Energy Storage Materials 34 (2021) 320–355

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Energy Storage Materials

journal homepage: www.elsevier.com/locate/ensm

Polymer gel electrolytes for flexible supercapacitors: Recent progress,

challenges, and perspectives
Hongliu Dai a, Gaixia Zhang a,∗∗, Diane Rawach a, Chaoying Fu a, Chao Wang b, Xianhu Liu c,
Marc Dubois d, Chao Lai b,∗∗∗, Shuhui Sun a,∗
a
Institut National de la Recherche Scientifique-Énergie Matériaux et Télécommunications, Varennes, Quebec, J3X 1S2, Canada
b
School of Chemistry and Materials Science, Jiangsu Normal University, 221116 Xuzhou, Jiangsu, China
c
Key Laboratory of Materials Processing and Mold, Ministry of Education, Zhengzhou University, Zhengzhou, 450002, China
d
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, F-6300 Clermont-Ferrand, France

a r t i c l e i n f o a b s t r a c t

Keywords: With the rapid development of portable electronic products, wearable flexible energy storage devices such as flex-
Flexible supercapacitors ible supercapacitors (FSCs) have attracted much attention. FSC devices possess various advantages, such as small
Gel electrolytes size, flexibility and lightness, smooth operation, wide operating temperature range, and high energy density and
Ionic conductivity
power density. However, there are still significant challenges to make FSC devices in large-scale applications, such
Flexibility
as poor gel electrolyte/electrode interface compatibility, poor cyclic stability under bending test conditions and
Stability
low ionic conductivity of the gel electrolyte. Therefore, to develop FSC devices with outstanding characteristics,
many efforts have been devoted to the development of polymer gel electrolytes which have excellent mechanical
properties and electrochemical performance. This review aims to provide an overview of recent progress towards
the development of advanced FSCs based on aqueous, non-aqueous, ionic liquid-based and redox gel electrolytes.
We systematically discussed the challenges and future development of various gel electrolytes for FSC devices.
Moreover, the development and performance evaluation of FSCs are also discussed.

1. Introduction
In recent years, the increasing demand for electronic devices such as
Google glasses, smartwatches and bracelets has promoted the rapid de-
velopment of flexible wearable electronic devices [1–3]. Compared with
traditional electronic devices, the flexible wearable electronic devices
have the unique advantages of flexibility, lightweight, and comfortabil-
ity, which has triggered their applications in flexible sensors, artificial
electronic skin and other wearable microelectronic devices [4–8]. With
this perspective, flexible wearable power sources are critical and in ur-
gent need for these devices.
The flexible wearable powers can be classified into two categories:
flexible electrochemical energy storage devices (FEESDs) including flex-
ible batteries [9] and FSCs [10], and the non-electrochemical energy
storage devices such as flexible photovoltaic cells [11]. Currently, the
FEESDs are the mainstream of flexible energy storage devices because
of their mature preparation process, no time limit, and easy commer-
cialization. However, due to the differences in materials utilization and
assembly methods, FEESDs also have their disadvantages, such as ther-
mal runaway and low energy density. Table 1 lists the performance and
basic parameters of flexible batteries and FSCs [12]. As can be seen,
FSCs have several advantages, such as high power density, fast charge
and discharge speed, wide operating temperature range, high efficiency,
and long cycle life, compared with flexible batteries [13]. FSCs also
provide higher security than flexible batteries, making them substan-
tial competitors in the field of flexible energy storage. FSCs are mainly
composed of flexible electrode materials, gel electrolyte, and packaging
materials. The difference between traditional supercapacitors and FSCs
lies in the electrode materials and electrolytes used which exhibit ex-
cellent flexibility. The flexibility property of the electrolytes allows the
device having a variety of shapes, lightweight, strong deformation abil-
ity and small size advantages [14,15], to be widely used in flexible and
wearable electronic devices.
However, to achieve FSC devices that can continuously provide sta-
ble electrochemical performance under repeated bending and folding
conditions, the development of flexible components such as electrodes,
separators, electrolytes, and housings is crucial. The key factors of the
FSCs are: (i) the necessity of the flexible electrodes to have multiple func-

∗
Corresponding author.
∗∗
Corresponding author.
∗∗∗
Corresponding author.
E-mail addresses: gaixia.zhang@emt.inrs.ca (G. Zhang), laichao@jsnu.edu.cn (C. Lai), shuhui@emt.inrs.ca (S. Sun).

https://doi.org/10.1016/j.ensm.2020.09.018
Received 10 June 2020; Received in revised form 23 September 2020; Accepted 26 September 2020
Available online 5 October 2020
2405-8297/© 2020 Elsevier B.V. All rights reserved.
H. Dai, G. Zhang, D. Rawach et al. Energy Storage Materials 34 (2021) 320–355

Table 1
Performance comparison between supercapacitors and lithium-ion bat-
teries [12].

Feature Supercapacitors Lithium-ion batteries

Power density (W/kg) 3000–40,000 1500

Gravimetric energy (Wh/kg) 4–10 100–265
Volumetric energy (Wh/L) 4–14 220–400
Efficiency (%) 97–98 75–90
Lifetime >10 k cycles 150 to 1500 cycles
Charge time 1–10 s 10–60 min
Risk of thermal runaway No Yes
Risk of explosion No Yes
Operating voltage (V) 0.8–1.23 1.2–4.2
Operating temperature ( °C) −40 to 85 −20 to 65

tions (such as a conductive electronic skeleton, an ion-conducting skele-

ton, and an active material carrier), and (ii) the electrolyte requirements
include outstanding ionic conductivity, excellent contact between elec-
trode and electrolyte, low electrode/electrolyte interfacial resistance,
flexibility and high stability under elevated temperatures [16–20]. Some
researchers have summarized the progress of the electrode materials for
SCs. Carbon-based electrode materials have been widely concerned by
researchers in the field of energy storage applications due to their advan-
tages including high specific surface area, good electrical conductivity,
large power density, and excellent chemical stability. For instance, Xia
et al. [21] systematically summarized the latest research progress and
electrochemical performance of graphene-based materials in terms of
graphene synthesis methods, corresponding composite materials, struc-
tural characterization, and design concepts. Chen et al. [22] resumed ad-
vanced flexible solid-state supercapacitors depending on carbon nano-
materials and introduced the mechanism, structure and electrochem-
ical performances for FSCs. Huang et al. [23] summarized the fabri-
cation, electrochemical properties and novel devices for the flexible
polypyrrole-based electrode. Apart from carbon materials, metal-based
electrode materials also have drawn great attention from scientific re-
searchers due to their excellent electrode/electrolyte contact area, fast
ion transmission channel and good electrical conductivity. To better un-
derstand the development of metal oxide electrodes, Fan et al. [24] give
an outline of solution-based methods for the controllable synthesis of
metal oxides and applications of corresponding materials in electro-
chemical energy storage. Moreover, Zhong et al. [25] resumed recent
progress in the synthesis and electrochemical application of transition
metal carbides (TMCs) and nitrides (TMNs) electrode for SCs, which
opened the door for new high-performance electrode materials in en-
ergy storage and conversion.
In this review, we mainly focus on the review of the most recent
processes of the utilization of various electrolytes, which are an essen-
tial component of FSCs due to numerous reasons [26]. First of all, the
electrolyte plays a crucial role in an electrochemical reaction. During
the FSC discharge progress, the electrode releases electrical energy by
absorbing the solute in the electrolyte. However, this step is not pos-
sible in the absence of the electrolyte, and therefore the FSC cannot
release electrical energy. Secondly, since the FSC electrodes are not in
contact, the current loop cannot be formed without the presence of an
electrolyte. Therefore, the electrolyte plays the essential role of the con-
ductive material in FSC devices. Thirdly, the presence of the electrolyte
determines the operating voltage of the FSCs, which affects both the en-
ergy and power density of the flexible supercapacitor. However, the use
of gel electrolytes in FSC devices has several challenges, such as poor
gel electrolyte/electrode interface compatibility, high volatility at high
temperature and low ionic conductivity, which need to be addressed to
obtain effective FSC devices. To solve these problems, researchers have
taken much effort on the further development of high-performance elec-
trolytes [27–31].
Herein, we will first demonstrate the development of electrolytes, the
reaction mechanism, the mechanical properties (e.g. length (L), bending
Fig. 1. An overview of FSCs based on various gel electrolytes.
angle (𝜃) and radius (R)) and the electrochemical performance of FSCs
in different electrolyte systems, which will help to further understand
the design principles of gel electrolytes and promote the commercial ap-
plication of FSC devices. The recent scientific development of gel elec-
trolytes for FSC devices is separated, into four categories as observed in
Fig. 1, which will be discussed throughout this review. Firstly, the de-
velopment of aqueous gel electrolytes using a conductive polymer as the
framework and acid/alkaline/salt as the electrolyte solute is discussed.
Secondly, the research progress in FSC devices based on non-aqueous
gel electrolytes is presented. Thirdly, a summary of the development
of ionic liquid gel electrolytes with a series of categories is presented.
Further, the scientific development of redox gel electrolyte is discussed.
Besides, we discuss the standard performance evaluation for FSCs from
the perspective of energy density, power density, and mechanical prop-
erties.
2. The overview and principles of FSCs
2.1. The energy storage mechanism of FSCs
FSCs have the same working mechanism as supercapacitors. There-
fore, based on the different energy storage mechanisms, FSCs can be
divided into the following two categories: (i) electric double-layer ca-
pacitors, and ii) pseudocapacitors. Electric double-layer capacitors can
store energy and release it through an adsorption/desorption process of
the electrolyte ions on the surface of the electrode material. However,
pseudocapacitors, also known as Faraday quasi-capacitors, have an en-
ergy storage mechanism composed of a series of fast and reversible redox
reactions with electrolyte ions at the surface or in the bulk phase of the
electrode material.
2.1.1. The energy storage mechanism of an electrical double layer
The electrical double-layer capacitance (EDLC) was first proposed by
the German physicist Helmholtz in 1853 [32]. As observed in Fig. 2a,
the electrical double-layer capacitance is produced by the confrontation
of charges caused by the directional arrangement of electrons or ions at
the electrode/solution interface [33,34]. For an electrode/solution sys-
tem, when an electric field is applied to both electrodes, the solvated
anions and cations in the solution migrate to the positive and negative

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H. Dai, G. Zhang, D. Rawach et al.
electrodes, respectively, which leads to the formation of a Helmholtz
double layer with a thickness of 1 nm at the electrode surface. Once the
electric field is removed, the positive and negative ions are released into
the electrolyte from the electrode surface. The electrical double-layer is
stabilized by the attraction of opposite charges which leads to the gen-
eration of a relatively stable potential difference between the positive
and negative electrodes. For each electrode, a certain amount of het-
erogeneous ionic charge equal to the charge on the electrode is gener-
ated within a certain distance (dispersion layer) to keep it electrically
neutral; when the two electrodes are connected to an external circuit,
the charge migrates to generate a current in the external circuit. The
ions migrate to the solution and become electrically neutral. Therefore,
EDLCs realize the accumulation of charge and the storage and release
of energy through the adsorption/desorption process of electrolyte ions
on the surface of the electrode material in the presence or absence of an
electric field. These are the charging and the discharging principle of the
EDLC. Based on this energy storage principle, the specific capacitance
of an EDLC is mainly determined by the electrode material. Generally
speaking, the larger the specific surface area of the electrode material,
the stronger the charge storage capacity.
2.1.2. Energy storage mechanism of pseudocapacitors
Pseudocapacitors will generate a capacitance related to the elec-
trode charging potential on a two-dimensional or quasi-two-dimensional
space on the electrode surface and near the surface or in the bulk phase,
due to the underpotential deposition or a highly reversible chemical ad-
sorption/desorption or oxidation/reduction reaction of the electroactive
material. For a Faraday quasi-capacitor, the process of storing charges
includes not only storage on the electric double layer but also redox
reactions between electrolyte ions and active electrode materials. Fara-
day pseudosupercapacitor electroactive materials include various no-
ble metals or cheap transition metal oxides/hydroxides (RuO2 , MnO2 ,
Co3 O4 , NiO,Co(OH)2 and Ni(OH)2 , conductive polymers (PANI, PPy and
polythiophene), oxygen-containing or nitrogen-containing surface func-
tional groups. For example, as shown in Fig. 2b, ruthenium oxide (RuO2 )
was used as pseudocapacitor electrode in the acid electrolyte system.
During the charging process, the electrolyte ions H+ diffuse from the so-
lution into the RuO2 electrode and the electrode/electrolyte interface,
then RuIV O2 will combine with the H+ ions to form RuIV 1-x RuIII x O2 Hx
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Energy Storage Materials 34 (2021) 320–355
Fig. 2. The energy storage mechanism of FSC de-
vices. (a) Electrochemical double-layer capacitance.
(b) Pseudocapacitance. Reproduced with permission
[35]. Copyright © 2015, American Association for the
Advancement of Science.
through a redox reaction. In the bulk phase, a large number of elec-
tric charges are stored in the electrode. During the discharge process,
H+ ions will be returned to the electrolyte again through the reverse
reaction of the above redox reaction and RuIV O2 is also formed by
RuIV 1-x RuIII x O2 Hx reaction, then the stored charge is released through
the external circuit. Although RuO2 -based SCs can obtain high specific
capacity, the poor conductivity of RuO2 and the collapse of the RuO2
electrode structure during the insertion/extraction of electrolyte ions
make the cycle stability of pseudocapacitor supercapacitors worse.
2.2. The performance evaluation standards for FSCs
The effect of different factors on the performance of FSCs are dis-
played in Fig. 3. Capacitor total specific capacity (Ctotal ), working volt-
age (V), equivalent series resistance (Resr ), power density (P) and energy
density (E) are the basic parameters of FSC devices. The Ctotal reflects
the ability of the FSCs to store electrical charges. Moreover, the Ctotal ,
V and charge resistance (Rcr ) are used to evaluate the P and E perfor-
mance of FSCs. The ionic conductivity of FSC devices can be calculated
via Eq. (1) [30].
The Ctotal and Csp of FSCs can be given by the following Eqs. (2)–(4)
[36–38].
D
σ= (1)
A ∗ Rb
1 1 1
= + (2)
Ctotal Ca Cc
εA
Cs = (3)
4πd
Ctotal
Csp = (4)
X
where 𝜎, D, A and Rb represent the ionic conductivity, thickness, area
and bulk resistance, respectively. The capacitance of the anode and cath-
ode is expressed as Ca and Cc , respectively. Cs is the capacitance of a
single electrode, 𝜀 is the dielectric constant, d is the thickness of the
electrical double layer. Csp is the capacitance of the FSC divided by the
total mass of the mass-specific capacitance (F g−1 ) or the areal specific
capacitance (F cm−2 ) or the volumetric specific capacitance (F cm−3 ) or
H. Dai, G. Zhang, D. Rawach et al.
Fig. 3. The effect of various factors on the performance of FSCs.
the length specific capacitance (F cm−1 ) of FSCs. X is the mass, volume,
surface area and the size of the electrodes.
Primarily, for a symmetric FSC (the same electrode material), the
εA
Ctotal = 8πd can be obtained from Eqs. (2) and (3). On the other hand,
the electrochemical capacitors are called asymmetric FSCs if the anode
and cathode are made of different electrode materials. Therefore, the to-
tal capacitance of the FSC is controlled by the electrode with the smaller
capacitance value. From Fig. 3, it can be observed that the Ctotal of the
FSCs can be obtained by constant current charge/discharge (CCCD) ex-
periments.
The P and E of FSCs are given by Eqs. (5) and (6), respectively [38],
which show
V2
P = (5)
4Resr
1 served, which all typically remained above 90%. Therefore, the author
E = C V2 (6)
2 sp
that both energy density and power density are proportional to the
square of the voltage and Csp . Therefore, improving the capacitor’s oper-
ating voltage will increase the FSCs’ power and energy density, thus en-
hancing the specific capacitance and reducing the capacitor’s resistance.
In general, the Csp of FSCs can be increased by improving the specific
capacitance of the electrode material and optimizing the structure of the
FSCs. Besides, the V mainly depends on the selected electrodes and elec-
trolyte materials. Meanwhile, reducing the equivalent series resistance
of the FSC is effective by using a conductive electrode material and an
electrolyte with high ion mobility to increase the ionic conductivity of
FSC devices.
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Energy Storage Materials 34 (2021) 320–355
In addition to the above performance parameters, researchers are
also attracted to the mechanical and bending properties, electrochem-
ical stability, and cycle life of FSCs [39]. Zhi et al. [40] evaluated the
performance of FSCs from the geometric parameters of the bending test.
The authors suggest using the 𝜃, the R, and the L of the device to eval-
uate the bending tolerance of flexible energy storage devices systemati-
cally. They also compared the capacity/capacitance retention of flexible
polypyrrole (PPy) symmetrical supercapacitors under different bending
parameters, revealing the effects of L, 𝜃, and R, respectively. It was ob-
served that if the L and the 𝜃 of the FSC device are set to 7 cm and 90°
respectively, the capacitance retention of the FSCs is maintained dur-
ing 100 bending cycles as it can be seen from Fig. 4. This is also true
for different compressive strain radiuses ranging from 1.0 to 3.0 cm. Al-
though the holding force decreases with decreasing R, all holding rates
are higher than 95%. Similarly, reduced capacitance retention was ob-
recommends that when capacity or capacitance retention is required,
the following three geometric parameters 𝜃, R, and L should be pro-
vided.
Moreover, FSC devices should allow high stretchability. The com-
monly used material for stretchable FSCs is a hydrogel electrolyte. As
shown in Fig. 5, the hydrogel electrolyte showed significant residual
strain (usually about 24% − 33%) after 100 stretching cycles, and the
maximum strain is 200%. Since residual strain eventually destroys the
mechanical stretchability and electrochemical properties of the stretch-
able FSCs, the authors recommend that researchers provide the residual
strain of the device after a tensile test, especially when a highly stretch-
able device is required. Therefore, developing highly elastic FSCs with
negligible residual strain remains a challenge.
H. Dai, G. Zhang, D. Rawach et al. Energy Storage Materials 34 (2021) 320–355

Fig. 4. Evaluation criteria of FSC devices. (a) Schematic illustration of the mechanical parameters test (L, 𝜃, R) for FSC devices. The electrochemical performance of
PPy supercapacitors under different conditions. (b) L = 7 cm and 𝜃 = 90° (c) L = 7 cm and R = 1.5 cm. (d) R = 1.5 cm and 𝜃 = 90°.The capacitance retention after
100 bending cycles is displayed in the inset. Reproduced with permission [40] Copyright © 2019 Elsevier Inc.

