrolyte to fulfill the rising perity. The characteristics of the voltage window, ion conductivity,
demands of SCs. In recent years, new hybrid electrolytes have emerged suitable temperature range, and so on are enhanced by hybrid mixing of
as potential possibilities for SC applications. the electrolytes, which increases the energy density. Details of some
typical redox couples used in SCs are listed in Table 4.
The employment of a solid-state gel electrolyte with flexible

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T.S. Bhat et al. Journal of Energy Storage 50 (2022) 104222

Table 1
Aqueous electrolyte-based supercapacitors and their performance.
Electrode materials Electrolyte Type of electrolyte Specific capacitance (F g ¡ 1) Energy density (W h kg¡1) Power density(W Ref.
kg¡1)

rGO-MnOx 1 M Na2SO4 Neutral electrolyte 398.8 at 5 23.3 2001 [28]

mV s − 1
GO-PPy-Ag 1 M H2SO4 Strong acid electrolyte 370.6 at 5 25.5 399.1 [29]
mV s − 1
RuO2–graphene 0.5 M H2SO4 Strong acid electrolyte 479 at 0.25 20.28 600 [30]
Ag− 1
1
Fe2O3/rGO 2 M KOH Strong alkaline 1090 at 2 A g − – – [31]
electrolyte
Graphene/mPANI 1 M H2SO4 Strong acid electrolyte 749 at 0.5 11.3 106.7 [32]
Ag− 1
Manganese oxide nanosheets 1 M Na2SO4 Neutral electrolyte 398 at 1 35.4 8000 [33]
Ag− 1
Highly porous graphene planes 6 M KOH Strong alkaline 303 at 0.5 6.5 ~ 50 [34]
electrolyte Ag− 1

Table 2
Organic electrolyte-based supercapacitors and their performance.
Electrode materials Electrolyte Cell voltage Temp.( Specific capacitance(F Energy density (W h Power density(W Ref.
(V) ◦
C) g ¡ 1) kg¡1) kg¡1)

Graphene - CNT composites 1 M TEABF4/PC 3 – 110 at 1 A g − 1 34.3 400 [39]

Heteroatom doped 1 M LiPF6/(EC–DEC 1: 1) 3 RT 126 at 1 A g-1 29 2243 [40]
porouscarbon flakes

MnO2 nanorods-rGO//V2O5 1 M LiTFSI/ACN 2 RT 36.9 15.4 436.5 [41]

1
Microporous carbide derived 1 M NaPF6/ 3.4 - 40 to 60 120 at 1 mV s − ~40 ~90 [42]
carbon (EC–DMC–PC–EA
1: 1: 1: 0.5)
− 1
AC 1.6 M TEAODFB/PC 2.5 - 40 to 60 21.4 at 1 A g ~28 ~1000 [43]

Fig. 4. Commonly used cations, anions of ILs for SCs. Reprinted with permission from ref. [46], Copyright 2021 MDPI.

electrodes that can be built in thin, light and smart designs of any form problems; and so on. Furthermore, solid-state electrolytes appear to hold
and size gives flexible solid-state SCs (FSSCs) an edge over traditional promise for th46construction of bending and FSSCs. In the meanwhile,
SCs, enhancing its potential for application in flexible and wearable they avoid using separators in the SC device, which is especially
electronics [21]. Solid-state electrolytes, more especially gel electro­ essential for planar micro-supercapacitors (MSCs). The selection of an
lytes, are nearly always used in FSSCs. Solid-state electrolytes have appropriate solid-state (gel) electrolyte is critical in the development of
several advantages, including relatively high ionic conductivity, a sim­ high- performance FSSCs [61]. Aqueous gel polymer electrolytes,
ple production method, easy and inexpensive packaging; no leakage organic gel polymer electrolytes, redox-active gel electrolytes and ionic

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T.S. Bhat et al. Journal of Energy Storage 50 (2022) 104222

Table 3
Comparison of hybrid electrolytes.
Electrode materials Electrolytes Cell voltage Temp. ( Safety Remarks Ref.
(V) ◦
C)