Fig. 5. The mechanical properties of FSCs. Reproduced with permission [40] Copyright © 2019 Elsevier Inc.

324
H. Dai, G. Zhang, D. Rawach et al.
3. The electrolyte of flexible supercapacitor
Except for the electrode materials, the electrolyte is one of the most
essential factors affecting the energy storage performance of FSCs. Even
though the aqueous electrolyte has high ionic conductivity, the decom-
position voltage of water is only 1.23 V, which severely limits the im-
provement of the energy density/power density of the FSCs [41]. In
addition, a liquid electrolyte can easily leak, which can bring particular
harm to the equipment and the user. To improve the practicality and
wearability of FSCs, the use of flexible polymer gel electrolytes in FSCs
is the best choice. The existing types of gel electrolytes can be divided
into four categories: i) when the organic polymer framework of the gel
electrolyte is easily soluble in water, it is named an aqueous gel polymer
electrolyte, ii) when the gel electrolyte uses an organic solvent or a non-
water-soluble organic polymer framework, it is called a non-aqueous gel
electrolyte iii) ionic liquid gel polymer electrolyte means that the sol-
vent is an ionic liquid vi) the redox type substance used as an additive in
the gel electrolyte is called a redox gel electrolyte (Table 2). Moreover,
the preparation of polymer gel electrolytes is mainly divided into two
categories: physical and chemical methods. Polymer gel formation by
physical methods is generally prepared through physical cross-linkings
which include hydrogen bonding, the entanglement of chains, and elec-
trostatic interactions. The physical methods commonly used to prepare
polymer gels are blending, spinning, and freeze-thaw methods. On the
other hand, chemical methods rely on chemical bonds to form three-
dimensional network gels, which are divided into 3 categories includ-
ing monomer polymerization cross-linking, polymer cross-linking, and
carrier graft copolymerization [42,43].
3.1. The aqueous gel polymer electrolyte for FSCs
3.1.1. The organic polymer-acid gel electrolyte
Polyvinyl alcohol (PVA) not only has the characteristics of easy
processing, easy film formation, and low price, but also has excellent
bending properties. Therefore, it is an alternative material for FSCs in
the field of aqueous gel electrolytes. As early as the 1980s, the scien-
tists Petty-Weeks, S. et al. developed polyvinyl alcohol (PVA)/H3 PO4
proton conductive polymer electrolyte and found that it has a high
ionic conductivity [103]. Ever since, researchers have developed dif-
ferent types of gel electrolytes, such as: PVA/H3 PO4 [104], PVA/H2 SO4
[46–48,51–53,105,106], PVA/KOH [54–57,107,108], PVA/LiOH [109],
PVA/Na2 SO4 [59,60,110], PVA/KNO3 [61], PVA/KCl [62], PVA/LiCl
[63,66,111] and etc. in order to make gel electrolytes more widely ap-
plicable under different conditions.
The FSC is always composed of a gel electrolyte sandwiched between
a pair of porous electrodes. The gel electrolyte must make full contact
with the internal pores of the electrode to form a charge-discharge in-
terface. Researchers have made many efforts to solve this problem. For
example, Shao et al. [44] used PVA as the polymer host, H3 PO4 as the
electrolyte (PVA/H3 PO4 ) and 3D honeycomb graphene film as the elec-
trode material to make FSCs, which demonstrated a low charge trans-
port resistance of 2.31 Ω. According to this result, the FSCs received a
0.9 mF cm−2 areal capacitance at a scan rate of 1000 Mv s−1 by cyclic
voltammetry (CV) experiments. In addition, the FSCs capacitance re-
tention remained at approximately 89.4% after the 1,000th cycle of
bending tests ranging from 0° to 120° The excellent electrochemical
performance of FSCs can be maintained due to the use of a 3D honey-
comb graphene film, which can not only be used as a high-performance
FSC electrode, but can also supply an ion library for the gel electrolyte,
thereby decreasing the ion diffusion resistance caused by high viscosity.
Moreover, a solid gel electrolyte using a filling method was proposed
by Li et al. [45] (Fig. 6), which solved the interface contact problem be-
tween solid gel electrolytes and thick porous electrodes. The authors
have reported a “bottom-up” filling method to overcome the aforemen-
tioned challenges. During the top-down gelation process (Fig. 6a), the
continuous evaporation of water leads to the formation of a thick gel
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Energy Storage Materials 34 (2021) 320–355
layer, resulting in the incomplete filling. However, a complete filling
of a flexible electrode can be obtained by using the bottom-up filling
approach with PVA/H3 PO4 gel electrolyte. This method is composed
of two steps. Firstly, casting the electrolyte solution directly onto the
porous electrode on a breathable substrate. Secondly, putting a water-
impermeable film on the surface of PVA/H3 PO4 , which forces the wa-
ter to vaporize downwards through the breathable substrate forming
a gel electrolyte that grows into the electrode. Using the “bottom-up”
filling method, the PVA/H3 PO4 solid gel electrolyte could be used to
fill MWNCT electrodes and MWCNT-PEDOT/PSS composite electrodes
with a thickness of 500 𝜇m, which delivered a low Resr of 9.3 Ω cm2 be-
tween the interface of electrode/electrolyte. This kind of electrode also
exhibited excellent mechanical properties. In essence, no cracks were
observed when crimped to 0.5 mm (Fig. 6c and d) and enhanced the ion
diffusion during the charge/discharge process. Fig. 6e and f displayed
the CV curves of rolled-up FSC devices with a thickness of 150 𝜇m elec-
trode using the two different methods (top-down and bottom-up ap-
proaches) at different R. With the decreasing rolled-up R, the current
values of the FSC device assembled by the bottom-up approach had
no visible change, which demonstrated the outstanding filling between
electrode and PVA/H3 PO4 gel electrolyte. In addition, as displayed in
Fig. 6g, the capacitance value of the FSC device was maintained at 95%
after 5000 cycles of bending with a radius of 5.7 mm. Moreover, the
FSC device based on a 500 𝜇m thick WMCNT-PEDOT/PSS obtained an
areal capacitance of 2662 mF cm−2 under 2 mV s−1 condition, which
was about five times the capacitance value of the most advanced FSCs.
Furthermore, Priyanka et al. [112] used a sol-gel method to prepare
graphene oxide and titanium dioxide hybrid (GO-TiO2 ) flexible elec-
trode and PVA/H3 PO4 was used as a gel electrolyte to fabricate an
FSC device. This device delivered a low Resr (0.82 Ω), which demon-
strated excellent contact and low resistance between the electrode and
electrolyte interface. In addition, the CV profiles had no change at the
𝜃 of 60° and the FSC device displayed excellent flexibility. This de-
vice also retained a specific capacitance of 73.43 mF cm−2 and a 92%
capacitance retention after 10,000 cycles. Subsequently, Wang et al.
[113] used polyacrylamide (PAM, 16 wt%) to improve the mechani-
cal property of PVA/H3 PO4 gel electrolyte by a chemical crosslinking
method. This gel electrolyte was able to put up with tensile strain ex-
ceeding 17.42 mm/mm and obtained an ionic conductivity of 138 mS
cm−2 . This kind of FSC device had a specific capacitance of 169.7 F g−1
at the bending angle of 230° and capacitance retention of 80.9% after
5000 cycles was maintained. Moreover, the device obtained capacitance
retention of 80.5% under the 100% tensile strain condition. According
to these results, this kind of gel electrolyte demonstrated great promise
in the field of wearable devices.
In the last few years, PVA/H2 SO4 gel electrolyte has also drawn
more and more attention among researchers [114–117]. For instance,
Karthika et al. [46] prepared a flexible paper-based supercapacitor com-
posed of carbon nanotube-coated electrodes with PVA/H2 SO4 gel elec-
trolyte. The assembled FSC device achieved a high specific capacitance
of 270 F g−1 and obtained an energy density of up to 37 Wh kg−1 . Li et al.
[47] used polypyrrole (PPy)/graphene/SnCl2 modified polyester textile
(PPy/RGO/M-PEFT) or polypyrrole/graphene/SnCl2 modified polyester
yarn (PPy/RGO/M-PEFY) as a flexible electrode and PVA/H2 SO4 gel
as the electrolyte to fabricate the FSC. When the PPy/RGO/M-PEFT
was paired with PVA/H2 SO4 gel electrolyte, this kind of FSC device
achieved about 100% capacitance retention after 10,000 cycles. It also
obtained 98.3% capacitance retention after 1000 cycles under a bind-
ing test from 0° to 180°. In addition, the device also acquired an energy
density of 0.0658 mWh cm−2 and a power density of 0.5 mW cm−2 .
Moreover, to obtain an intimate electrode-electrolyte contact, Guo et al.
[48] utilized a physical cross-linking method to prepare a self-healing
composite hydrogel electrolyte and modified the nanocomposite elec-
trode material to the surface of the hydrogel electrolyte by in-situ poly-
merization and deposition methods (Fig. 7a). Thereby developing a flex-
ible repairable all-in-one supercapacitor with excellent flexibility, re-
H. Dai, G. Zhang, D. Rawach et al. Energy Storage Materials 34 (2021) 320–355

Table 2
Comparison of the properties of polymer gel electrolyte.

Ionic conductivity Working Resr/ct (Ω) or Cycle stability Bending angel/radius

Electrolyte (mS cm−1 ) potential (V) Csp (Ω cm2 ) (retention/cycles) (°/mm) Ref.

Aqueous polymer gel electrolytes

PVA/H3 PO4 – 1.0 2.47 mF cm−2 2.31 89.4%/1000 120 [44]
PVA/H3 PO4 – 1.2 2662 mF cm−2 11.2 95%/5000 5.7 mm [45]
PVA/H2 SO4 – 1.0 267 F g−1 1.2 99.5%/6000 – [46]
PVA/H2 SO4 – 1.0 239.6 F g−1 0.2 97.6%/1000 180 [47]
PVA/H2 SO4 136.4 1.0 15.8 mF cm−2 13.2 80% 60 [48]
PVA/H2 SO4 – 0.8 376 F g−1 15 99% 180 [49]
PVA/H2 SO4 – 0.6 347 mF cm−2 – 91.1%/20,000 180 [50]
PVA/H2 SO4 – 1.0 28.3 F cm−3 2.48 100%/2500 – [51]
PVA/H2 SO4 17.3 2.5 296 F g−1 11.7 91.9%/1000 – [52]
PVA/H2 SO4 – 0.8 3.55 F cm−3 55.3 83%/10,000 90 [53]
PVA/KOH – 1.2 14.9 F cm−3 – 85%/1700 180 [54]
PVA/KOH – 2.0 1590 F g−1 – 95%/5000 180 [55]
PVA/KOH – 1.5 290 F g−11 – 74%/1000 180 [56]
PVA/KOH – 1.8 288 mF cm−2 3.0 100%/10,000 – [57]
PVA/Na2 SO4 – 2.0 176 F g−1 1.5 89.6%/5000 – [58]
PVA/Na2 SO4 – 2.0 689 F g−1 – 74%/10,000 – [59]
PVA/Na2 SO4 – 0.8 1.4 F cm−3 4.6 96.3%/500 180 [60]
PVA/KNO3 – 1.0 4.17 mF cm−2 – 78%/2000 – [61]
PVA/KC 210 470 F g−1 0.48 90%/100 90 [30]
PVA/KCl 38 0.8 224 mF cm−2 2.24 92%/2000 180 [62]
PVA/LiTFSI 7.51 1.8 541.9 mF cm−2 1.5 80.8%/500 (80 180 [63]
°C)
PVA/MMT 0.017 (−50 °C) 0.8 153 F g−1 7.6 91%/10,000 180 [64]
PPDP/LiCl 10.0 2.0 300.8 F cm−3 40.54 103%/10,000 90 [65]
PVA/LiCl – 2.2 152.1 mF cm−2 184 92%/2000 135 [36]
PVA/LiCl – 0.8 0.11 F cm−1 17 82%/10,000 180 [66]
PVA/LiCl/EG 2.38 (−40 °C) 1.0 – – 90.1%/1000 180 [67]
Non-aqueous polymer gel electrolytes
PC/LiClO4 – 1.4 145 F g−1 3.1 – 120 [68]
PC/LiClO4 4.7 2.5 111 F g−1 2.2 80%/11,000 – [69]
PC/LiClO4 /PEG-TBBPA 1.09 2.7 166.69 F g−1 1.8 78%/3000 90 [70]
AEO/ LiClO4 / AC 31.1 1.5 130.3 F g−1 2.16 90.1%/5000 – [71]
s-PAA 15.0 1.0 216 F F g−1 – 85%/8000 – [72]
EW-GPE 7.61 0.8 214.3 F g−1 1.67 94.5%/6000 90 [73]
Ionic liquid-based polymer gel electrolytes
EMIMBF4 – 3.5 133 F g −1 ~3 94%/10,000 90 [74]
PVDF-HFP/EMIMBF4 – 3.5 201 F g −1 1.3 80.1%/10,000 180 [75]
PVDF-HFP/[EMIM][NTf2 ] 9.5 2.5 153 F g −1 10 97%/10,000 – [76]
PVDF-HFP/EMIMBF4 – 3.0 71.26 F cm−3 ~5 80%/10,000 – [77]
PVDF-HFP/EMIMBF4 – 3.5 180 F g −1 1.5 88.3%/1000 180 [78]
PVDF-HFP/EMIMBF4 – 3.5 174 F g −1 ~5 82.4%/10,000 180 [79]
PVDF/EMIMBF4 – 3.2 – – 98.4%/2000 180 [80]
PVA/BMIMCl/Li2 SO4 37 1.5 136 F g −1 2 82%/1000 135 [81]
PVA/BMIMCl based 15.2 1.6 – – 93.4%/10,000 180 [82]
electrolyte
IL composite 8.7 2.5 43 mF cm−2 – 90%/10,000 – [83]
N1114 TFSI – 2.5 140 F g−1 47 80%/15,000 – [84]
DMIM 22.4 2.5 174 F g−1 11 94%/200 90 [85]
MEHPO3 -[BMIM][TFSI]
EMIM-NTF2 -FS – 3.0 52 mF cm−2 2.0 80.5%/2000 – [86]
Redox polymer gel electrolytes
−1
PVA/KOH/K3 [Fe(CN)6 ] 45.56 2.0 430.95 F g 4.42 89.3%/1000 – [87]
PVA/KOH/KI 12.73 1.0 236.9 F g−1 0.53 – – [88]
PVA/KOH/KI 13.21 1.6 185.88 C g−1 1.709 89.3%/5000 – [89]
PVA/KOH/PNA 16.84 1.8 423.2 F g−1 1.582 88.32%/5000 – [90]
PVA/H2 SO4 /P- 34.8 1.0 474.29 F g−1 2.45 – – [91]
benzenediol
PVA/H2 SO4 /BAAS 21.4 1.5 390 F g −1 3.3 -/500 90 [92]
PVA/H2 SO4 /HQ – 1.0 644.4 F g −1 0.39 73%/2000 – [93]
PVA/PDA 125 1.0 427 F g −1 3 92%/30,000 180 [94]
PVA/Li2 SO4 /BMIMI 46 1.5 384.1 F g−11 2.5 80.9%/10,000 135 [38]
PVA/LiClO4 /10 wt% 31.3 1.0 114 F g−11 2.75 ~94%/5000 90 [95]
phloroglucinol
PEO/LiClO4 /NaI/I2 20 1.0 209 C g−1 – – – [96]
PMMA/LiClO4 /PC/HQ – 1.2 88.5 F cm−3 24.1 90%/4000 2.5 mm [97]
3+
PAA/KCl/Fe 90 1.0 349.6 F g−11 ~4.5 89%/5000 – [98]
PPDE/LiCl/EV 20 2.4 677 F g−11 3.89 No obvious 120 [99]
fade/100
PAMPS/Mox – 2.0 530 F g−11 0.28 92%/2500 60 [100]
PAMPS/MMT 59.1 1.5 22 F g−11 ~0.75 90%/1000 – [101]
SPI/Li2 SO4 /KI 2.54 1.5 224.19 F g−11 5 58.21%/1500 135 [102]

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H. Dai, G. Zhang, D. Rawach et al.
Fig. 6. The performance of the FSC device with PVA/H3 PO4 gel electrolyte by filling method. (a-g) The mechanism of the gel filling method and the performance
of the FSC device under different bending radius. Reproduced with permission [45]. Copyright © 2018 Springer Nature.
liable self-healing ability and high electrochemical performance. The
mechanical property of the physically crosslinked PVA/H2 SO4 hydro-
gel was measured in Fig. 7b and c. Fig. 7b showed the stretchability
of the PVA/H2 SO4 hydrogel, which was stretched up to 3.8 times com-
pared to its original length. The stress of this hydrogel electrolyte at-
tained 4.7 × 105 Pa after stretching up to 7.6 cm (Fig. 7c). In addition,
compared with any other chemically crosslinked hydrogel, the physi-
cally crosslinked PVA/H2 SO4 hydrogel film had the unique advantage
of repairing itself without any stimulus. As displayed in Fig. 7d and e,
the self-healing efficiency was well kept at approximately 80% after the
fifth self-healing cycle representing a good self-healing ability. The FSC
also obtained an areal capacitance of 15.8 mF cm−2 at a current density
of 0.044 mA cm−2 . Similarly, Wang et al. [50] reported a simple and
cost-effective magnetic hydrothermal synthesis method to fabricate 1T-
MoS2 /Ti3 C2 MXene (graphene-like) heterostructure flexible electrode
with 3D interconnect network microstructure (Fig. 7f) and was paired
with PVA/H2 SO4 gel electrolyte to fabricate the FSC device. To confirm
the flexibility of the symmetric FSC device, the mechanical parameters
such as L, R and 𝜃 were conducted as displayed in Fig. 7g-i. The CV
profiles illustrated the excellent repeatability, which demonstrated the
high flexibility and stability that the symmetric FSC obtained. More-
over, the assembled device exhibited 91.1% capacitance after 20,000
cycles at a current density of 30 mA cm−2 . Also, Yang et al. [117] used
a free radical photopolymerization method to prepare a PVA/poly(N-
hydroxyethyl acrylamide)/H2 SO4 (PVA/PHEA/H2 SO4 ) gel electrolyte
with high strength, high toughness, rapid self-recovery, fatigue resis-
tant and self-healing capabilities. The PVA/PHEA/H2 SO4 gel electrolyte
could be easily stretched about 5 times the original length under dif-
ferent test states (i.e. large, twisted and crossed stretch) and has ob-
tained excellent ionic conductivity of 85 mS cm−1 and a wide operating
window (0–3 V). With the increase of the recovery times, the recovery
ratio of PVA/PHEA/H2 SO4 gel electrolyte was enhanced from 62% to
91% under the stiffness recovery condition. The FSC obtained excellent
overlapping CV profiles under different bending angles (0–180°), which
demonstrated the outstanding flexibility of FSC devices. In addition, the
FSC also achieved a high specific capacitance of 98 mF cm−2 and 84%
capacitance retention after the 7th self-healing cycle.
Therefore, various strategies, including designing a reasonable elec-
trode structure, manufacturing unique electrolyte by physical cross-
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Energy Storage Materials 34 (2021) 320–355
linking methods, or developing a new electrolyte filling method, have
drawn wide attention to increasing the electrode/electrolyte contact
area. However, the low operating voltage window limits the develop-
ment of this type of polymer gel electrolyte in the field of FSCs. There-
fore, increasing the voltage window of this electrolyte is a challenge and
requires more attention.
Recently, some researchers also introduced the use of PVA/H2 SO4
gel electrolyte into the development of micro-supercapacitors (MSC).
Ye et al. [118] made a multilayered graphene-based MSC by direct laser
writing, which reached an optimized capacitance of 3.8 mF cm−2 using
a PVA/H2 SO4 hydrogel electrolyte. Subsequently, Li et al. [119] used a
new, low-cost, designable, and straightforward method to directly com-
bine inkjet printing and heat treatment to assemble a flexible all-solid-
state MSC based on RGO/MoO3 nanosheets. This symmetrical MSC with
PVA/H2 SO4 gel electrolyte had a wide voltage window of 0–0.8 V, ex-
cellent flexibility and high-volume specific capacitance of 22.5 F cm−3
at a current density of 0.044 A cm−3 . Moreover, Qin et al. [49] also
proposed the material of 2D dual-mesoporous polypyrrole/graphene
nanosheets with hierarchically ordered dual-mesopores for the micro-
supercapacitor. The manufactured device gained a maximum areal ca-
pacitance of 38 mF cm−2 at 1 mV s−1 and the capacitance retention
reached up to 82% after 4500 cycles utilizing an electrolyte system of
PVA/H2 SO4 gel. Furthermore, this device also obtained a high volumet-
ric energy density of 2.5 mWh cm−3 and a volumetric power density of
397 mW cm−3 at an energy density of 0.9 mWh cm−3 .
Overall, although H2 SO4 is highly corrosive and easily corrodes the
electrode material and shell, the FSC devices with polymer-H2 SO4 gel
electrolytes illustrate a higher specific capacity than other polymer-acid
gel electrolytes, and therefore this kind of gel electrolyte has a certain
application prospect in the future.
3.1.2. The organic polymer-salt gel electrolyte
Generally, organic polymer-salt gel electrolytes have been
widely used in pseudocapacitors, especially metal oxide-based FSCs
[37,58,66,110,120–122]. Typical neutral salts include Li (such as LiCl
and LiClO4 ), Na (such as NaCl and Na2 SO4 ) and K (such as KCl and
KNO3 ) salts. For example, Moon et al. [123] exhibited a superficial
method to integrate a NaCl-agarose gel electrolyte for use in FSCs.
The device obtained a high specific capacitance of 286.9 F g−1 and
H. Dai, G. Zhang, D. Rawach et al. Energy Storage Materials 34 (2021) 320–355

Fig. 7. The mechanical and electrochemical performance of the FSC device. (a) The preparation process of a flexible healable hydrogel film. (b-c) The mechanical
properties of PVA-H2 SO4 hydrogel film under stretching and stress-strain tests. (d) The electrochemical performance of an FSC device at different healing times.
(e) Healing efficiency of the FSC device at different healing times. Reproduced with permission [48]. Copyright © 2018 WILEY‐VCH Verlag GmbH & Co. KGaA,
Weinheim. (f) The fabrication process of the 1T‐MoS2 /Ti3 C2 MXene, 2H‐MoS2 /Ti3 C2 MXene 3D, 2H‐MoS2 and 1T‐MoS2 . (g-i) The flexibility and electrochemical
performances of FSC at different bending conditions. Reproduced with permission [50]. Copyright © 2020 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

about 80% of the maximum capacity was maintained after 1200 cycles.
The excellent performance could be attributed to the following factors
of NaCl-agarose gel electrolyte. Firstly, the backbone of the agarose
matrix gives the gel unique mechanical properties as a network. The
hydrogen bonding between agarose polymers promotes the formation
of a 3D framework while enhancing mechanical stability. Secondly,
the accessibility of ions in the electrolyte pore network relies on the
type of ions and pores. The internal diameter of the NaCl-agarose
gel electrolyte pores is at the sub-micron level, which is sufficient to
contain sodium and chloride ions. Finally, adding sodium chloride as
an electrolyte salt to the agarose gel increases the ion conductivity.
Among organic polymer-salt gel electrolytes, Na2 SO4 are widely
used in FSC devices (Table 2). For instance, Zhang et al. [60] used
Ni/MnO2 -filter paper and Ni/activated carbon filter paper as the pos-
itive and negative electrode respectively. The electrodes were separated
by a PVA/Na2 SO4 gel electrolyte to prepare a flexible asymmetric all-
solid-state supercapacitor (FAASS). The working potential of the FAASS
reached was up to 2.5 V and the device gained a high energy density
of 0.78 mWh cm−3 at a power density of 2.5 mW cm−3 (Fig. 8a). As
can be seen from Fig. 8b, the outstanding electrochemical performance
of FAAS is owed to the lunar crater-like morphology as well as a large
number of pores on the electrode improving the electrode-electrolyte
interface. Afterward, Lu et al. [59] manufactured the flexible hybrid su-
percapacitor with a PVA/Na2 SO4 gel electrolyte consigned a maximal
energy density of 67.8 Wh kg−1 at a power density of 1003 W kg−1 and
obtained 74% capacitance retention of initial capacitance after 10,000

328
H. Dai, G. Zhang, D. Rawach et al. Energy Storage Materials 34 (2021) 320–355

Fig. 8. The performance of FSC devices in different gel electrolyte systems. (a) The values of energy density and power density for FSC devices. (b) SEM images of
Ni(II)-FP. Reproduced with permission [60]. Copyright © 2016, American Chemical Society. (c) The structure of FSCs with PVA/Na2 SO4 organic polymer-salt gel
electrolytes. (d) Ragone plot of the flexible SC compared with the other reported hybrid SCs. Reproduced with permission [59]. Copyright © 2017 Elsevier B.V. All
rights reserved. (e) The morphology and electrochemical performance of FSCs using PVA/KCl gel electrolyte. Reproduced with permission [62]. Copyright © 2019,
American Chemical Society.

cycles (Fig. 8c and d). As displayed in Fig. 8e, Sun et al. [62] suc-
cessfully designed and developed an integrated FSC device with elec-
trode/electrolyte/electrode configuration by integrating the electrode
(polypyrrole) and electrolyte (boron cross-linked PVA/KCl hydrogel)
materials, which obtained a large energy density of 20 𝜇Wh cm−2 at
a power density of 600 𝜇W cm−2 and achieved capacitance retention
of up to 97% after 500 bending-releasing cycles. The excellent electro-
chemical performances are due to the improved mechanical property
and higher ionic conductivity (38 mS cm−1 ) of the PVA/KCl hydrogel
electrolyte. Similarly, Peng et al. [124] developed a new self-healing
hydrogel electrolyte by doping graphite oxide (GO) into the framework
of PVA and reached an ionic conductivity of up to 47.5 mS cm−1 . In

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H. Dai, G. Zhang, D. Rawach et al.
addition, Wang et al. [61] designed a flexible in-plane solid-state super-
capacitor with PVA/KNO3 organic polymer-salt gel electrolyte and used
the high-quality VSe2 nanosheets as the electrode material, which was
made by a simple chemical vapor deposition (CVD) method. The man-
ufactured supercapacitor showed high energy density in the region of
10−3 to 10−4 Wh cm−3 and demonstrated good mechanical stability to
both bending (40°) and fatigue tests up to 10,000 cycles.
Nevertheless, except for Na2 SO4 , KNO3 and KCl are used as elec-
trolyte salts. On the other hand, lithium salts are also introduced in the
aqueous polymer gel electrolyte to produce electrolyte salts. For exam-
ple, Wang et al. [111] presented the first demonstration of using the
organic polymer-salt gel electrolyte (LiCl/PVA) to stabilize vanadium
oxide (V3 O7 ) electrodes. This kind of gel electrolyte has the following
advantages: (i) the diminution of water content and the neutral pH of the
LiCl/PVA gel electrolyte decreases the corrosion of amphoteric V3 O7 ;
(ii) it can completely fill with V3 O7 electrode which increases the con-
tact area between the electrolyte and electrode. Due to the aforemen-
tioned reasons, the FSC was able to achieve a maximum areal capaci-
tance of 236 mF cm−2 at a current density of 0.2 mA cm−2 and a capac-
itance fading ratio of less than 15% after 5000 cycles. Liu et al. [66] de-
signed a lightweight, highly flexible, and sustained flexible electrode via
electroless deposition and electrochemical deposition. This device was
composed of PVA/LiCl as the gel electrolyte and reduced graphene oxide
(rGO)/Ni cotton composite as the electrodes. This FSC device obtained
82% capacitance retention after 10,000 cycles. In addition, there was no
noticeable change of CV profiles after 1000 cycles at the bending angle
of 180°, demonstrating that the device retained excellent cyclic stability.
In addition, this device obtained high energy density and power density
up to 6.1 mWh cm−3 and 1400 mW cm−3 respectively. Moreover, Peng
et al. [65] proposed a novel FSC using polyzwitterionic poly (propylsul-
fonate dimethylammonium propylmethacrylamide) (PPDP)/LiCl as the
gel electrolyte and graphene thin film as the electrodes. The device was
able to obtain a high energy density of 41.78 Wh L−1 at a power density
of 400 W L−1 and reached a volume capacitance of 300.8 F cm−3 at a
current density of 800 mA cm−3 . Also, with increasing the current den-
sity from 0.8 to 20 A cm−3 , the device was capable of obtaining 85.1%
capacitance retention. These excellent electrochemical performances of
the device are due to a variety of reasons. Firstly, the polyzwitterion ex-
hibited exceptional water retention ability due to the presence of dozens
of zwitterionic functional groups. Secondly, the zwitterionic group en-
hanced ion transmission which has lead to high ionic conductivity. Fi-
nally, the PPDP/LiCl gel electrolyte exhibited good mechanical strength
due to the dipole/dipole interactions between the zwitterionic groups.
The mechanism of PPDP/LiCl gel electrolyte in the FSC device is pre-
sented in Fig. 9a. The excellent electrochemical performances of the
FSC device is due to its high water retention ability. Fig. 9b indicated
the cycle performance of the FSC device using different gel electrolyte.
The PPDP/LiCl gel electrolyte-based FSC has achieved cycle stability
over 10,000 cycles, and the capacitance retention reached 103%, which
was 1.12 times what was obtained with the PVA gel electrolyte-based
FSC. Fig. 9c displayed the contact angle in different gel electrolyte sys-
tems. The contact angle of the PPDP-based gel electrolyte was 22°, which
was less than the PVA-based gel electrolyte (37°). These results demon-
strate that the PPDP gel electrolyte could completely fill the multilayer
graphene electrodes as well as enhance the electrolyte/electrode inter-
face compatibility of the gel. Viscoelasticity of a gel electrolyte is a cru-
cial mechanical property because the device’s stability depends on it. As
the viscoelasticity increases the device will reach higher stability. With
this perspective, the authors conducted viscoelastic measurements in
different gel electrolyte systems, as displayed in Fig. 9d. These results
demonstrate that the two electrodes held together very well with the
use of PPDP-based gel electrolyte. Fig. 9e shows that the PPDP/LiCl gel
electrolyte presented high water retention ability via differential scan-
ning calorimetry. Fig. 9f displays the EIS measurements of PPDP/LiCl gel
electrolyte which determined the equivalent series resistance of PVA-
based gel electrolyte sample obtained to be 122.6 Ω, a result 3 times
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Energy Storage Materials 34 (2021) 320–355
much higher than that of PPDP-based gel electrolyte (40.54 Ω). So the
PPDP provided an excellent ion migration channel. The analysis of the
data results above explains why an FSC using PPDP/LiCl gel electrolyte
can obtain excellent electrochemical performance. Furthermore, Deng
et al. [125] reported a novel gel electrolyte urea-LiClO4 /PVA (ULP), and
prepared 3D framework V2 O5 flexible electrode to form the FSC devices.
The ULP gel electrolyte obtained an ionic conductivity of 6 mS cm−1 . In
addition, this electrolyte could not only dope into the conductive ink to
reduce the resistance of the conductive printing paper but also enhance
the stability of V2 O5 -based electrodes under the working potential of
4.0 V condition (Fig. 10a). As can be seen in Fig. 10b, there was no
obvious change of the charge/discharge curves at different bending an-
gles, which demonstrate the excellent flexibility for FSC devices. The
device obtained high cyclic stability with 91.1% capacitance retention
after 5000 cycles in the ULP gel electrolyte system (Fig. 10c). In addi-
tion, as shown in Fig. 10d, the EIS curves were obtained for both the
V2 O5 3D network and porous V2 O5 FSCs after the 1st and 5000th cycle.
According to the EIS results, the ULP gel electrolyte can be illustrated
as a protection layer retaining the 3D structure of the V2 O5 electrode.
To further study the charge storage mechanism of the electrode in the
ULP gel electrolyte, the operando K-edge XAS technique was conducted.
The V K-edge X-ray absorption near edge structure (XANES) spectra was
obtained at different working potentials as observed in Fig. 10e. The in-
creasing working potential, ranging from 0 to 4 V, shifts the adsorption
growth edge of the XANES spectrum to higher energy. In contrast, when
the working voltage returned to the initial voltage, the curves almost
went back to the early position. The Fourier transforms (FT) spectra of
3D framework V2 O5 with UPL gel electrolyte was obtained (Fig. 10f).
These results show that the symmetry of the absorbing V ions and their
radial distribution distance were achieved. A peak at 1.5 Å was observed
which demonstrated the interaction with oxygen. However, the decreas-
ing working potential from 4 to 0 V shows a peak at 1.6 Å which is
explained by the V5+ /V4+ reaction. The V-V distance between coordina-
tion units was also observed at the 2.8 Å peak. In addition, during the
charge/discharge process, the change of V oxidation state compensated
by the cations according to the decrease of the V-V distance between
units under the condition of the improvement of voltage. Furthermore,
there was no obvious change in the peaks of V-O and V-V with a potential
decrease from 4 V to 0 V, which demonstrated that the reaction of V5+ /
V4+ could be compensated by the cations of ULP gel electrolyte dur-
ing the fast-cycling process. Therefore, these results mentioned above
demonstrated that the ULP gel electrolyte could protect the 3D V2 O5
network structure from disappearance or merger. Moreover, the FSC de-
vice obtained an energy density of 355 Wh kg−1 at a high power density
of 60 kW kg−1 . All in all, the ULP gel electrolyte not only enhanced the
mechanical stability and minimized the chemical dissolution of V2 O5 ,
but also enhanced the operating voltage without sacrificing high perfor-
mance.
Gel electrolytes are also playing a significant role in the field of FSC
devices under a different range of temperatures [113]. However, the
dehydration of gel electrolytes at higher temperatures inhibits the de-
velopment of FSCs [126]. The ability of ion migration of aqueous gel
electrolytes would be decreased or spoiled due to the effect of dehy-
dration. Therefore, it is necessary to promote the water retention abil-
ity of aqueous gel electrolytes in high-temperature environments. With
this perspective, the novel electrolyte “water-in-salt” (WIS), also named,
super-concentrated aqueous electrolyte, present the following advan-
tages: (i) the water molecules collaborate to lithium ions actively; (ii)
expanding the electrochemical stability window has increasingly gained
the attention of numerous researchers.
For instance, the application of 21 m LiTFSI/PVA WIS gel electrolyte
has been proven to ensure that SCs work at high temperatures by Liu
et al. [63]. When the temperature was under 100 °C, the WIS gel elec-
trolyte demonstrated excellent water retention and absorption, as well
as expanded the working potential up to 1.8 V. The authors utilized
density functional theory molecular dynamics (DFTMD) simulations to
H. Dai, G. Zhang, D. Rawach et al. Energy Storage Materials 34 (2021) 320–355

Fig. 9. The mechanism and electrochemical performance of zwitterionic gel electrolyte. (a) The mechanism of PPDP gel electrolyte. (b) The capacitance retention of
the FSC device in different gel electrolyte systems. (c) The experiment of contact angle with PPDP-based and PVA-based electrolyte. (d) The mechanical property of
the PPDP gel electrolyte. (e) The water retention ability of PPDP. (f) The measurements of FSC device with different kinds of electrolytes. Reproduced with permission
[65]. Copyright © 2016 Springer Nature.