Carbon based materials Aqueos and organic ~ 2.5 - 20 to 100 non-flammability high conductivity [47]–
[48]
Carbon based and pseudocapacitive Aqueous and gel ~ 2.2 − 20 to direct contact with microscale devices miniaturization, [49]–
materials polymer 120 human skin wearable devices [50]
Carbon based materials ILs and organic ~ 3.7 − 100 to no corrosiveness high boiling points, low melting points [51]–
25 [52]
Carbon based and pseudocapacitive ILs and gel polymer ~ 3.5 25 to 90 non-flammability miniaturized portable and wearable [53]–
materials electronics [54]

performance of SCs. Each electrolyte of a single component has its own

Table 4
disadvantages and hybrid electrolytes of several components can com­
Some typical redox additive in aqueous electrolyte from selected literature and
plement one another to provide broad voltage window expansion,
their electrochemical performances forsupercapacitors.
decreased viscosity, better ionic conductivity, increased stability,
Electrode Electrolyte Redox Species Performance Ref.
reduced ionic size and so on [75–77]. When coupled with
Materials
high-performance electrode materials, the energy density of the device
Porous carbon H2SO4 + CuSO4 Cu2+ and Fe2+ 223 mAh g − 1
[55] may be increased, making it more suitable to the practical development
+ FeSO4
and deployment of energy storage devices. Table 7 shows electro­
AC H2SO4 + MoO42− 841 F g − 1
[56] chemical performance analysis of flexible solid-state asymmetric designs
Na2MoO4 based on gel-electrolyte.
1
AC KI I- 1840 F g − [57]
2.2.1. Aqueous gel polymer electrolytes
AC HQ + H2SO4 HQ 5017 F g − 1
[58] The essential components of aqueous gel polymer electrolytes are a
host polymer matrix, an electrolytic salt, and a plasticizer. Aqueous gel
Co-Al LDH K3Fe(CN)6 + Fe(CN)63− 712 F g − 1
[59] polymer electrolytes are also regarded as hydrogel electrolytes. These
KOH are the most frequently used gel electrolytes because of their low cost,
− 1 high ionic conductivity and environmental friendliness. However,
Honeycomb- H2SO4 + Indole-based 205 F g [60]
like carbon dopamine + conjugated aqueous electrolytes often have restricted electrochemical windows [82,
dopamine macromolecule 83]. Typical polymer matrix include polyvinyl alcohol (PVA), peracetic
chloride acid (PAA) and polyethylene oxide (PEO); the plasticizer is usually
water; and the electrolytic salt can be a neutral salt (LiCl or Na2SO4), a
strong acid (H2SO4 or H3PO4) or a strong base (KOH) [84]. PVA has been
liquid-based gel polymer electrolytes are the four primary types of GPEs
extensively applied due to its facile preparation procedure, high hy­
[62]. Table 5 summarizes various combinations of polymer host
drophilicity, excellent chemical stability, good mechanical property,
matrices and electrolytic salts, as well as their associated ionic con­
high ability to form a transparent film with superior quality, low cost
ductivities. All of novel hybrid electrolytes described in Table 6 are
and nontoxicity [85]. PVA is a more appealing polymer for super­
produced by combining two or more components.
capacitor applications, according to a few studies on hydrogel electro­
Many factors can have an impact on the electrochemical
lytes. This is owing to its good chemical stability, nontoxicity, and
biodegradability. PVA is a watersoluble polymer with the greatest syn­
Table 5 thetic resin manufacturing volume in the world. Unlike the many vinyl
Advances in gel–polymer electrolytes based on combinations of different plas­ polymers, PVA does not prepare from the vinyl alcohol monomer due to
ticizers and polymer host matrices. its unstable nature. This polymer is prepared by hydrolyzing the vinyl
Electrolytic salt Polymer Ionic Type of Ref. acetate under alkaline conditions, and the complete or partial hydrolysis
host conductivity (mS electrolyte process separates acetate groups from polyvinyl acetate [84]. The
cm-1)
greater the degree of hydrolysis, the fewer acetate groups are present in
GO doped KOH PVA 200 Aqueous [63] the polymer. PVA is a linear polymer with hydroxyl groups that are
H2SO4 PVA 30 Aqueous [64]
smaller than the remaining acetate groups and do not interfere with the
LiCl PAM 10 Aqueous [65]
KOH PEO 1 to 10 Aqueous [66] polymer’s creation of crystalline areas. In other words, hydroxyl groups
KOH PVA 0.1 Aqueous [67] in one chain can form hydrogen bonds with hydroxyl groups in another.
LiClO4 PAN-b-PEG- 11 Organic [68] These chains are organised in a crystal lattice in this manner. In PVA
b-PAN solutions, hydrogen bonding occurs between the water and the polymer
DMF–LiClO4 PAN-b-PEG- 6.9 Organic [69]
chains in addition to intra-chain and intermediate chain hydrogen
b-PAN
EMIMBF4 doped PVA 39.3 Redox active [70] bonding [86]. Moreover, the –OH groups of PVA absorb a large amount
H3PO4 ionic liquid of water and consequently enhance the ionic conductivity of the elec­
p-Benzenediol PVA 34.8 Redox active [71] trolyte [87] .
(PB) doped aqueous
Patil et al. [88] fabricated porous β-MnO2 nanospheres and O-SnS
H2SO4
BAAS doped PVA 21.4 Redox active [70] nanoflowers on flexible stainless steel substrates (FSSS). Fabricated
H2SO4 aqueous (β-MnO2/SS//O-SnS/SS) asymmetric solid-state supercapacitor elec­
PC-Fc doped PMMA 1.89 Redox active [72] trodes reach Cs of 122 Fg− 1 (at 5 mV s − 1) with excellent cycling per­
TEABF4 organic formance (stable at 95.3% after only 5000 GCD cycles, 10 mA), which
PC-4-oxo TEMPO PMMA 1.73 Redox active [72]
denotes the excellent ability of the supercapacitor device using PVA-­
doped TEABF4 organic
EMITf PVdF–HFP 13 Ionic liquid [73] LiClO4 gel electrolyte membrane between electrodes. The large capaci­
[EMIM][TFSI] PEGDA 9.4 Ionic liquid [74] tance and high single ASSCs device voltage of +1.6 V allow high energy