Fig. 10. The electrochemical performance of the ULP gel electrolyte. (a) CV profiles of the FSC device with a 3D network V2 O5 electrode at different voltages.
(b) The flexible measurements of FSC at different bending angles. (b) The electrochemical performance of the FSC with different kinds of electrodes. (d) The EIS
experiments of the porous V2 O5 FSC and the 3D network V2 O5 FSC devices at the first cycle and 5000th cycle. (e) V K-edge XANES spectra of the 3D network V2 O5
electrode at different working potentials. (f) The FT spectra of 3D framework V2 O5 FSC device. Reproduced with permission [125]. Copyright © 2019, American
Chemical Society.

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H. Dai, G. Zhang, D. Rawach et al.
Fig. 11. The performance of FCE devices with gel electrolyte at high temperature. (a-b) The structure of different electrolytes calculated by the DFT approach. (c) The
water retention ability of different electrolytes at 80 °C. (d) The electrochemical performance of an FSC device at different temperatures. (e) The EIS measurements of
FSC devices under high-temperature conditions. (f) The cyclic stability of an FSC device under 80 °C-50% RH conditions. Reproduced with permission [63]. Copyright
© The Royal Society of Chemistry 2019.
determine the effect of the introduction of PVA into 21 m LiTFSI. As can
be seen from Fig. 11a, the lithium ions (Li+ ) in the gel system of 1 M
LiCl/PVA, were separated by four water molecules, and the other free
water molecules were connected through hydrogen bonding. The oxy-
gen atoms on the PVA chain were only connected to the water molecule
via hydrogen bonds which indicated that most of the water molecules
in the system were still free. However, it was demonstrated that the Li+
ions were coordinated with water molecules through oxygen atoms in
the 21 m LiTFSI/PVA gel electrolyte, as observed in Fig. 11b. Due to
the limited amount of water, unsaturated Li+ ions were also partially
bonded to the TFSI− anion, resulting in a robust cation-anion interac-
tion. In addition, the simulation results show a strong interaction be-
tween Li+ ions and water molecules in the 21 m LiTFSI/PVA gel improv-
ing the water-retaining ability of the gel electrolyte. Fig. 11c showed
the water retention properties of the two gels. Under the condition of
80 °C-50% RH, the residual mass of the 21 m LiTFSI/PVA gel exhibits
water-absorption ability (118% after 12 h). To study the effect of gel the
electrolyte’s water retention on the performance of FSC devices working
at high temperatures, experiments of two gel-based devices at various
high-temperature conditions were conducted. The rate and EIS measure-
ments of an FSC device using a 21 m LiTFSI/PVA gel electrolyte at differ-
ent temperatures are displayed in Fig. 11d and e respectively. Since this
gel electrolyte obtained high electrochemical activity and fast ion migra-
tion, the FSC exhibited at 80 °C an areal capacitance of 936.4 mF cm−2
at a current density of 4 mA cm−2 (Fig. 11d). An increase in the temper-
ature leads to an increase in the charge transfer resistance as observed in
Fig. 11e. The use of 21 m LiTFSI/PVA as the gel electrolyte has allowed
the FSC to exhibit excellent cyclic stability (Fig. 11f). The FSC device ob-
tained capacitance retention of 80.8% after approximately 500 cycles at
80 °C. These results indicate the effective strategy used for improving
thermal durability using a WIS gel electrolyte. Wang et al. [36] also
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Energy Storage Materials 34 (2021) 320–355
used a WIS electrolyte (8.96 M PVA/LiCl, with a molar ratio of LiCl:
H2 O = 1:5.2) and N-doped rGO fiber (NRGF) electrodes to fabricate
high operating potential FSCs (Fig. 12a). The FSCs using these WIS gel
electrolytes achieved high energy density varying from 8.4 𝜇Wh cm−2
to 36.6 𝜇Wh cm−2 in a temperature range of −20– 70 °C. Furthermore,
the authors demonstrated the reason an FSC device using an aqueous
electrolyte can work at a high voltage of 2.2 V. The reason explaning
this result is the stability improvement of the aqueous gel electrolyte
once the lithium salt was introduced into water, which is illustrated by
linear sweep voltammetry measurements. The areal capacitance of this
FSC device, as observed in Fig. 12b presents capacitance retention of
92% after 2000 cycles at an 𝜃 of 135° The EIS results provide a good
explanation for the electrochemical performance of FSAS at different
temperatures (Fig. 12c). The energy density of the FSAS was continu-
ously raised, as it can be predicted based on EIS measurements, and has
demonstrated 8.4 𝜇Wh cm−2 (7.4 mWh cm−3 ) at −20 °C, 23.5 𝜇Wh cm−2
(20.9 mWh cm−3 ) at 25 °C and 36.6 𝜇Wh cm−2 (32.5 mWh cm−3 ) at
70 °C, when a current density of 0.5 mA cm−2 was applied (Fig. 12d).
Lu et al. [64] reported a low-temperature MMT/PVA hydrogel elec-
trolyte, resistant to extreme temperatures, and successfully retained a
full-temperature FSC stably operational under the −50 ~ 90 °C tem-
perature range (Fig. 13a). The MMT/PVA membrane was prepared via
the vacuum method, as displayed in Fig. 13a. The addition of layered
MMT formed conductive channels in the hydrogel electrolyte, which en-
hanced its ionic conductance. The ionic conductivity of MMT/PVA gel
electrolyte was 0.017 mS cm−1 at −50 °C, which enough to make the
device functioning (Fig. 13b). As exhibited in Fig. 13c and d, the stress-
strain and TGA measurements both demonstrated that the MMT/PVA
maintained excellent mechanical property and thermal stability. More-
over, even under bending, torsion, and stretching conditions, the FSC
device also obtained stable power density (Fig. 13e) and exhibited 91%
H. Dai, G. Zhang, D. Rawach et al.
Fig. 12. The electrochemical performance of FSCs at different temperatures. (a) The CV test of FSCs at different temperatures. (b) The areal capacitance of the FSC
at the bending angle of 135°. (c) The EIS experiments of the FSC devices at different temperatures. (d) The volumetric energy density and areal energy density of the
FSCs under different temperatures. Reproduced with permission [36]. Copyright © 2019 Elsevier B.V. All rights reserved.
capacitance retention after 1000 cycles with a bending test. Overall, this
work provides an encouraging way to create a flexible electrochemical
energy storage device with a wide operating temperature range and ex-
cellent flexibility.
The interest in the use of gel electrolytes is not only growing in the
field of high-temperature FSCs but also for the low-temperature FSCs
[30,67,127]. However, because the conventional hydrogel electrolyte
accommodates a large amount of solvent water, inescapably curdles at
the temperature below zero and inhibits the migration of ions, which
fundamentally hinders the use of FSCs at shallow temperatures. Re-
cently, Rong et al. [67] proposed a novel organohydrogel electrolyte
composed of PVA frameworks, H2 O/ethylene glycol (H2 O/EG) solvent,
and LiCl salts (Fig. 13f). The anti-freezing properties of PVA-based gel
electrolytes were improved by modifying the ratio of H2 O/EG in the
organohydrogel electrolyte system. Due to the excellent frost resistance
of the H2 O/EG binary solvent, even at temperatures reaching −40 °C,
Fig. 13g demonstrates the outstanding flexibility of organohydrogel
electrolyte compared with hydrogel electrolyte. As displayed in Fig. 13h
and i, the synthesis of the organohydrogel electrolyte via the physical
cross-linking method substantially promotes the mechanical properties
of this novel gel electrolyte, thereby easily stretched to 300% strain,
and without the presence of any cracks with compression of up to 85%.
As exhibited in Fig. 13j, a decrease in temperature of the FSC using
the organohydrogel electrolyte, from 25 to −40 °C does not present
any obvious change of the G’ curves, demonstrating the stable mechan-
ical properties and excellent anti-freezing performance of this gel elec-
trolyte. These excellent results illustrate that the FSC device has out-
standing flexibility and good low-temperature performance. When the
mass ratio of H2 O and EG was 2:1, the FSCs evinced the best electro-
chemical performance and highest capacitance at −40 °C, as displayed
333
Energy Storage Materials 34 (2021) 320–355
in Fig. 13k. This might be caused by the high ionic conductivity (2.38
mS cm−1 ) of the electrolyte at low temperatures, as shown in Fig. 13l. In
addition, Fig. 13m-n display good electrochemical performance of the
FSC using the organohydrogel electrolyte. Also, at the low operating
temperature of −20 °C, this FSC device obtained capacitance retention
of 88.3% at the 5,000th cycle. On the other hand, under the bending
angle of 180°, this device exhibited a 90.1% capacitance retention after
1000 cycles. These results indicate the excellent unprecedented flexi-
bility and electrochemical performance at low temperatures of this FSC
device. This study has paved the way for the development of flexible
energy devices functional in subzero temperatures.
In a word, compared with organic polymer-acid/alkaline gel elec-
trolytes, FSCs with organic polymer-salt gel electrolytes can provide a
wider and more stable operation voltage window. Because the concen-
tration of hydrogen ion and hydroxide ion in neutral salts are much
lower than that of acidic/alkaline compounds, hydrogen evolution and
oxygen evolution are less, therefore, the working voltage of organic
polymer-salt gel electrolyte can be greatly increased.
3.1.3. Organic polymer-alkaline gel electrolyte
The development of alkaline FSCs leads to an increase of interest
in the alkaline gel electrolytes [109,128–130]. Among various elec-
trolyte salts, KOH is the most widely studied for OH− ion conductive
aqueous gel electrolyte applications due to its low price and is eco-
logical [131]. Some important studies on KOH-based gel electrolytes
for FSCs have been reported [54–56,108,132–134]. For example, Zhao
et al. [135] firstly reported a novel monolayer Ni-Co hydroxyl carbonate
(1.07 nm) as the electrode to assemble an asymmetric FSC device with
PVA/KOH gel electrolyte within the working voltage of 1.6 V, as dis-
played in Fig. 14a. As can be seen from the CV curves (Fig. 14b), the de-
H. Dai, G. Zhang, D. Rawach et al. Energy Storage Materials 34 (2021) 320–355