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T.S. Bhat et al. Journal of Energy Storage 50 (2022) 104222

Table 6
Various hybrid electrolyte based SCs and their performance evaluation.
Type of electrolyte Electrode materials Electrolyte Cell voltage Specific capacitance Energy density Power Ref.
(V) density
1 1
Aqueous and organic Rose petal-derived porous 20 M LiTFSI WIS 2.4 63F g − at 0.5 A g − 44 W h kg− 1 564 W kg− 1
[47]
carbons (60 ◦ C) (60 ◦ C)
− 1 − 1 1 1
Aqueous and gel AC-derived carbon CMC–Na/Na2SO4 1.8 175.8 F g at 1 A g 19.8 W h kg− 225 W kg− [75]
polymer
1 1 1 1
ILs and organic 1.5 M EMI-PC-DME AC 3.0 131 F g − at 1 A g − 38.5 W h kg− 900 W kg− [76]
electrolyte
1 1 1
ILs and gel polymer Honeycomb porous carbon EMIMBF4 gel 3.5 48.4 F g − at 0.5 A g − 94.1 W h kg− 350 W kg− [77]
1
electrolyte

Table 7
Summary of electrochemical performances of flexible solid-state asymmetric designs based on gel-electrolytes.
Positive electrode Negative Electrolyte Voltagewindow Specific Max. Max. Cycling Ref.
electrode capacitance energydensity powerdensity stability

CoMoO4@NiMoO4⋅xH2O Fe2O3 KOH/PVA 1.6 V 153.6 F g-1 at 1 A g-1 41.8 W h kg-1 12 kW kg-1 89.3% after 5000 [78]
cycles
CuS/3D graphene 3D graphene KOH/PVA 1.6 V 32 F g-1 at 1 A g-1 5 W h kg-1 3.2 kW kg-1 77% after 1000 [79]
cycles
-2
Co3O4 AC KOH/PVA 1.5 V 215 mF cm at 1.5 – – 90.7% after 1000 [80]
mA cm-2 cycles
MnO2 CoP LiCl/PVA 1.6 V 1.94 F cm-3 at 1 mA 0.69 mW h 114.2 mW 82% after 5000 [81]
cm-2 cm-3 cycles