Fig. 13. The electrochemical performance of FSCs at low temperatures. (a) Illustrated the fabrication of MMT/PVA hydrogel electrolyte. The enlarged figure is
the hydrogen-bond interactions in the electrolyte. (b) The ionic conductivity of the gel electrolyte at different working temperatures. (c) The experiments of stress-
strain with different electrolytes. (d) The TGA analysis of the electrolytes under the nitrogen atmosphere. (e) GCD curves of the MMT/PVA-based FSC devices
under different test conditions. Reproduced with permission [64]. Copyright © 2020, American Chemical Society. (f) Illustration of the hydrogel electrolyte and
organohydrogel electrolyte on a flexible electrode. (g-i) The physical performance of the hydrogel electrolyte and organohydrogel electrolyte. (j-n) The mechanical
and electrochemical performance of hydrogel electrolyte and organohydrogel electrolyte. Reproduced with permission [67]. Copyright © 2018 WILEY‐VCH Verlag
GmbH & Co. KGaA, Weinheim.
334
H. Dai, G. Zhang, D. Rawach et al.
Fig. 14. The FSC device performance. (a) The preparation progress of the FSC device. (b) CV curves at various scan rates in PVA/KOH gel electrolyte system. (d)
Electrochemical performance of FSC device with PVA/KOH gel electrolyte. Reproduced with permission [135]. Copyright © 2016, American Chemical Society.
vice illustrated excellent reversibility from 5 mV s−1 to 2 V s−1 . The de-
vice with PVA/KOH gel electrolyte delivered a high volumetric capacity
of 566 mF cm−2 at a current density of 100 mA g−1 . Moreover, even un-
der the condition of 2 A g−1 , the FSC device could achieve 100% capacity
retention after 19,000 cycles, which demonstrated good cyclic stability
(Fig. 14c). The high electrochemical performance could be attributed
to the distinctive structure with a short ion diffusion channel and offer
more exposed atoms in the electrochemical reactions, which are pre-
sented in Fig. 14d. Zhao and co-workers [136] also used PVA/KOH as
gel electrolytes to manufacture a symmetric FSC device with two similar
N-P-O co-doped 3D graphene electrodes. As displayed in CV curves, the
voltage window of the device can be extended to 1.4 V, which may be at-
tributed to the excellent stability of the PVA/KOH gel electrolyte. There-
fore, the device demonstrated a high specific capacitance of 426 F g−1
and delivered a good energy density of 25.3 Wh kg−1 at a power density
of 93.1 W kg−1 . Moreover, the symmetric device illustrated excellent cy-
cling stability with 96.2% capacity retention after 10,000 cycles.
Subsequently, as shown in Fig. 15, Jiang et al. [57] designed a new
asymmetric FSC using PVA/KOH gel electrolyte (Fig. 15a). Fig. 15b
and c display the FSC working at high operating potentials (1.8 V),
which obtained a high volumetric energy density of 1.39 mWh cm−3
and a power density of 440 mW cm−3 . The GCD curve at a current
density of 5–50 mA cm−2 is indicated in Fig. 15c, and the correspond-
ing capacitance and current density curves are further demonstrated in
Fig. 15d. The discharge curve of this device was almost linear at various
current densities. The calculated area capacitance at 5 mA cm−2 was
about 288 mF cm−2 . When the current was increased to 50 mA cm−2
(~ 245 mF cm−2 ), about 85% of the capacitance was still obtained.
Fig. 15e presents the voltage curve of the capacitor current (calculated
red shaded area) compared to the total measured current recorded at
50 mV s−1 . It was forecasted that the capacitance effect accounts for
77.3% of the total capacitance. As displayed in Fig. 15f, the Ni@CNT-
based FSC exposed good electrochemical stability (without capacitance
loss) up to 10,000 cycles even with an alternative change of the charg-
ing direction. Moreover, Xu et al. [137] also illustrated the high electro-
335
Energy Storage Materials 34 (2021) 320–355
chemical performance FSCs with acicular Co9 S8 arrays as the positive
electrode and Co3 O4 @RuO2 nanosheet arrays as negative electrodes in
the PVA/KOH organic-alkaline gel electrolyte system. The FSC deliv-
ered high volumetric capacitance of 4.28 F cm−3 and an energy den-
sity of 1.44 mWh cm−3 at a power density of 0.89 W cm−3 and oper-
ating potential of 1.6 V. Similarly, Choi et al. [107] proposed a carbon
natotubes (CNT)/MnO2 yarn electrode via electrochemical deposition
and fabricated FSCs using PVA/KOH aqueous gel electrolyte. This FSC
displayed excellent electrochemical performance of energy density up
to 3.52 mWh cm−3 at the volumetric power density of 127 mW cm−3
and no noticeable fading of capacitance with bending angle reaching
up to 90° after 1000 cycles. Similarly, Zhao et al. [138] fabricated an
MCPP-based symmetric FSC with Ni foam as the current collector and
PVA/KOH gel as the electrolyte. This device indicated a specific capac-
itance of 380 F g−1 at 0.25 A g−1 and obtained an energy density of
13.2 Wh kg−1 at a power density of 0.126 kW kg−1 or an energy density
of 4.86 Wh kg−1 at a current density of 10 A g−1 . Chen et al. [139] fab-
ricated the FSC with PVA/KOH gel electrolyte. This device obtained a
specific capacitance of 183.9 F g−1 under the condition of 2 mV s−1
and maintained an energy density of 16.35 Wh kg−1 and a power den-
sity of 147 W kg−1 . In addition, the FSC displayed excellent flexibil-
ity because no obvious change was observed in the CV profiles under
the condition of the bending test from 0° to 90° This FSC exhibited a
20.3% capacitance fading after 10,000 cycles. Furthermore, Wang et al.
[140] proposed a new gel electrolyte through poly(acrylic acid) (PAA)
backbone cross-linked with waterborne polyurethane that maintained
an ionic conductivity of 10 mS cm−1 .
To improve the ionic conductivity of the gel electrolyte, Huang et al.
[141] introduced GO into the boron cross-linked polyvinyl alcohol gel
electrolyte, named GO-B-PVA/KOH gel electrolyte. The ionic conduc-
tivity reached up to about 20 mS cm−1 with 20 wt% GO doping and
obtained good mechanical properties in tension and compression. The
capacitance of this device with 20wt% GO-B-PVA/KOH gel electrolyte
presented a 129% increase compared to the device using KOH aqueous
electrolyte. Similarly, incorporating hyperbranched poly (amine ester)
H. Dai, G. Zhang, D. Rawach et al.
nano-silica (HBPAESiO2 ) into PVA/KOH gel electrolyte, a new strategy
for promoting ionic conductivity and forming an excellent electrode-
electrolyte interface was proposed by Hou et al. [142]. The effort to fur-
ther promote the performance of HBPAE-SiO2 was to establish the HB-
PAE charged structure through the treatment of KOH because hydrolysis
of the ester units is proposed to generate carboxylic acid ions attached to
the branched structure. This kind of electrolyte (7.09 mS cm−1 ) was over
five times higher than the pure PVA/KOH electrolyte (1.32 mS cm−1 )
and obtained about 88% capacitance retention after 10,000 cycles.
In general, the working voltage window of the aqueous gel elec-
trolyte is relatively low, which in turn causes the energy density and
power density of the FSC to fail to meet the market demands. However,
aqueous gel electrolyte has the advantages of being environmentally
friendly, nontoxic, cheap, and have high conductivity. Therefore, the
majority of researchers still use aqueous gel electrolyte for academic
research.
3.2. The non-aqueous gel polymer electrolyte for FSCs
The introduction of non-aqueous gel polymer electrolytes into FSC
devices to replace the liquid electrolyte will resolve a variety of issues
such as flammability, low chemical stability, etc. With this perspec-
tive, the development of non-aqueous gel polymer electrolytes (NAGEs)
has been gaining considerably more attention from researchers. [143–
145]. However, the tricky issues including low ionic conductivity, poor
electrochemical performance and poor interfacial conductance between
the electrolyte-electrode interface hinder the practical applications of
NAGEAs. Many works have been done by researchers to solve these
problems. For instance, Rakhi et al. [68] proposed asymmetric FSC with
NAGE propylene carbonate (PC)/LiClO4 . The FSC indicated a specific
336
Energy Storage Materials 34 (2021) 320–355
Fig. 15. The electrochemical performance of
FSCs. (a) The structure of the FSC device and the
mechanism of charge storage. (b-c) The electro-
chemical performance of the FASC device. (d) The
rate performance of the FSC device at different test
states. (e) The voltage profile for the capacitive
current (calculated shaded region) compared with
the total measured current at 50 Mv s−1 . (f) Cy-
cle performance of the FSC device at different test
states. Reproduced with permission [57]. Copy-
right © 2017 Published by Elsevier B.V.
capacitance of 145 F g−1 and exhibited a device capacitance of 36 F g−1
at a discharge current density of 1000 mA g−1 .
Similarly, Vijayakumar et al. [69] proposed a method for the syn-
thesis of a NAGE in which a liquid electrolyte (LiClO4 /PC) was trapped
in poly (2‑hydroxy-3-phenoxy UV-assisted in-situ polymerization strat-
egy in propyl acrylate) matrix. The ionic conductivity of this electrolyte
reached levels up to 4.71 mS cm−1 . This device was able to work at a
potential of 2.5 V and was found to display a mass-specific capacitance
of 111 F g−1 at a current density of 0.25 A g−1 (1 mA cm−2 ). How-
ever, the low ionic conductivity, poor interfacial conductance between
the polymer electrolyte membrane and electrode materials, low elec-
trochemical performance hindered the practical applications of NAGEs.
Basically, the introduction of aqueous ionic liquid (such as NaCl) in the
gel electrolyte can promote the ionic conductivity of the gel electrolyte.
For example, Na et al. [73] reported a novel NAGE for FSCs by using
NaCl electrolyte salt, broken eggshell and rice husks as egg white gel
polymer electrolyte. The manufactured novel NAGE offers many advan-
tages including high ionic conductivity (approximately 7.61 mS cm−1 ),
high electrolyte retention, adequate mechanical properties and thermal
stability, and is environmentally friendly. The reasons why the novel
NAGE presents numerous advantages include the high affinity between
the egg white and eggshell membranes as well as the optimization of
the electrolyte salt. Even at the high temperature of 60 °C, the ionic
conductivity of this kind of gel electrolyte also can be retained at 7.82
mS cm−1 . In addition, the device obtained a high specific capacitance
of 214.3 F g−1 at 0.2 A g−1 and 204.4 F g−1 at 1 A g−1 and after 6000
cycles, the capacitance retention obtained was up to 94.5%.
Moreover, Na et al. [71] proposed a new polymer gel elec-
trolyte (alcohol ethoxylate/acrylamide/LiClO4 ) containing abundant
ion-conductive amine and ethylene oxide functional groups, which de-
H. Dai, G. Zhang, D. Rawach et al.
livered high ionic conductivity of 31.1 mS cm−1 at room temperature.
The device displayed outstanding electrochemical performance with a
specific capacitance of 130.3 F g−1 at 0.5 A g−1 and capacitance reten-
tion of 90.1% after 5000 cycles. Also, the FSC gained a maximum energy
density of 8.99 Wh kg−1 at a power density of 67.84 W kg−1 . In addition,
there was nearly no difference in the CV curves for FSC using this gel
electrolyte under various bending angles (45°, 90°). Subsequently, Xun
et al. [146] proposed a new NAGE composed of crosslinked renewable
and environmentally friendly soybean protein isolate (SPI) and hydrox-
yethyl cellulose (HEC) with 1.0 M Li2 SO4 (SPI/HEC/Li2 SO4 ) which ex-
hibited an ionic conductivity of 8.4 mS cm−1 . The FSC device displayed
excellent flexibility because there was no obvious change of CV curves
at different bending angles. In addition, the device obtained a specific
capacitance of 91.79 F g−1 and an energy density of 7.17 Wh kg−1 and
delivered almost a 100% capacitance retention after 5000 cycles.
The high energy density and the resolution of safety concerns are
critical factors for various energy storage devices. Wang et al. [70] pro-
posed the synthesis of high-performance flame-retardant NAGEs by
cross-linking novel flame retardants with brominated epoxy resins
utilizing functional poly (ethylene glycol) copolymers and a simple
epoxy ring-opening polymerization strategy. In this method, tetrabro-
mobisphenol A was used as a matrix, and an organic liquid electrolyte
(a lithium salt in a propylene carbonate solvent) was used to swell.
The polyethylene glycol portion of the flame-retardant gel polymer elec-
trolyte ensures high ionic conductivity, with a recorded ionic conduc-
tivity as high as 1.09 mS cm−1 . In addition, because the flame retardant
tetrabromobisphenol A is polymerized onto the polymer electrolyte ma-
trix instead of dissolving tetrabromobisphenol A directly into the elec-
trolyte. Therefore, this kind of NAGE exhibited very safe flame retar-
dancy as well as no negative impact on electrochemical performances.
This device demonstrated good electrochemical performance, that is,
a high specific capacitance of 166.69 F g−1 at 0.5 A g−1 , and the re-
markable flexibility under bending conditions is superior to FSCs with
corresponding liquid organic electrolytes. Furthermore, the maximum
energy density of the present device with NAGE was calculated to be
42.19 Wh kg−1 at a power density of 203.83 W kg−1 , an energy den-
sity of 31.3 Wh kg−1 was maintained at 5230 W kg−1 . Moreover, the
FSCs with good mechanical toughness and self-healable properties have
played an essential role in modern electronics. Liao et al. [72] fabri-
cated a new electrolyte mechanically robust and endowed self-healing
via micelle co-polymerization of acrylic acid and octadecyl methacry-
late (OMA) in the vinyl-treated sponge and in-situ gelatinized. This dual
polymer network based on physical bonding is reversible, harmless to
ion transport, and imparts self-healing properties to the hydrogel. Cova-
lent grafting of polymer chains onto 3D interconnect sponges through
vinyl. The strong covalent bond between the sponge and the PAA/OMA
chain establishes a physical framework that can dissipate energy signif-
icantly when larger stains are applied. Therefore, the device obtained
a specific capacitance of 368 F g−1 at a current of 0.1 mA. The capaci-
tance still gained 110 F g−1 when the current was as high as 5 mA. In
addition, the bending measurements showed no evidence of capacitance
attenuation, and there was a 95% initial capacitance reserve.
Although the FSC devices with non-aqueous gel electrolytes illus-
trated its lower specific capacity and poor cyclic stability in comparison
to aqueous gel electrolytes, the working voltage window of FSC has been
improved and can reach up to 2.7 V. Therefore, further increasing the
specific capacitance of non-aqueous gel electrolytes through reasonable
methods will become the main research content in the next step.
3.3. Non-aqueous ionic-based gel polymer electrolyte for FSCs
We need to know that the specific energy of FSCs is lower than that
of lithium-ion batteries. Therefore, while obtaining high specific power,
increasing the specific energy is an urgent problem that is crucial to
solving. To enhance the specific energy of the FSC, it is necessary to
promote the specific capacitance while increasing the operating volt-
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Energy Storage Materials 34 (2021) 320–355
age. Presently, the electrolytes of FSCs are mainly organic electrolytes.
However, organic solvents are volatile, their conductivity is difficult to
increase, and they are toxic and harmful to the environment. Compared
with aqueous and organic electrolytes, ionic liquid-based gel electrolytes
show other advantages, including high ionic conductivity, non-volatile,
non-flammable, and a wide operation potential window (Fig. 16). Ionic
liquids (IL) can be used directly as liquid electrolytes for supercapac-
itors, or as electrolyte salts in organic solvents and can also be intro-
duced into solid polymer electrolytes to improve related performances
[147]. The anions of ionic liquids are mainly composed of bis (triflu-
oromethylsulfonyl) imide (TFSI− ), BF4 − , PF6 − and so on. The cations
of ionic liquids are mainly composed of organic large-volume ions such
as imidazoles, pyrroles, and short-chain fatty quaternary amine salts.
Fig. 16a-c displays the molecular structure of conventional ILs. In addi-
tion, Fig. 16d-f shows the stability of the working potential of some ILs
at different electrodes, which indicated the ILs could operate at a wide
voltage window.
3.3.1. Natural ionic liquid electrolyte
Because the ILs can be directly used as the electrolyte, researchers
have used them to widen the working voltage window and therefore
increasing the energy density of the energy storage systems [149–152].
For instance, Chen et al. [153] utilized the 1‑butyl‑3-methylimidazolium
hexafluorophosphate (BMIPF6 ) as the electrolyte and redox graphene
oxide as the electrode, which was fabricated by hydrobromic acid to
prepare the supercapacitor. With BMIPF6 IL electrolyte, the device op-
erated at 22.4 V and gained a specific capacitance of 158 F g−1 at
a current density of 0.2 A g−1 . In addition, another imidazole ILs,
such as 1-ethyl-3-methylmidazolium tetrafluoroborate (EMIMBF4 ), 1-
ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4 ) and 1-ethyl-3-
methylimidazolium bis(trifluoromethylsulfonyl)imide (EMITFSI), have
also received great attention from researchers [154–156]. For example,
Sun et al. [157] used EMIMBF4 as the electrolyte, and the device ob-
tained a high specific capacitance of 147 F g−1 . The carbon-based de-
vice delivered an energy density of 20 Wh kg−1 at a power density of
3100 W kg−1 . He et al. [158] reported an FSC device by using EMIBF4
as the electrolyte and poly(vinylidene fluoride-co-hexafluoropropylene)
(PVdF-HFP)/single-walled carbon nanotube (SWCNT) as the electrode
material. This device worked at 2.5 V and had low equivalent series re-
sistance which increased the power and energy densities of the FSC to
11 kW kg−1 and 23 Wh kg−1 , respectively. Shen et al. [88] reported the
asymmetric SC with the IL EMIMBF4 electrolyte, and the device showed
excellent cycling performance with 98.5% capacitance retention after
100,000 cycles. It demonstrated a high energy density of 103 Wh kg−1
with the operating potential of 3.8 V. Wang et al. [74] proposed an
FSC using IL EMIMBF4 as the electrolyte and double-capillary carbon
nanofibers (DCNF) as an electrode (Fig. 17a). This device showed a sta-
ble cycle performance obtaining 94% capacitance retention after 10,000
cycles at a current density of 4 A g−1 and obtained a maximum en-
ergy density and power density of 56.6 Wh kg−1 and 114 kW kg−1 , re-
spectively. The flexibility of this device is demonstrated in Fig. 17b and
no obvious change in CV curves at the 𝜃 of 0° and 90° were observed
(Fig. 17c). Zhao et al. [159] utilized EMIMBF4 as IL electrolytes cou-
pling with O–N-S co-doped hierarchical porous carbons electrode. This
device showed a wide working potential window (0–3.6 V) and indi-
cated high capacitance retention (69%) at a current density of 10 A g−1
and the outstanding energy density was 107 Wh kg−1 at a power density
of 900 W kg−1 . In addition, a remarkable energy density of 67 Wh kg−1
was gained even at a power density of 18,000 W kg−1 . Shi et al. [77] as-
sembled a high-voltage FSC device by using EMIMBF4 IL electrolyte
and proposed a film electrode based on dual-confined FeOOH quantum
dots (FQDs) with superior pseudocapacitive behavior at high-voltage.
According to the measurements of contact angle and surface tension,
the FQDs/CNTC displayed a small contact angle (20.3°) and large sur-
face tension (50.2 mJ m−2 ) in the EMIMBF4 IL electrolyte system, which
demonstrates the use of EMIMBF4 IL electrolyte increased the contact
H. Dai, G. Zhang, D. Rawach et al.
Fig. 16. The molecular structure of common ILs (a) EMI-BF4 , (b) BMI-PF6 , and (c) Et4 N-TFSI. (d-f) Electrochemical stability of typical ILs on the electrode of Pt and
carbon. Reproduced with permission [148]. Copyright © 2017 Elsevier B.V. All rights reserved.
area between the electrode and electrolyte. This device obtained a high
energy density of 77.12 mWh cm−3 and gained 80% capacitance reten-
tion after 10,000 cycles.
Silva et al. [160] used three kinds of IL electrolytes (SET3 TFSI,
EMIFSI, and EMITFSI) and graphene nanosheets/multiwalled carbon
nanotubes as the electrode to fabricate the supercapacitor. According to
the results, the EMITFSI was observed to display the best performance,
such as high ionic conductivity (10 mS cm−1 ) and wide operating po-
tential window (4.1 V). The device obtained a specific capacitance of
153.7 F g−1 at a current density of 0.2 A g−1 and displayed 88% capaci-
tance retention after 2000 cycles. The maximum energy and power den-
sities were calculated to be 41.3 Wh kg−1 and 3.5 kW kg−1 , respectively.
Moreover, some other ILs are used as electrolyte salts in the supercapac-
itors. For example, Aradilla et al. [84] used butyl trimethylammonium
bis((trifluoromethyl)-sulfonyl)imide aprotic IL as the electrolyte and
PEDOT-Diamond@SiNWs as the electrode to prepare symmetric micro-
supercapacitors (Fig. 17d). In the 2.5 V potential window, the energy
and power density of the device were 26 mJ cm−2 and 1.3 mW cm−2 ,
respectively. In addition, as presented in Fig. 17e, the system also ex-
hibited 80% capacitance retention of its initial capacitance while main-
taining a coulomb efficiency of approximately 100% at a current den-
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Energy Storage Materials 34 (2021) 320–355
sity of 1 mA cm−2 after 15,000 cycles. And Gao et al. [161] introduced
the 1-Methyl-1-propylpyrrolidinium bis(trifluoromethyl-sulfonyl)imide
(PMPyrrTFSI) into the electrolyte system, enhancing the potential win-
dow up to 4 V. Under this condition, the device exhibited an energy
density of 84 𝜇J cm−2 and a high-power density of 0.94 mW cm−2 over
10,000 charging/discharging cycles.
Modern high-performance energy storage electronics are susceptible
to accidental fires due to overheating, low capacitance retention and
electrolyte leakage. These issues present huge challenges for companies
to fabricate modern electronic equipment. To solve these problems and
ensure safe devices, electrolyte-imprinted electrodes have been studied
in this field. The electrolyte-imprinted electrodes exhibit many excel-
lent advantages including their lightweight, high flexibility, safety and
lack of electrolyte leakage and short-circuit problems. Therefore, Sel-
vam et al. [162] reported an IL electrolyte-imprinted GO-chitosan (CS)-
copper composite electrode by using BMIMBF4 IL (Fig. 18a). The device
obtained an excellent cycling performance consisting of 78% capaci-
tance retention after 200,000 cycles (Fig. 18b), 94% capacitance reten-
tion after 50,000 cycles and 97% capacitance retention after 10,000 cy-
cles. Even after 150 days, the CV curves still present excellent repeata-
bility, demonstrating the excellent stability of this FSC device at 100 °C
H. Dai, G. Zhang, D. Rawach et al.
(Fig. 18c). The good electrochemical performance of this FSC may be
attributed to its excellent surface morphology leading to a cavity forma-
tion with a less film-like structure, present in Fig. 18d.
Energy storage devices with IL electrolytes may be safer and can re-
place dangerous energy storage devices prone to fires and electrolyte
leakage. In addition, manufactured supercapacitors meet the energy
storage models required for wearable and flexible electronic devices and
are therefore potential candidates for these devices.
3.3.2. Ionic liquid-mixture electrolyte
IL can also be applied as a supporting electrolyte because they have
similar functions to other salts, and supply mainly cations and anions in
organic solutions for charge transport [27,28,163–167]. For instance,
Oh et al. [168] designed a device using IL EMIBF4 as the salt in ace-
tonitrile (AN) electrolyte and the device delivered a volumetric specific
capacitance of 31.14 F cm−3 . Similarly, Fuertes et al. [169] introduced
EMImTFSI/AN electrolyte into the proposed porous carbon-based super-
capacitor. This device obtained a specific capacitance of 140–150 F g−1
at 150 A g−1 and exhibited an energy density of 25–30 Wh kg−1 at
a power density of 97–100 kW kg−1 . However, these kinds of elec-
trolytes (ILs/AN) are based on aqueous solutions, which may cause
some safety issues such as leakage and rapid evaporation of electrolyte-
solvent. Therefore, it is necessary to explore new electrolytes. With this
perspective, PVA-based IL gel electrolytes have gained much attention
from researchers due to their environmentally friendly feature along
with their chemical and physical properties such as high thermal stabil-
ity, high electrochemical stability, non-flammability, non-toxicity and
good flexibility [158,163]. For instance, Jeong et al. [163] reported
a PVA-based IL gel electrolyte, which was executed with IL BMIMBF4
and using reduced graphene oxide (rGO)/single-wall carbon nanotubes
(SWCNTs) as electrodes to fabricate the FSC device. As indicated in
Fig. 18e, the FSC device presents rectangular CV curves with a large
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Energy Storage Materials 34 (2021) 320–355
Fig. 17. The performance and preparation prohress of
FSCs. (a) The preparation process of the electrode. (b) Pho-
tographs of the FSC device at different bending angles. (c)
The CV profiles were conducted at different bent states.
Reproduced with permission [74]. Copyright © 2016 El-
sevier Ltd. All rights reserved. (d) The CV curve of the
FSC with butyltrimethylammonium bis((trifluoromethyl)-
sulfonyl) imide aprotic ionic liquid electrolyte. (e) The
cyclic stability of the FSC device at a current density of
1 mA cm−2 . Reproduced with permission [84]. Copyright
© 2016, American Chemical Society.
current when utilizing PVA/H3 PO4 /BMIMBF4 as the gel electrolyte,
which demonstrates that the polymer-ILs complex in the system has
high ionic conductivity. This result is consistent with the measurements
of EIS in Fig. 18f. The internal resistance (20 Ω) of the FSC device us-
ing the PVA/H3 PO4 /BMIMBF4 gel electrolyte was lower than the in-
ternal resistance (105 Ω) of the FSC utilizing the PVA/H3 PO4 gel elec-
trolyte. Therefore, as displayed in Fig. 18g, the FSC device maintained
a 64.6% capacitance retention after 300 bending with the application
of GCD 4000 cycles. These results exhibited high flexibility and sta-
bility of the FSC composed of the PVA/H3 PO4 /BMIMBF4 electrolyte.
However, the working potential window of this device is low (1 V).
Consequently, to improve the operating potential window, Zhang et al.
[81] introduced Li2 SO4 and IL BMIMCl into the PVA-based IL gel elec-
trolyte to enhance its ionic conductivity and also the potential win-
dow of the FSC device (1.5 V). Fig. 19a displays the preparation pro-
cess of the PVA/BMIMCl/Li2 SO4 gel electrolyte. At the weight ratio
of PVA:BMIMCl:Li2 SO4 = 1:3:2.2, the ionic conductivity of electrolyte
reached a maximum value of 37 mS cm−1 (Fig. 19b). Additionally, no
change in the ionic conductivity was observed even as the bending an-
gle went up to 180° Fig. 19c shows the high flexibility of the FSC using
PVA/BMIMCl/Li2 SO4 as the gel electrolyte since no change in the capac-
itance was observed following the bending tests ranging from 0° to 135°
Also, the FSC device obtained 82% capacitance retention after 1000 cy-
cles at 135° bending angle, indicating the good cycling stability of the
FSC device.
Tang et al. [82] utilized PVA/BMIMCl-based IL gel electrolyte
and cellulose paper electrode to prepare the FSC device. As shown
in Fig. 19d, the acidic PVA/BMIMCl/lactic acid/LiBr and neutral
PVA/BMIMCl/sodium acetate/LiBr hydrogel polymer electrolytes were
utilized as catholyte and anolyte, respectively. Fig. 19e displays the
CV curves of the FSC device with two PVA/IL-based gel electrolytes
under different bending angles. According to these results, no obvi-
H. Dai, G. Zhang, D. Rawach et al. Energy Storage Materials 34 (2021) 320–355