density and power density of 29.8 and 1.3 kW kg− 1, respectively. Fig. 5 subsequently penetrates in the diffusion process. The creation of
shows a series combination of two ASSCs devices (+3.2 V) glows four hydrogen bonds with other water molecules reduces the rate of pene­
yellow, four red, one yellow, and one green LEDs up to 2, 3, and 4 min, tration. The proton penetration rate is slower and has a larger activation
confirming the storage ability of the SCs device. energy than the hopping process. The mobility of polymer chains in the
Zhang et al. [89] created a biaxially stretchy supercapacitor based on amorphous phase is the mechanism of direct transfer. The mobility of
porous singlewalled carbon nanotube/poly- (3, 4 ethylene dioxythio­ the polymer chain in the amorphous phase enhances the transfer of
phene) (SWCNT/PEDOT) hybrid fiber using PVA/H3PO4 with an protons. Polymer chain segmental movements can produce proton
optimal component ratio by weight (6/5) as both binder and stretchable mobility in the amorphous phase above the polymer’s glass transition
gel polymer electrolyte. The stretchability, capacitance, energy density temperature. The proton conduction mechanism is temperature depen­
of 6 Wh. Kg− 1, and power density of 19.2 kW. Kg− 1 of the super­ dent and increases with temperature and humidity. As a result, the
capacitor. GPEs works on Grotthuss or hopping mechanism [84]. The diffusion mechanism outperforms the Grotthuss mechanism [90].
rate of creation and breaking of the hydrogen bond between the hy­ In general, organic solvents and their mixes utilized as plasticizers in
dronium ion and the water molecule determines proton mobility in the GPEs. The polymer to plasticizer ratio decides the degree of plasticiza­
Grotthuss or hopping process. The proton leaps from one location to tion of the gel electrolytes which influences the glass transition tem­
another with differing potential energy, separated by a minor energy perature of the gel electrolytes. The amount of plasticizers can be
barrier caused by the development of the strong hydrogen bond. As a adjusted to separate the amorphous area from the ion aggregates. As a
result, decreased activation energy leads to increased proton mobility. result of this, ionic conduction occurs along polymer chains, and an
The proton forms a combination with the water molecules and amorphous region’s connected network increases ion mobility, ionic

Fig. 5. Electrochemical performance of β-MnO2/SS//O-SnS/SS ASSCs device using PVA-LiClO4 aqueous gel polymer electrolyte. Reprinted with permission from ref.
[88], Copyright 2018 American Chemical Society.

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T.S. Bhat et al. Journal of Energy Storage 50 (2022) 104222

conductivity of gel electrolytes [84] . Water molecules in aqueous gel voltage window of 2.1 V. Furthermore, the cell demonstrated good
polymer electrolytes are trapped by 3D polymeric networks. The choice stability, with very little capacitance degradation over 30,000 cycles.
of the electrolyte salt depends on the electrode materials. It should be The electrolyte salt and salt/host polymer ratio have a substantial
noted that acidic or alkaline solutions might harm many dispensing impact on ionic conductivity.
nozzles; therefore, caution should be exercised while printing aqueous
electrolytes. 2.2.3. Redox-active gel electrolytes
Several groups have investigated the possibility of enhancing energy
2.2.2. Organic gel polymer electrolytes density and capacitance by introducing redox-active species into the
Generally aqueous gel polymer electrolytes have narrow operating electrolyte. Such species undergo oxidation at the positive electrode and
voltage window. This problem can be overcome by using organic gel reduction at the negative electrode during charging, thus producing
polymer electrolytes. The cell voltage could be increased to 2.5 - 3 V pseudocapacitance [94–96].
[62]. Generally, organic gel polymer electrolytes are prepared by Tiny-sized ions may easily enter the micropores and small mesopores
physically blending a polymer with high molecular weight, e.g., Poly­ of hollow porous electrodes. A large number of redox couples, such as
vinylidene fluoride-co-hexafluoropropene (PVDF-HFP) and Polymethyl iodides (KI) [97], K3Fe(CN)6 [98] and Na2MoO4 [99] and organic redox
methacrylate (PMMA) or, with a conducting salt in a nonaqueous sol­ mediators, such as hydroquinone [55], and P-phenylenediamine (PPD)
vent system followed by gelation. Organic solvents, like dimethyl [100] have been used to prepare redox-active gel electrolytes. Among
formamide (DMF), propylene carbonate (PC), ethylene carbonate (EC) redox electrolytes, the K3Fe(CN)6/K4Fe(CN)6 (ferricyanide/ferrocya­
and their mixtures, have been commonly employed as plasticizers to nide) redox couple is particularly popular due to its low toxicity, high
broaden the operating voltage range [91]. It is preferable to expand the solubility in water, high stability, and high theoretical specific capaci­
cell voltage window in order to improve the energy density of SCs. tance (283.6 F g − 1) [101].
A high-performance, thin, planar supercapacitor with dynamic Kundu et al. [102] fabricated a compact, lightweight, all-solid state,
stretchability is created by carefully selecting electrode and electrolyte symmetric supercapacitor device composed of PVA-K3Fe(CN)6-K4Fe
materials and creating a soft substrate layer by Lee and co-workers [92]. (CN)6 (PVA-PFC) redox-active gel electrolyte. The gel polymer plays the
A porous elastomer film is used as a prestrained substrate, leading to dual role of electrolyte and separator. Fig. 7(a) shows the charge storage
deposition of a buckled manganese/molybdenum (Mn/Mo) mixed oxi­ mechanism in the symmetric two-terminal supercapacitor device with
de@multiwalled carbon nanotube (MWCNT) electrodes. Use of an buckypaper /graphitic petals (BP/GP) electrodes and PVA-PFC gel
organic gel polymer electrolyte is made up of adiponitrile/succinoni­ polymer electrolyte. It exhibits a high area-normalized capacitance of
trile/lithium bis(trifluoromethanesulfonyl)imide/poly(methyl methac­ 390 mF/cm2 at a low current density of 2 mA/cm2, which is twice and
rylate) (ADN/SN/LiTFSI/PMMA). Fig. 6 shows the schematic four times that of devices composed of conventional PVA-H3PO4 and
illustration of the structure and fabrication process of a biaxially PVA-KOH gel electrolytes, respectively. Furthermore, cyclic voltamme­
stretchable planar supercapacitor. The operation cell voltage is try tests and long-term stability tests demonstrate a large stability
increased to 2 V, and the stability under air-ambient conditions is voltage window of 1.5 V, compared to only 1.0 and 0.4 V, respectively,
enhanced up to one month without encapsulation. Fabricated planar for the PVA-H3PO4 and PVA-KOH devices as shown in Fig. 7(b). High
supercapacitor exhibits an areal capacitance of 7.5 mF cm− 2 at a current capacitance combined with a wide voltage window leads to a maximum
density of 0.3 mA cm− 2, an areal energy density of 4.2 μWh cm− 2 at a volumetric energy density value of 2.47 mWh cm− 3 and maximum
power density of 0.3 mW cm− 2 and a power density of 1.0 mW cm− 2 at power density value of 0.6 W cm− 3.
an energy density of 1.4 μWh cm− 2. The supercapacitor exhibits stability Zhou et al. [103][102,103] developed a PEO/LiClO4-acetonitrile
under both static and dynamic stretching deformation with strains up to organic gel with two different redox mediators, NaI/I2 and K3Fe
50 and 30%, respectively. (CN)6/K4Fe(CN)6. The cells with NaI/I2 and K3Fe(CN)6/K4Fe(CN)6
Huang et al. [93] developed an OGE using a PEO–PAN blend could deliver specific energy densities of 49.1 Wh kg− 1 and 33.6 Wh
(PAN-b-PEG-b-PAN) as host, DMF as plasticiser and LiClO4 as an elec­ kg− 1 respectively.
trolytic salt for an AC-based SC. This OGE had an ionic conductivity of
6.9 mS cm− 1 and was extremely compatible with carbon electrodes. The 2.2.4. IL-based gel polymer electrolytes
constructed cell had a capacitance of 101 F g − 1 at 0.125 A g − 1 and IL-based gel electrolytes have several benefits over aqueous and
produced 11.5 W h kg− 1 of energy at a high power of 10 kW kg− 1 over a organic electrolytes. Ionic liquids (ILs) act as plasticizing salts in GPEs

Fig. 6. Schematic illustration of the structure and fabrication process of a biaxially stretchable planar supercapacitor using organic gel polymer electrolyte. GCD
curve dynamically recorded during finger bending/spreading motion (green) while the planar supercapacitor is attached to an index finger. GCD curve taken prior to
the finger motion (w/o motion) is presented in yellow color. Reprinted with permission from ref. [92], Copyright 2019 American Chemical Society.