Fig. 18. The electrochemical performance of BMIMBF4 -based gel electrolyte. (a) The mechanism of GO–CS-copper crosslinked composite preparation. (b) The
electrochemical performance of FSC device at different temperatures. (c) The CV curves of CC3 electrode at 100 °C. (d) SEM images of the CC3 electrode at the
temperature of 100 °C. Reproduced with permission [162]. Copyright © The Royal Society of Chemistry 2017. (e) CV profiles of the FSC device with rGO/ASWCNTs
electrode in different electrolyte systems at 0.1 V s−1 . (f) The EIS measurements of the FSC device with different types of electrolytes. (g) The electrochemical
performance of the FSC device with BMIMBF4 -based gel electrolyte. Reproduced with permission [163]. Copyright © 2017 Wiley‐VCH Verlag GmbH & Co. KGaA,
Weinheim.

Fig. 19. The performance and preparation progress of FSC devices with IL-based gel electrolyte. (a) Schematic illustration of PVA/BMIMCl/Li2 SO4 gel electrolyte.
(b) Ionic conductivity of PVA/BMIMCl/Li2 SO4 gel electrolyte with different counts of Li2 SO4 . (c) The electrochemical performance of the FSC device at a current
density of 0.15 A g−1 under the different bending angles conditions. Reproduced with permission [81]. Copyright © 2015 WILEY‐VCH Verlag GmbH & Co. KGaA,
Weinheim. (d) Schematic illustration of the supercapacitor. (e) CV profiles of the device at different bending angles. (f) The electrochemical performance of the FSC
device at the current density of 10 A g−1 , and the coulombic efficiency and the digital photo of the light-emitting diode were displayed in the inset. Reproduced with
permission [82]. Copyright © 2017, American Chemical Society.

ous changes were observed in the CV curves under different bend-
ing angles, demonstrating that the bending test does not affect the
performance of the capacitive property. In addition, at a current of
1000 mA g−1 , the FSC device delivered an outstanding capacitive per-
formance, 93.4% capacitance retention after 10,000 cycles, as dis-
played in Fig. 19f. To further enhance the stability of electrolyte and
the interface between electrode and electrolyte, Wang et al. [18] re-
ported a sodium-ion conducting PVA-based IL gel polymer electrolyte,
1-Ethyl-3 methylimidazolium trifluoromethanesulfonate (EMITf) which
was used as the plasticizer. This kind of gel electrolyte exhibited ex-
cellent thermal stability (150 °C) and a wide operating potential win-
dow of 4.7 V with a composition of PVA, 30% sodium triflate (NaTf)
and 10% EMITf. In addition, the ionic conductivity of PVA/NaTf/EMITf
reached up to 3.8 mS cm−1 . The device obtained a specific capaci-
tance of 103.7 and 127.8 F g−1 at the cut-off voltage of 1.6 and 2.0 V,
respectively.

340
H. Dai, G. Zhang, D. Rawach et al.
Furthermore, the PVDF-based IL gel electrolyte has also attracted
more and more attention from researchers due to its superior elec-
trochemical and chemical stability as well as good compatibility with
other materials [80,164,165,170]. For instance, Kumar et al. [171] pro-
posed a PVDF-based IL gel electrolyte that had an ionic conductivity
reaching up to 10−3 S cm−1 , which was composed of lithium triflu-
oromethanesulfonate (LiTf), ionic liquid 1-ethyl-3-methylimidazolium
trifluoromethanesulfonate (EMITf) and polymer matrix PVDF-HFP. In
addition, the ethylene carbonate and propylene carbonate were mixed to
improve the flexibility of this PVDF-based IL gel electrolyte. The device
obtained a long cycle performance with MWCNT-based EDLCs (50,000
cycles). Liu et al. [75] also used PVDF-HFP as the gel electrolyte matrix
and IL EMIMBF4 was incorporated to form a PVDF-based IL gel elec-
trolyte (EMIMBF4 /PVDF-HFP). With this gel electrolyte, the authors de-
signed a 3.5 V FSC device by using hierarchical carbon as the electrode.
The device obtained a specific capacitance of 201 F g−1 at a current
density of 0.5 A g−1 and exhibited 90.1% capacitance retention after
1000 bending cycles from 0° to 180° Feng et al. [78] used hierarchi-
cally graphene nanocomposite as the electrode material and utilized
EMIMBF4 /PVDF-HEP as the gel polymer electrolyte to make the FSC
device. The cyclic stability of this device was confirmed by the galvano-
static charge/discharge method. As displayed in Fig. 20a, this device ob-
tained 85% capacitance retention after 10,000 cycles. Fig. 20b demon-
strates the CV profiles under different bending angles. The curves are
overlapped very well, which confirms the good flexibility of the FSC de-
vice. Furthermore, the specific capacitance of the device under different
bending states was calculated from the galvanostatic charge/discharge
at 1 A g−1 , which was 180 F g−1 under flat state and 91.1% of initial spe-
cific capacitance was maintained at 180° after 1,000th cycle (Fig. 20c).
Deng et al. [79] reported asymmetric FSC devices by using the
EMIMBF4 /PVDF-HEP as the gel electrolyte. The CV curves of the de-
vice at various bending angles (0°, 60°, 120° and 180°) were obtained
as observed in Fig. 20d. The CV curves demonstrate excellent repeata-
bility, which indicates the outstanding mechanical stability of the de-
vice. In addition, the device obtained 71% capacitance retention after
the10,000th cycle. Most importantly, the FSC device is prepared as an
effective energy supplier for power electronic devices. For example, a
2 ∗ 2 cm2 square of the device can lighten up a pattern of “TJU” for
1 min after being charged at 5 A g−1 , which is manufactured by 19 red
LEDs (Fig. 20e). Furthermore, Yang et al. [172] reported a novel PVDF-
based IL gel electrolyte, named as PVDF-HFP/tetraethylammonium
tetrafluoroborate-acetonitrile (Et4 NBF4 -AN), with a highly porous struc-
ture and chemical cross-linking prepared by an immersion approach.
This kind of gel electrolyte demonstrated excellent properties such as
non-flammability, a broad electrochemical stable window of 2.9 V, and
high ionic conductivity of 14.4 mS cm−1 . Therefore, this FSC device
maintained a volumetric capacitance of 5.2 F cm−3 and a high energy
density of 5.16 mWh cm−3 . In addition, the FSC device retained almost
100% capacitance retention at the bending angle of 145°.
It is well accepted that if the temperature of the gel electrolyte
is higher than its sol-gel transition temperature, it will lose the abil-
ity to separate the electrodes. This will put a strict temperature limit
on any device constructed, without an additional mechanical separator
and the safety concerns of the device due to unexpected overheating or
harsh conditions. With this perspective, Zhang et al. [76] reported two
kinds of PVDF-based IL gel electrolytes: (i) Cell 1: [EMIM][NTf2]/PVDF-
HFP; and (ii) Cell 2: [C4mpyr][eFAP]/PVDF-HFP that could operate at
a wide range of temperatures from 25 °C to 100 °C. The ionic con-
ductivity of Cell 1 is 8.6 mS cm−1 at 25 °C. Fig. 20f displays the gel
state of IL/PVDF-HFP gel electrolyte with different temperatures. Tgel
of the gel electrolyte used in Cell 2 was uniformly higher than that of
the gel electrolyte used in Cell 1. The high Tgel might be attributed to
[C4mpyr][eFAP] being more viscous and hence Cell 2 is not a promis-
ing candidate as a gel electrolyte. Fig. 20g exhibits a temperature de-
pendence of the ionic conductivities of Cell 1 and Cell 2 with several
different supports. Fig. 20h demonstrates that the FSC device obtained
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Energy Storage Materials 34 (2021) 320–355
a high specific capacitance with Cell 1 (115 F g−1 ) compared with Cell 2
(8.5 F g−1 ). The device also attained 97% capacitance retention even at
the 10,000th cycle. Yin et al. [83] reported a novel FSC device consisting
of EMIMBF4 /PVDF-HFP-based gel electrolyte and bucky gel electrodes
through a one-step method. This gel electrolyte has not only exhibited
78% of mechanical robustness after 300 cycles at 60% strain test as well
as maintained a high ionic conductivity of 8.7 mS cm−1 , but has also in-
creased the contact area of electrolyte/electrode due to the cation-𝜋 or
𝜋-𝜋 interactions of the imidazolium ion component of the ionic liquid.
The device retained an areal capacitance between 22 and 81 mF cm−2
over a more extensive working temperature range of −40 °C to 100 °C
at 0.2 mA cm−2 . Moreover, Song et al. [173] reported an FSC device
with EMIMBF4 /PEG IL/gel electrolyte. The assembled device obtained
a wide working potential window of 3.5 V. This device retained a sta-
ble electrochemical performance at different temperatures (0–80 °C),
demonstrating that the device delivered good thermal stability. The FSC
device also exhibited high energy density of 90.9 Wh kg−1 and main-
tained 91.6% capacitance retention after 10,000 cycles. In addition, the
FSC device gained a specific capacitance of 180 F g−1 even at the bend-
ing angle of 180° These results provide new promising opportunities for
wearable devices.
Furthermore, Rana et al. [85] reported a renewable cellulose-
based dual network IL-mixture gel electrolyte. This kind of elec-
trolyte was prepared by phosphorylation and the dissolution of a
microcrystalline cellulose network in a tailor-made fashion of 1,3-
dimethylimidazolium methyl phosphite [DMIM][MeO(H)PO3 ] ionic liq-
uid mixture, followed by a subsequent polymerization of 2-hydroxyethyl
methacrylate monomer in the presence of a cellulose network (Fig. 21a
and b). This IL-mixture gel electrolyte presented a high ionic conductiv-
ity (2.6–22.4 mS cm−1 ) at a wide temperature range between 30 °C to
120 °C. Fig. 21c displays the SEM image of a cross-section of the elec-
trode/electrolyte interface which was continuous and therefore demon-
strated good adhesion between the electrode and electrolyte. The IL-
mixture gel electrolyte film with an equal weight percentage of C-
pHEMA and p-cellulose was manually stretched up to 350% of its origi-
nal length to confirm the outstanding stretchability and dimensional sta-
bility of the C-pHEMA/Cp-cellulose IL-mixture gel electrolyte (Fig. 21d).
Moreover, to indicate the remarkable durability of this device, the cycle
performance was conducted at a current of 2 A g−1 at 120 °C. As dis-
played in Fig. 21e, the FSC device obtained 93% capacitance retention
after 10,000 cycles, and the coulombic efficiency was improved to 97%.
The figure inset of Fig. 21e demonstrates that the device maintained its
stability under the bent state.
During the past years, researchers have made many efforts to de-
velop other kinds of IL-mixture gel polymer electrolytes [86,173–182].
Among them, due to the similar structures between the polymer and
ionic liquid electrolytes, the polymeric ionic liquids or poly(ionic liq-
uid)s (PILs) has been of interest because of their numerous advantages
such as high mechanical stability, processability, durability and better
compatibility between the polymeric matrix. Therefore, PILs have
attracted great attention in the manufacturing of FSCs [167,183–185].
For instance, as can be seen from Fig. 22a, Yang et al. [186] reported
an FSC device with a 6 V potential window using poly(VAC-co-EVImBr)
electrolyte. Generally, the ionic conductivity of the polymerized ionic
liquid is in the range of 0.01–0.1 mS cm−1 [187]. However, this
electrolyte obtained an ionic conductivity of 0.309 mS cm−1 , a value 3
times higher than previously reported, even at 60 °C (Fig. 22b). There-
fore, the device delivered a high specific capacitance of 75 F g−1 after
5000 cycles (Fig. 22c). The outstanding electrochemical performance
of the FSC is attributed to the highly flexible poly (VAc-co-EVImBr)
film electrolyte, which not only provides sufficient conductive anions
but also promotes charge transfer between the electrolyte/electrode
interface. Tiruye et al. [188] reported an FSC device with an IL-based
polymer electrolyte, which is fabricated from the mixture of PIL
poly(diallyldimethylammonium)bis(trifluoromethanesulfonyl)imide
(pDADMATFSI) and IL N‑butyl‑N-methylpyrrolidinium
H. Dai, G. Zhang, D. Rawach et al. Energy Storage Materials 34 (2021) 320–355

Fig. 20. FSC device with different IL-Based electrolytes. (a) Cyclic stability of the FSC device at the current density of 10 A g−1 . (b) The CV analysis of the FSC device
at different bending angles. (c) Cycling stability of device at different bent test. Inset are the digital photographs of the device. Reproduced with permission [78].
Copyright © 2017 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim. (d) CV profiles of FSC devices at different bending angles. (e) Cycle performance of the FSC
device at the current density of 5 A g − 1 . Inset in (e) is the optical image of LED. Reproduced with permission [79]. Copyright © 2019 Published by Elsevier B.V. (f)
Sol-gel transition temperatures in different electrolytes. (g) The ionic conductivities of different kinds of IL electrolytes. (h) The electrochemical performance of two
kinds of FSC devices. Reproduced with permission [76]. Copyright © 2018 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

bis(trifluoromethylsulfonyl)imide (PYR14 TFSI) in a mass ratio of
4:6 (Fig. 22d). Since PIL and IL both have pyrrolidinium cations and
TFSI anions, which were the wide electrochemical stability window in
FSC devices. Therefore, the device could operate at 3.5 V. The device
also exhibited excellent thermal stability due to containing PYR14 TFSI
(400 °C) and obtained an ionic conductivity of 3 mS cm−1 at 60 °C. In
addition, this device demonstrated a specific capacitance of 100 F g−1
and an energy density of 32 Wh kg−1 at 60 °C. Subsequently, Alexandre
et al. [189] proposed another PIL/IL gel polymer electrolyte, which
was prepared by the mixture of poly(1-vinyl-3-propylimidazolium
bis(fluorosulfonyl)imide) (poly(VPIFSI)) and EMIFSI in a mass ratio of
50:50. The ionic conductivity of poly(VPIFSI)/EMIFSI gel electrolyte
obtained reached up to 3.7 mS cm−1 . Additionally, the FSC device
with poly(VPIFSI)/EMIFSI gel electrolyte obtained 80% capacitance
retention after the 5,000th cycle, which demonstrated good cyclic
stability. Also, no capacitance loss at different bending angles (30°, 60°)
was observed.
Moreover, other IL-based gel electrolytes also have been devel-
oping rapidly [31,190]. For instance, as displayed in Fig. 22e, Kang
et al. [191] reported a graft copolymer gel electrolyte (PEGBEM-g-
PAEMA/EMIMBF4 ) via a free-radical polymerization approach. This IL-
mixture gel electrolyte obtained an ionic conductivity of 1.23 mS cm−1
due to the fast ion transmission channel of the polymer’s high polar-
ity [192]. This electrolyte obtained the original physical state and no IL
leakage was observed after the 200% EMIMBF4 was introduced, demon-
strating the high flexibility of PEGBEM-g-PAEMA/EMIMBF4 electrolyte.
The assembled FSC device obtained a 75% capacitance retention after
5000 cycles and retained the 3 V operating potential window at the
bent state (Fig. 22e). Lee et al. [193] proposed a novel IL mixture gel
electrolyte of diglycidyl ether of bisphenol-A/methyl tetrahydropthalic
anhydride/N-benzyldimethyl-amine/EMIMTFSI/LiTFSI, which was fab-
ricated by a poly(dimethylsiloxane) (PDMS) stamp method. This kind of
ionic gel electrolyte has not only enhanced the safety of the assembled
FSC device but also obtained high ionic conductivity of 230 mS cm−1 .
In addition, the CV profiles overlapped very well under the condition
of bending (R = 3 mm) and rolling (R = 1.5 mm) and no obvious
changes of the resistance values among the flat, bent, and rolled states
were observed. Therefore, the electrolyte of the FSC device exhibited