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T.S. Bhat et al. Journal of Energy Storage 50 (2022) 104222

Fig. 7. (a) Charge storage mechanism in the symmetric two-terminal supercapacitor device with PVA-PFC gel polymer electrolyte. (b) Variation of energy density
and Coulombic efficiency with variation in operating cell voltage for the PVA-PFC, PVA-H3PO4, and PVA-KOH devices. The results are derived from galvanostatic
charge/discharge tests performed at a constant current density of 2 mA cm− 2. The dotted line corresponds to a coulombic efficiency value of 90%. The green circles
represent the energy density values corresponding to operation of the solid-state supercapacitor devices at the respective maximum charging voltage. Reprinted with
permission from ref. [102], Copyright 2018 American Chemical Society.

and increase the amorphous phase of the gels, improving the ionic Gao et al. [108] synthesised and used a 1-ethyl-3-methylimidazolium
conductivity, thermal, chemical, and mechanical properties, non­ bis(trifluoromethylsulfonyl)imide–poly(vinyl­
volatility, large working voltage windows (up to 3.5 V) and nonflam­ idenefluoride)-hexafluoropropylene [EMIM][NTf2]–PVdF(HFP) ILGE to
mability [62,104,105]. ILs are categorised into three types based on MnO2/CNT/carbon nano-onions. When employing the [EMIM][NTf2]–
anion and cation combinations: aprotic, protic, and zwitterionic, which PVdF(HFP) gel electrolyte, the FSSCs had an energy density of 16.4 Wh
are suitable for lithium batteries and supercapacitors, fuel cells, and kg− 1 and a power density of 33.3 kW kg− 1.
membranes, respectively [84]. As a result, they have a high potential for Because of the unique properties of ILs such as non-volatility, non-
use in flexible and stretchy SCs. Furthermore, because of their higher flammability, good electrochemical and thermal stability, low vapor
stability and absence of corrosion behavior to printing nozzles, they are pressure, and a wide electrochemical potential window, ILs, also known
better suited for printed SCs. There have been several reports of flexible as room temperature molten salts with melting points below 100 ◦ C, are
solid-state SCs employing ionic liquid gel electrolytes. Similar to appealing for use in energy storage devices [84]. Because ILs normally
aqueous gel polymer electrolytes and organic gel polymer electrolytes, a have a melting point over 0 ◦ C, eutectic IL combinations have been
variety of polymer hosts, such as PVA, PVDFHFP and PEO, have been investigated in order to lower the melting temperature and expand the
studied for ionic liquid gel electrolytes [106]. liquid range as shown in Fig. 9 [109]. A eutectic mixture is a combi­
Yang et al. [107] reported all-solid-state ASCs by using MnO2 coated nation of organic salt and additional molecules (such as urea or acetic
on a carbon cloth (CC) (MnO2@CC) as the positive electrode, reduced acid) that inhibit the crystallization of one another at certain ratios,
GO (rGO) coated on a CC (rGO@CC) as the negative electrode, and the resulting in a decrease in melting point [110]. It was demonstrated that
PVA:BMIMBF4:TBABF4 gels as solid-state electrolytes as shown in Fig. 8 the crystallization process is mainly affected by anions. Simon et al.
(a). It was found that the PVA:BMIMBF4:TBABF4 gel electrolytes [109] were able to extend the temperature range from − 50 ◦ C to 100 ◦ C
exhibited an enhanced ionic conductivity of 21.7 mS/cm compared to by mixing [PIP13][FSI] and [Pyr14][FSI]. To prevent an ordered
that (1.9 mS/ cm) of the PVA:BMIMBF4 gel electrolytes. ASCs exhibited arrangement and crystallization, the appropriate combination of cations
an operational window of 3.0 V, an energy density of 61.2 W h/kg at the with the same anion is essential. This combination restrains the forma­
power density of 1049 W/kg, and more than 80% capacitance retention tion of lattice [110][109,110]. GPEs may also suffer from narrow
after 3000 charge/discharge cycles. Moreover, ASCs are used to light operative temperature due to the presence of water and relatively poor
different LEDs with different turn-on voltages as shown in Fig. 8(b). mechanical strength [12].

Fig. 8. (a) Schematic illustration of the ASC device configuration with PVA:BMIMBF4:TBABF4 IL gel electrolyte (b) Different LEDs lighted by two series-connected
ASCs. Reprinted with permission from ref. [107], Copyright 2020 American Chemical Society.

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T.S. Bhat et al. Journal of Energy Storage 50 (2022) 104222

Fig. 9. Extended operating temperature range of SCs based on eutectic ILs mixture. Reprinted with permission from ref. [109], Copyright 2011 American Chem­
ical Society.

All these results demonstrated that developed ASCs have great po­ methyltriethylammonium tetrafluoroborate (Et3MeNBF4) in acetonitrile
tential applications in the high-performance wearable and portable de­ (AN) or propylene carbonate (PC) solution is the most often used com­
vices. A comparison of different representative research studies can be mercial supercapacitor electrolyte. There is a significant gap between
found in Table 8. the required top voltage limit of 2.7 V (AN system) or 2.8 V (PC system)
Tetraethylammonium tetrafluoroborate (Et4NBF4) or [119,120]. The most straightforward and practical solution to overcome

Table 8
Properties and components of SCs with different hybrid electrolytes.
Electrode materials Configuration Electrolyte Type of Electrochemical performance Ref.
Electrolyte

V2O5/GO//G-VNQDs/GO Asymmetric, PVA/LiCl Aqueous gel A potential window of 1.6 V, an areal capacitance of 207.9 mF/cm2, an [111]
planar polymer areal energy density of 73.9 mWh/cm2
electrolytes
Graphene/PEDOT:PSS Symmetric, PVA/H2SO4 Aqueous gel A volumetric capacitance of 348 F cm− 3, an energydensity of 12 mW h cm− 3
[112]
planar polymer at a power density of4386 W cm− 3
electrolytes
GOMnO2//AC Asymmetric, PVA/LiCl Aqueous gel 1.586 F cm− 2 (1023 F g − 1) at 4 mA cm− 2, an energy density of 22 mW h [113]
sandwiched polymer cm− 3 at a power density of0.099 W cm− 3
electrolytes
Ti3C2Tx Symmetric, PVA/H2SO4 Aqueous gel Areal and volumetric capacitances of 27 mF cm− 2 and 357 F cm− 3, [114]
planar polymer specifically at 20 mV s − 1, an energy density of 18 mW h cm− 3 at a power
electrolytes density of 15 W cm− 3
FunctionalizedMWCNT Symmetric, [EMIM][BF4]/ Organic gel A specific capacitance of 235 F g − 1 at 5 mV s − 1 in awide operating [115]
(fMWCNT) sandwiched [PVdF-HFP] polymer potential range of 3 V, an energydensity of 16.2 W h kg− 1 and a power
electrolytes density45 kW kg− 1 at 1 A g − 1
AC Symmetric, PVA-Li2SO4- Redox-active gel A specific capacitance of 139.1- 384 F g − 1 at 0.25 A g − 1, an energy density [116]
planar BMIMI electrolytes of 10.4–29.3 Wh kg− 1 with 80.9% capacitanceretention after 10,000 cycles
Activated-carbon/CNTs/Ag Symmetric, [BMIM][BF4]/ IL-based gel A working voltage window of up to 2.0 V, 100 mF cm− 2 [117]
NW= planar ETPTA polymer
electrolytes
Phosphorene and Symmetric, BMIMPF6 IL-based gel An areal capacitance of 9.8 mF cm− 2, a volumetriccapacitance of 37.0 F [118]
graphene planar polymer cm− 3, an energy density of11.6 mW h cm− 3
electrolytes

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T.S. Bhat et al. Journal of Energy Storage 50 (2022) 104222

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