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H. Dai, G. Zhang, D. Rawach et al. Energy Storage Materials 34 (2021) 320–355

Fig. 21. The performance and schematic illustration of C-pHEMA/C-p-cellulose ionic gel electrolytes. (a-b) The preparation process of C-pHEMA/C-p-cellulose ionic
gel electrolytes. (c) SEM image of a side view of the interface of electrode/electrolyte. (d) Photographic images of manual stretching of C-pHEMA/C-p-cellulose
ionic gel electrolytes. (e) Cycle performance of FSC at the current density of 2 A g−1 under the working temperature of 120 °C condition. The CV profiled of FSC at
different bending states was displayed in the inset. Reproduced with permission [85]. Copyright © 2019 Elsevier B.V. All rights reserved.

excellent flexibility and cyclic stability. Ha et al. [180] reported an
EMIMTFSI/PMMA/PC IL-mixture gel electrolyte with a working poten-
tial of 2.5 V by a dip-coating approach. The FSC device maintained
a 99% capacitance retention after 100 cycles under the bending con-
dition with a radius of 0.7 cm and a bending angle of 360°, demon-
strating the excellent flexibility and cyclic stability of the device using
EMIMTFSI/PMMA/PC IL-mixture gel electrolyte.
3.4. Redox gel electrolyte for flexible supercapacitors
Aqueous polymer gel electrolytes, organic polymer gel electrolytes
and ionic liquid-based polymer gel electrolytes are mainly used as ionic
mediators for charge storage in FSCs. However, it is well known that
they can’t enhance the specific capacitance of FSCs. Recently, a new
direction in the electrolyte field has been discovered, namely the use
of redox additives to enhance the performance of FSCs [194]. Dif-
ferent redox-active materials, such as vanadyl sulfate (VOSO4 ), hex-
acyanoferrate (II)/(III) (K3 Fe(CN)6 /K4 Fe(CN)6 ), alizarin red (AR), P-
phenyldiamine (PPD) and potassium iodide (KI) are added to the so-
lution as electrolytes for their use in supercapacitor energy storage de-
vices, which allows the use of their electron transfers to generate redox
reactions to introduce additional pseudocapacitance, thereby improving
the total specific capacitance and energy density of the device, which

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H. Dai, G. Zhang, D. Rawach et al. Energy Storage Materials 34 (2021) 320–355

Fig. 22. The schematic illustration and electrochemical performance of IL electrolytes. (a) The working potential window of different IL electrolytes. (b) The
ionic conductivity of different kinds of IL electrolytes at the temperature range from 25 to 85 °C. (c) The specific capacitance of the FSC with different kinds of
IL electrolytes at the temperature of 60 °C. Reproduced with permission [186]. Copyright © 2017 Published by Elsevier B.V. (d) The preparation process of the
FSC devices. Reproduced with permission [188] Copyright © 2015 Elsevier B.V. All rights reserved. (e) The preparation process and the mechanical property of
PEGBEM-g-PAEMA/EMIMBF4 gel electrolyte. Reproduced with permission [191] Copyright © 2019 Elsevier B.V. All rights reserved.

has attracted the attention of researchers [195–198]. Redox additives
can be divided into three categories: redox gel electrolyte with inorganic
compound additives, redox gel electrolyte with organic compound addi-
tives and redox gel electrolyte with IL additives with different polymer
framework (Fig. 23).
3.4.1. Redox gel electrolyte with inorganic compound additives
To promote the specific capacitance of FSC devices, some inor-
ganic compounds are used as additives in the gel electrolyte systems
[199,200]. For instance, Zhou et al. [96] introduced the NaI and I2
into the PEO-based polymer electrolyte (PEO/LiClO4 ) as mediators to
both enhance the conductivity of the polymer electrolyte and the spe-
cific capacitance of the device. This mediator-gel polymer electrolyte
exhibited a high average ionic conductivity of 20.2 mS cm−1 . This was
due to the reaction between two iodine molecules quickly reacting to
form triiodide as shown in Eq. (7). In summary, the total conductivity is
the sum of two components, the physical migration of the ionic species
and the electron exchange reaction that causes an apparent charge dis-

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H. Dai, G. Zhang, D. Rawach et al. Energy Storage Materials 34 (2021) 320–355

Fig. 23. FSC with different redox additives in gel electrolyte systems. (a) CV measurements of the FSC device with and without RM. (b) The redox mechanism of
the RM in the gel electrolyte system. (c) Schematic illustration and digital photos of the FSC with RM additives under the condition of different bending angles.
Reproduced with permission [201] Copyright © 2020, American Chemical Society. (d) Tensible property of flexible PVA/KOH/K3 [Fe(CN)6 ] gel polymer. (e) Charge-
discharge profiles of FSC devices with different kinds of gel electrolytes. (f) Ionic conductivity of PKF gel polymer with the additive of K3 [Fe(CN)6 ] at different
concentrations. Reproduced with permission [87]. Copyright © 2014 Published by Elsevier B.V. (g) Schematic illustration of FSCs. (h) The energy density and
power density of FSC with different gel electrolytes. Reproduced with permission [202]. Copyright © 2016 Elsevier Ltd. All rights reserved. (i) The charge/discharge
mechanism of the FSC device with additives. (j) The energy density and power density of FSC with gel electrolyte. (k) The ionic conductivity of the gel electrolyte
with EV additives at different concentrations. Reproduced with permission [99]. Copyright © 2019 Elsevier Ltd. All rights reserved.

345
H. Dai, G. Zhang, D. Rawach et al.
placement. The device obtained 90% capacitance retention after 3000
charge/discharge cycles and enhanced the energy/power density due
to the addition of NaI/I2 . Generally, PVA’s characteristics include a
secure processing, an easy film formation, a low price, and excellent
bending properties. It has been playing an essential role as the frame-
work for gel electrolytes [141,142]. In addition, potassium iodide (KI)
is also usually used as an inorganic redox additive due to its nontoxic-
ity, relatively low molecular weight, and high solubility. For example,
Yu et al. [88] reported a quasi-solid-state supercapacitor via utilizing
alkaline PVA as the network and inorganic material KI as the additive
to form gel electrolyte (PVA/KOH/KI) and activated carbons as elec-
trodes. When the KI (0.6 g) was introduced into the electrolyte system
and occurred a reversible redox process on the electrolyte/electrode in-
terface (Eq. (7)), the ionic conductivity of the electrolyte was enhanced
(12.73 mS cm−1 ). The pseudocapacitance (236.90 F g−1 ) of the electrode
was increased thus improving by 74.28% compared to the PVA/KOH
system at the same current density. In addition, the device gained an
energy density and power density of 7.80 Wh kg−1 and 15.34 kW kg−1 ,
respectively. Moreover, Kim et al. [89] also used PVA/KOH/KI as the gel
electrolyte and MgCo2 O4 nanoneedles as the electrode to assemble the
redox-active FSCs. This electrolyte demonstrated an ionic conductivity
of 13.21 mS cm−1 with 3 mmol of KI. Furthermore, the device exhib-
ited an excellent capacitive performance (185.88 C g−1 at 5 mV s−1 ),
according to Eqs. (8)–(11). Also, according to Eq. (5)–(6), the device ex-
hibited a maximum energy density of 41.308 Wh kg−1 at 464.72 W kg−1
power density. Furthermore, Park et al. [201] introduced the redox me-
diator (RM) of KI into the PVA/H3 PO4 gel electrolyte, which improved
the specific capacitance. As can be seen from Fig. 23a, the gel elec-
trolyte with KI additive exhibited a CV area 7.3 times larger than the
blank electrolyte. In addition, there was an obvious oxidation peak at
0.72 V and two reduction peaks at 0.24 and 0.48 V, demonstrating mul-
tiple Faradic capacitive behaviors. These redox reactions are depicted
by Eq. (8) and (9) (Fig. 23b). To further illustrate the flexibility of the
FSC device, the authors conducted CV experiments at different bend-
ing angles (Fig. 23c). Compared with no bending stress, the FSC device
with KI RM displayed no obvious change as the bending angle was var-
ied from 135° to 0°. The authors also assembled an FSC device with the
length of 47 cm and obtained 75.7 mF charge storage ability. These re-
sults provide a novel and advanced strategy to improve the capacitance
in flexible supercapacitors.
I− + I2 ↔ I−
3
(7)
3 I − ↔ I− +2e− (8)
3
2I− ↔ I2 +2e− (9)
3 ↔ 3I 2 + 2 e
2I− −
(10)
I2 +6H2 O ↔ 2IO− +
3 +12H +10e
−
(11)
[ ]3− [ ]4−
Fe(CN)6 + e− ↔ Fe(CN)6 (12)
Ma et al. [87] proposed an FSC device using a redox-active gel elec-
trolyte, which was fabricated by PVA as the electrolyte framework,
KOH as the electrolyte salt and K3 [Fe(CN)6 ] as the inorganic addi-
tive (PKF for PVA-KOH-K3 [Fe(CN)6 ]). The redox-active gel electrolyte
exhibited a good stretching property, which was about 2.5-fold the
length it was originally (Fig. 23d). As can be seen from Fig. 23e, the
charge/discharge time of the FSC with PKF4 (PVA–KOH–K3 [Fe(CN)6 ])
with 1:1:0.04) was much longer than that of the FSC with PK. The de-
vice with PKF4 gel polymer delivered a smaller IR drop comparing with
the FSC device using PVA-KOH (PK) gel polymer as the electrolyte.
This could be attributed to the higher ionic conductivity of the PKF4
gel polymer compared to the PK gel polymer, as exhibited in Fig. 23f.
346
Energy Storage Materials 34 (2021) 320–355
When 0.04 g of K3 [Fe(CN)6 ] was used, the ionic conductivity of PKF4
gel polymer obtained was 45.56 mS cm−1 . However, increasing the
amount of K3 [Fe(CN)6 ] leads to a decrease in its ionic conductivity
which was caused by the aggregation of free ions and the crystalliza-
tion of K3 [Fe(CN)6 ] in the PVA system. The device indicated a high
electrode specific capacitance of 430.95 F g−1 , a high energy density of
57.94 Wh kg−1, and obtained 89.3% capacitance retention after 1000
cycles. The total capacitance of the FSC consists of an electrical dou-
ble layer capacitance formed by the ions on the surface of an activated
carbon electrode and pseudocapacitance through reversible redox reac-
tion from [Fe(CN)6 ]3− /[Fe(CN)6 ]4− on the electrolyte/electrode inter-
face (Eq. (12)). In addition, as displayed in Fig. 23g, Veerasubramani
et al. [202] used PVA/H3 PO4 /Na2 MoO4 as the gel electrolyte (inor-
ganic Na2 MoO4 was used as an additive) and reduced graphene ox-
ide (rGO) nanosheets as the electrode to fabricate the FSC. As exhib-
ited in Fig. 23h, the FSC delivered a maximum length energy density,
using PVA/H3 PO4 /Na2 MoO4 as the redox-active gel electrolyte, of 2.6
mWh cm−1 at a length power density of 31.25 mW cm−1 . This was due
to the redox reaction between possible redox couples Mo(VI)/Mo(V)
and Mo(VI)/Mo(IV). Moreover, as exhibited in Fig. 24a, Feng et al.
[92] introduced bromamide acid sodium (BAAS) as an inorganic ad-
ditive into the PVA/H2 SO4 gel electrolyte. The PVA/H2 SO4 /BAAS gel
electrolyte demonstrated high toughness under the large deformations
and displayed good strength under stretching conditions. In addition,
this electrolyte film had many porous microstructures and the high de-
gree of continuous and interconnected porous microstructure network
promoted ion transport and diffusion in gel systems that made the ionic
conductivity reach 21.4 mS cm−1 . Fig. 24b displays the schematic il-
lustration of BAAS during the charge/discharge process, which demon-
strated why the device obtained an outstanding electrochemical per-
formance (Fig. 24c). The device expressed a specific capacitance of
390 F g−1 at a current density of 800 mA g−1 , and exhibited a high
energy density of 30.5 W h kg−1 at a power density of 600 W kg−1 .
In addition, the device also indicated a small capacitance loss when
the gel polymer was subjected to the large tensile strain of 100% or
high pressures of 2000 kPa. Meanwhile, the capacitance of the de-
vice remained very well after 500 complete bending cycles. Subse-
quently, Feng et al. [203] also used BAAS as redox additive to pre-
pare a multifunctional (3-dimethyl (methacryloyloxyethyl)ammonium
propane sulfonate (DMAPS)/PAA/H2 SO4 /BAAS gel electrolyte, which
demonstrated high self-healing within 8 min, an excellent ionic con-
ductivity of 40 mS cm−1 and an outstanding stretch strain of 2000%.
Therefore, the manufactured FSC device obtained a specific capacitance
of 240 F g−1 and maintained a 96% capacitance retention at the bending
angles from varying from 0° to 180° after 400 cycles.
Apart from the use of PVA and PEO polymers as electrolyte frame-
work, the PAMPS (poly (2-acrylamido-2-methyl-1-propanesulfonic
acid)) was also used as a framework of gel electrolyte. For example,
cross-linked PAMPS/MMT hydrogels were synthesized and used for elec-
trochemical measurements along with KOH as an inorganic additive
[101]. Furthermore, Cevik et al. [100] manufactured an FSC with the
novel redox-active polymer electrolyte (PAMPS/Mox ), where x repre-
sented the amount of Mo in PAMPS gel electrolyte, which displayed
good thermal stability (Fig. 25a). The ability of an FSC to have faster
discharge time and charging performance relayed not only on the ac-
tive electrode substance but also on the electrolyte. Fig. 25b displays
the specific capacitances of different concentrations of PAMPS and
PAMPS/Mox containing hydrogels at various current densities (1, 2, 3,
5 and 10 mA). The maximum specific capacitance of the supercapaci-
tor, including PAMPS/Mo3 electrolyte, was calculated as 530 F g−1 at
1 A g−1 . The device delivered an energy density of 73 Wh g−1 at a power
density of 580 W kg−1 using the PAMPS/Mo3 electrolyte (Fig. 25c). As
shown in Fig. 25d, there was no obvious change in the specific capac-
itance at the 60° angle bending test. Similarly, Cevik and co-workers
[204] reported another gel electrolyte, using poly (vinylphosphonic
acid) (PVPA) as the network and ammonium molybdate (Mox where
H. Dai, G. Zhang, D. Rawach et al. Energy Storage Materials 34 (2021) 320–355

Fig. 24. The mechanism and performance of BAAS. (a) The strength property of PVA/H2 SO4 /BAAS gel electrolyte and the original length was displayed in the inset.
(b) The redox mechanism of BAAS. (c) The electrochemical performance of Device 2 in different gel electrolyte systems. Reproduced with permission [92]. Copyright
© The Royal Society of Chemistry and the center National de la Recherche Scientifique 2017.

Fig. 25. FSC devices with PAMPS gel electrolytes. (a) TGA analysis of PAMPS hydrogels with different counts of Mo. (b) Electrochemical performance of FSCs.
(c) The power density and energy density of FSCs. (d) The performance of the PAMPS/Mo3 FSC device at different bent test. Reproduced with permission [100].
Copyright © 2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim.

x is the weight percent (w/w) of Mo in PVPA) the inorganic redox addi-
tive. The FSC device with PVPA/Mo10 (10 w/w of Mo) redox gel elec-
trolyte (4.1 mS cm−1 ) demonstrated a specific capacitance of 1276 F g−1 ,
which was 50 times larger than pure PVPA gel electrolyte and main-
tained an 85% capacitance retention after 2500 cycles. In addition, the
FSC device obtained a specific capacitance of 987, 980, 978.5 F g−1
under the condition of free-standing, 60° bent state and twisted
state, respectively, which illustrated the excellent flexibility of this
FSC.
Xun et al. [102] reported a series of gel polymer electrolytes. The
renewable soy protein isolate (SPI) was used as the polymer matrix, and
Li2 SO4 was utilized as the electrolyte salt to obtain a wider potential
window (1.5 V). In addition, the redox mediator KI was introduced to
enhance the energy density of the FSC assembled with the prepared gel
polymer electrolyte sandwiched by activated carbon electrodes. After
the KI mediator was added, the ionic conductivity of the gel polymer
electrolyte was increased (2.54 mS cm−1 ), and a pseudocapacitance was
discovered. The specific capacitance of the supercapacitor using SPI-

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H. Dai, G. Zhang, D. Rawach et al. Energy Storage Materials 34 (2021) 320–355

Fig. 26. The performance of HQ redox additive in gel electrolytes. (a) The redox mechanism of hydroquinone. (b) The energy density and power density of the
FSC device. (c) Digital photograph of the prepared flexible device with a scale bar of 1 cm. Reproduced with permission [97]. Copyright © The Royal Society of
Chemistry 2016.

Fig. 27. The preparation progress and electrochemical performance of the FSC device. (a) Illustrated the preparation process of the PDA. (b) Contact angle mea-
surements with different kinds of electrolytes. (c) CV profiles of the FSC device at the current density of 10 mV s−1 . (d) Cycling performances of FSC with different
kinds of electrolytes. Reproduced with permission [94]. Copyright © 2019 Elsevier B.V. All rights reserved.

Li2 SO4 –100 wt% KI electrolyte is 224.19 F g−1 , which is an increase times higher than that of the device without the HQ additive but also
of 1.56 times compared with the SPI-Li2 SO4 system at the same cur- reduced the equivalent series resistance from 28.7 Ω to 24.1 Ω. Fig. 26a
rent density. At the same time, the energy density of supercapacitors shows the schematic illustration of HQ redox additive, which demon-
increased from 5.90 W h kg−1 to 16.02 W h kg−1 . strated that each HQ molecule reversibly produced and deposited two
electrons and two protons as a high-performance pseudocapacitor ma-
terial. Therefore, the introduction of HQ improved capacitance by gen-
3.4.2. Redox gel electrolyte with organic compound additives
erating additional pseudocapacitors. The results of Fig. 26b displays the
Except for inorganic materials as gel electrolyte additives, some or-
energy density of the FSC which can be improved by adding the HQ
ganic materials are also introduced into gel electrolytes [91,194,205–
as a redox-active additive to the electrolyte. Fig. 26c exhibits an op-
207]. Since the redox reaction of the hydroquinone (HQ) could improve
tical image of the encapsulated double-sided MSC while bending to a
the ion transfer, the ionic conductivity of the gel electrolyte system is
radius of 5 mm, which demonstrated that the device had good mechan-
improved by introducing the HQ into a gel electrolyte system [91]. For
ical properties. Jinisha et al. [208] also utilized HQ as an additive to
instance, as can be seen from Fig. 26a-c, Kim et al. [97] proposed the
manufacture the PVA/KOH/HQ redox gel electrolyte, which exhibited
manufacturing process of a high-performance FSC using a redox-active
a high ionic conductivity of 53 mS cm−1 . The assembled FSC device
additive, which was called resorcinol (PMMA/PC/LiClO4 /HQ) organic
obtained a specific capacitance of 326.53 F g−1 and capacitance reten-
gel electrolyte. Adding HQ as a redox-active additive not only signif-
tion of 84.2% was maintained at the 1,000th cycle. Xu et al. [209] used
icantly promoted the energy density of the FSC, which was about 35

348
H. Dai, G. Zhang, D. Rawach et al. Energy Storage Materials 34 (2021) 320–355

Fig. 28. The schematic process of PNA in the PVA/H2 SO4 gel electrolyte system. Reproduced with permission [90]. Copyright © 2017 Elsevier B.V. All rights
reserved.

Fig. 29. The electrochemical performance of IL-based redox additive. (a) Ionic conductivities of PVA/Li2 SO4 /BMIMX (X = Cl, I) gel electrolyte. (b) The measurements
of stress-strain of PVA/Li2 SO4 /BMIMX gel electrolyte. (c) The values of energy density and power density of FSC device with PVA/Li2 SO4 /BMIMX gel electrolyte.
Reproduced with permission [38]. Copyright © 2018 Elsevier Ltd. All rights reserved.

PVA/H2 SO4 /HQ (0.3 g) as the electrolyte and CNT-PPy as the flexible
electrode to assemble the FSC device, which demonstrated a high ionic
conductivity of 23.2 mS cm−1 . This device obtained an areal capaci-
tance of 1168 mF cm−2 due to the redox reaction of HQ and benzo-
quinone. Subsequently, Potohode et al. [93] also used reversible redox-
active HQ as an organic additive in the PVA/H2 SO4 gel electrolyte
and polymer grafted morphology of nanocomposite as electrode ma-
terials to prepare the symmetric FSC. The device obtained a 78% ca-
pacitive retention after 2000 cycles. Moreover, Kim et al. [90] utilized
p-nitroaniline (PNA) as organic additive and micro- and mesoporous sil-
icon carbide/ferroferric oxide composites as the electrode to fabricate
the FSC. When 0.18 mmol of PNA was used, the ionic conductivity of the
gel electrolyte reached 16.84 mS cm−1 . Fig. 28 displays the achievable
redox reaction mechanisms of the PVA/KOH/PNA electrolyte. Based on
this mechanism, the device obtained an excellent specific capacitance of
97.6 F g−1 at 5 mV s−1 with a maximum energy density of 48.94 Wh kg−1
at a power density of 463.64 W kg−1 . Subsequently, Shumakovich et al.
[210] proposed a new redox gel electrolyte PVA/H2 SO4 /sodium 1,2-
naphthoquinone-4-sulfonate (NQS) to fabricate asymmetric FSC device
with two similar PANI/MWCNT flexible electrodes. This device with
13 mM NQS additive maintained an energy density of 23.3 Wh kg−1
at a power density of 1800 W kg−1 and achieved 93% capacitance re-
tention after 3000 cycles. Similarly, Feng et al. [211] fabricated a new
FSC device with PVA/H2 SO4 / anthraquinone-2-sulfonic acid sodium
salt (AQSA-Na). This device retained a specific capacitance of 430 F g−1
due to the redox reaction of AQSA-Na and retained an energy density of
33.4 Wh kg−1 . In addition, under the condition of folded/unfolded, the
FSC device exhibited 91% capacitance retention after 500 cycles.
Yin et al. [94] reported an FSC using polydopamine (PDA) as the
organic additive to make a redox-active PVA/PDA gel electrolyte. As
can be seen from Fig. 27a, the manufactured PDA conjugated macro-
molecules significantly decrease the large HOMO-LUMO gap and pro-
mote the electron transfer kinetics, thereby improving the power den-
sity and the reversibility of the redox reaction through simple polymer-
ization. Therefore, the ionic conductivity of the gel electrolyte was en-
hanced from 85 mS cm−1 to 125 mS cm−1 . After the addition of PDA,
the contact area between the electrolyte and the electrode increased,
improving the electrochemical performance of the device (Fig. 27b).
Fig. 27c indicates the CV curves of the device with the redox-active
PVA/PDA gel electrolyte at different bending test conditions. As shown
in Fig. 27d, the FSC maintained 92% capacitance retention after 30,000
cycles at a current density of 1 A g−1 , and obtained a maximum energy
density of 38 W h kg−1 at a power density of 500 W kg−1 . Similarly, Le
et al.[95]. proposed a new and environmentally friendly phlorogluci-
nol additive incorporated PVA/LiClO4 gel polymer electrolyte for sym-
metric FSCs. Compared with the gel electrolyte without phloroglucinol
(60 F g−1 ), the introduction of 10 wt% phloroglucinol into PVA/LiClO4
gel polymer electrolytes as organic additive obtained a much higher
specific capacitance (114 F g−1 ), which could be attributed to the redox
reaction of phloroglucinol in the system. Furthermore, the device exhib-
ited an energy density of 2.3 Wh kg−1 at a power density of 150 W kg−1
with the PVA/LiClO4 electrolyte containing the phloroglucinol organic
redox additive.
3.4.3. Redox gel electrolyte with IL additives
Although ILs have been used as an electrolyte for energy storage
systems [74,162,186,212], the utilization of ILs as additives in the field
of gel electrolytes to improve the electrochemical performance of FSCs
have not gained much attention. This is because ILs often require com-
plex purification and the assembly procedures must be done in a strictly
controlled environment to avoid the introduction of moisture. In ad-
dition, other disadvantages, such as safety issues related to the high
viscosity and high cost of ILs have also limited their practical appli-
cation in FSCs. Therefore, to obtain an FSC with high energy density,
it is a novel and effective way to develop excellent polymer-based gel
electrolyte that can promote pseudocapacitors, deliver a wide voltage
window, and have outstanding mechanical properties. With this per-
spective, Tu et al. [38] proposed 1‑butyl‑3-methylimidazolium iodide
(BMIMI) and 1‑butyl‑3-methylimidazolium chloride (BMIMCl) as redox-
active additive material to enhance the specific capacitance by a faradic
reaction and Li2 SO4 was used to enhance the operating potential win-
dow (1.6 V). Fig.29a presents the ionic conductivity of the two kinds of

349
H. Dai, G. Zhang, D. Rawach et al.
IL additives. When the mass ratio of BMIMX: PVA is 3:1, the highest ionic
conductivity was obtained (46.0 mS cm−1 for the PVA/Li2 SO4 /BMIMI
and 37.2 mS cm−1 for the PVA/Li2 SO4 /BMIMCl). The ionic conductivity
was improved by proper addition of BMIMX, which is attributed to two
reasons: (i) the increase in ion concentration; and (ii) the strong plasti-
cizing effect, which softens the polymer main chain, thereby enhancing
the flexibility of the polymer matrix and promoting segmented motion
and ion migration of polymers. Fig. 29b demonstrates the stress-strain
curves of this gel electrolyte with different kinds of IL additives. Accord-
ing to the results, PVA/Li2 SO4 /BMIMI displayed an outstanding tensile
property with the elongation at break of up to about 1200% and tensile
strength of about 2.0 MPa compared with the PVA/Li2 SO4 /BMIMCl (the
elongation at break at 300%). So, the FSC obtained an energy density
of 29.3 Wh kg−1 with a redox-active PVA/Li2 SO4 /BMIMI gel electrolyte
(Fig. 29c).
For the redox gel electrolyte, the redox medium moving back and
forth between the two electrodes will cause a reduction in the coulom-
bic efficiency, which will cause side effects and hinder its commercial
application. The performance can be improved through the following
strategies: Firstly, replace the ordinary separation membrane with a
special separation membrane (ion-selective membrane) to prevent the
crossover of mixed electrolytes. Secondly, another strategy is to use a
special active media (that is, adding an external stabilizer), which can
be converted into the insoluble matter on the electrode surface. Thirdly,
to couple the redox mediator to the electrode material through covalent
or non-covalent bonding.
4. Conclusion and perspectives
In recent years, FSCs have drawn more attention compared to tra-
ditional supercapacitors due to their excellent characteristics including
high stability, high safety, low cost, good mechanical properties, fast
charge and discharge, and high efficiency. However, the FSCs devices
still face many challenges, such as low energy density in practical ap-
plications, high production cost, low voltage per unit, and high self-
discharge, which need to be addressed. Apart from the points mentioned
above, it is also essential to develop the new generation of flexible gel
polymer electrolytes with high ionic conductivities, high working poten-
tial and flexibility. This is important because the electrolyte is an impor-
tant part of FSCs, which produces ion conductivity and charge compen-
sation on both electrodes. The electrolyte not only plays an important
role in the energy storage mechanism (EDLCs and pseudocapacitors),
but also further affects the electrochemical performance of the FSCs de-
vices. Therefore, a large amount of research has been concentrated on
the development of gel electrolytes with high capacity, good cyclic sta-
bility and excellent high ionic conductivity. In this review, the most
recent progress and mechanical properties of gel electrolytes for FSC
devices have been systematically discussed. In addition, we also give a
synopsis of reaction mechanisms and performance evaluation standards
for FSCs.
The gel electrolytes of FSC devices can be divided into four cate-
gories, including aqueous gel electrolytes, non-aqueous gel electrolytes,
ionic liquid-based gel electrolytes and redox gel electrolytes. (i) The
aqueous gel electrolytes are simple to manufacture, environmentally
friendly and can prevent leakage. When applied to FSCs, the device costs
can be effectively reduced, and the FSCs also demonstrate good cyclic
stability and high energy/power density. Recently, PVA polymers have
been widely used in FSCs. It can be cross-linked with a cross-linking
agent to make a polymer gel electrolyte, which can be synthesized in
three different environments including acid, alkali and neutral. As such,
they have very broad application prospects. Although PVA has high
structural integrity, and good mechanical and good water absorption
properties, this polymer has a long carbon chain that lacks hydrophilic
groups, thus the polymer substrate demonstrates low water retention,
low ionic conductivity and a low voltage window hindering the prac-
tical applications. Nevertheless, natural polymer hydrogels have many
350
Energy Storage Materials 34 (2021) 320–355
hydrophilic groups making them highly hydrophilic. Therefore, the ad-
vantage can help polymerization the substrate retains moisture and in-
creases ionic conductivity, which has attracted wide attention from re-
searchers[213]. Therefore, in view of the global development and use
of environmentally friendly energy, the application of natural polymers
in FSCs needs further development. (ii) When the non-aqueous gel elec-
trolytes are used in FSC devices, they exhibit high working voltage and
high specific capacitance values. Yet, they do not present good cycle
stability which needs to be further improved. (iii) For the application of
ionic liquid-based gel electrolytes in FSC devices, ionic gel electrolytes
illustrate a wider range of operating potential window than other mate-
rials but have a poor energy density, power density, and cycle stability.
Imidazole-based ionic liquids have high conductivity and low viscosity
and have been extensively studied as FSC electrolytes, but the stabil-
ity and cyclic performance of some ionic liquids need to be improved.
Pyrrole-based ionic liquids demonstrate excellent electrochemical per-
formance and maintain excellent electrochemical performance at high
temperatures. So, the pyrrole-based ionic liquid gel electrolytes exhibit
a high application prospect in high-temperature FSC devices due to their
excellent cyclic performance and thermal stability. Short-chain fatty
quaternary ammonium salt ionic liquids have a wide voltage window,
high conductivity and good stability, both high- and low-temperature
performance, which can improve the high-temperature safety perfor-
mance and stability of FSCs. Therefore, the development of ionic liq-
uids suitable for use as supercapacitor electrolytes with excellent perfor-
mance is an important way to realize the industrialization of ionic liquid
FSC electrolytes. (iv) FSC devices with redox gel electrolytes can ob-
tain high specific capacitance, high ionic conductivity, and good cyclic
stability. While on the premise of ensuring the cyclic stability of super-
capacitors, to further enhance the energy density and power density of
FSC devices may be the main research directions in the future. However,
there are still quite a few scientific and technical problems to be solved.
Firstly, redox additives are mainly used in aqueous electrolytes but not
in organic electrolytes. Secondly, there are many available redox-active
substances or compounds, which, however, have not been used as re-
dox additives in electrolytes for FSC commercialized applications. Fi-
nally, the microscopic interaction mechanism between the redox-active
materials and polymer materials is not clear. The uniform dispersion of
redox-active materials in the polymer matrix needs to be solved. Also,
designing and constructing a good electrode/electrolyte interface is a
future research hotspot.
Apart from the four categories of gel electrolytes, self-repairing poly-
mer electrolytes have become a hot topic for research because they can
spontaneously restore the original electrochemical performance and ex-
hibit outstanding reliability and safety [29]. For example, Huang and
co-workers [214] designed a self-healing gel electrolyte to drive flexi-
ble electrode materials to realize the self-healing of the capacitor struc-
ture and function. The device exhibited excellent ductility and self-
healing characteristics. It delivered good electrochemical characteristics
under 600% mechanical conditions and presented a retention capac-
ity of 100% after 20 cuts/repairs. Pan et al. [215] utilized boron ester
bonds to obtain a gel electrolyte with self-healing properties (PVA-g-
PAA/KCl). The device displayed approximately 100% capacity retention
after 10 cuts/repairs at room temperature. Therefore, to make FSC de-
vices with higher performance reliability, longer service life and wider
environmental adaptability, the self-healing gel electrolytes are criti-
cal. The future research focus of self-healing gel electrolytes could be
mainly concentrated in the following aspects: (i) self-repairing poly-
electrolytes with multiple repair mechanisms. Presently, it is known
that polymer repair is possible through different mechanisms. Repair
methods based on reversible covalent bonds include Diels-Alder reac-
tion, disulfide bonds, boron bonds, and phthalocyanine bonds. Repair
methods based on dynamic interactions include hydrogen bonds, metal
coordination, supramolecular interactions, and monoliths. Comprehen-
sive utilization of these repair methods is the best way to further im-
prove the self-repairing performance of self-repairing polyelectrolytes.
H. Dai, G. Zhang, D. Rawach et al.
(ii) Self-healing gel electrolytes that work stably in harsh environments.
For example, under the condition of low or high temperatures, the sta-
bility of the self-healing gel electrolytes directly determines the safety
and reliability of energy devices. To realize the widespread use of self-
healing polyelectrolytes, improving its performance stability under ex-
treme conditions is a very important and urgent research direction.
In summary, based on the comprehensive considerations of the
safety, wide temperature range and flexibility, the use of gel polymer
electrolytes to replace the liquid electrolytes is one of the key research
directions for the development of FSC devices. The ideal FSC gel elec-
trolyte needs to have the following merits: (i) good mechanical proper-
ties and flexibility, (ii) high ionic conductivity equivalent to that of the
liquid electrolyte, (iii) excellent chemical inertness to satisfy the longer
shelf life and cycle life for the practical applications, (iv) good chemical
stability and interface compatibility when in contact with an electrode,
and (v) high moisture retention rate and ultra-high safety in extreme
environments. Therefore, to solve these problems at the same time, the
design and application of redox self-healing gel electrolyte may be a new
research direction. Moreover, the redox self-healing gel electrolytes pro-
vide new space for the application of flexible supercapacitors as high-
energy storage devices and thus are promoting for the large-scale ap-
plication of flexible electronic devices. However, while improving the
performance of the redox self-healing gel electrolyte, it is necessary to
thoroughly analyze the reaction mechanism of this type of electrolyte
by different in situ approaches such as in-situ hard and soft X-ray ab-
sorption spectroscopy, in-situ Fourier-transform infrared spectroscopy
to promote the development of new electrolytes.
Author contributions
G. Zhang, C. Lai and S. Sun conceived and designed the review pa-
per. H. Dai conducted manuscript planning and writing. D. Rawach, C.
Fu, C. Wang and M. Dubois participated in manuscript discussion and
revision. S. Sun supervised the project. All authors contributed to the
final preparation of the manuscript.
Declaration of Competing Interest
There are no conflicts to declare.
Acknowledgments
This work was financially supported by the Natural Sciences and En-
gineering Research Council of Canada (NSERC), Fonds de Recherche du
Québec‐Nature et Technologies (FRQNT), Canada Foundation for Inno-
vation (CFI), center Québécois sur les Materiaux Fonctionnels (CQMF),
and Institut National de la Recherche Scientifique (INRS), 111 project
(D18023). Dr. C. Fu acknowledges the support by the Natural Science
Foundation of China (Grant No.21902063). H. Dai thanks the scholar-
ship from The Fonds de recherche du Québec - Nature et technologies
(FRQNT).
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