j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1

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

Review Article

Electrode polymer binders for supercapacitor

applications: A review

Nor Azmira Salleh a, Soorathep Kheawhom b, Noor Ashrina A Hamid c,

Wan Rahiman d, Ahmad Azmin Mohamad a,*
a
Energy Materials Research Group (EMRG), School of Materials and Mineral Resources Engineering, Universiti Sains
Malaysia, 14300, Nibong Tebal, Pulau Pinang, Malaysia
b
Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand
c
School of Chemical Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Pulau Pinang, Malaysia
d
School of Electrical and Electronic, Universiti Sains Malaysia, 14300 Nibong Tebal, Pulau Pinang, Malaysia

article info abstract

Article history: With the fast growth of supercapacitors, there are growing demands for more flexible,
Received 9 September 2022 stable, safer and cost-effective devices. One of the significant challenges is introducing
Accepted 3 February 2023 polymers binders in supercapacitors electrodes to improve durable, malleable and eco-
Available online 8 February 2023 friendly devices. A comprehensive review of electrode preparation and physical and
electrochemical properties is crucial to understand how various types of binders contribute
Keywords: to the performance of supercapacitor electrodes. This review summarises the application
Supercapacitor and effect of polymer binders on their performance as supercapacitor electrodes. Polymer
Polymer binder binders have an essential role to play in improving supercapacitor electrodes. Notably,
Electrode materials binders act as a glue among the current collectors and active materials and can also in-
Electrochemical performance crease supercapacitors’ performance and flexibility.
Morphology © 2023 The Author(s). Published by Elsevier B.V. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

used as alternative power supplies for handy devices like

1. Introduction
Supercapacitors are an example of an alternative energy
storage technology that can offer high power densities, large
specific capacitance, quick charge, discharge times, prolonged
cycle life, and hygienic electrochemical energy storage [1e3].
Other than that, supercapacitors are unconventional energy
devices working on the principle of electrochemical energy
conversion. Supercapacitors are transparent, small, thin,
lightweight, and flexible and come in various forms. They are
laptops, smartphones, medical devices, video cameras, MP3
players and robotic vacuum cleaners [4e7].
A design supercapacitor is usually constructed with two
electrodes soaked in an electrolyte solution, and the separator
separates the electrode. For the electrical double-layer
capacitor (EDLC), capacitance accumulates pure electrostatic
charge at the electrode/electrolyte interface. It is important to
note that the capacitance value is greatly influenced by the
surface area of the electrode materials readily accessible to
the electrolyte ions [3,8]. In recent years, the performance of

* Corresponding author.
E-mail address: aam@usm.my (A.A. Mohamad).
https://doi.org/10.1016/j.jmrt.2023.02.013
2238-7854/© 2023 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1
Fig. 1 e Schematic representation for (a) supercapacitor components, (b) components in the electrode, and (c) classification of
binder material for supercapacitor application.
supercapacitors has improved significantly. Much research
has been conducted on developing active materials with su-
perior specific capacitance from carbonaceous and transition
metal oxides [9e11]. Among these materials, pre-dominantly
carbon-based materials behave as EDLC properties, whilst
metal oxides or hydroxides show pseudocapacitive proper-
ties. In the pseudocapacitive mechanism, the active materials
undergo a faradaic redox reaction. In parallel, new categories
of electrolytes, such as ionic liquids and organic electrolytes,
have been proposed to increase their operative voltage
[12e14].
Developing high-performance supercapacitors can be
made possible through these studies by providing valuable
insights into the materials and strategies utilised. Despite this,
relatively little work has been reviewed to assess inactive
components such as conductive materials and binders.
Though binder materials are likely less important than active
materials that affect the capacitance of supercapacitors, they
can provide flexibility and mechanical support. This is espe-
cially for hybrid supercapacitors that involve the faradaic
3471
redox reaction, which can cause volume change and physi-
cally damage the electrode's structure. The presence of binder
materials can suppress the volume change in active materials
during the faradaic redox reaction.
Pseudocapacitive materials can increase the super-
capacitors' capacitance performance. Nevertheless, the binder
properties may affect electrode stability and irreversible ca-
pacity losses [15,16]. Consequently, a binder has a crucial role
in electrode processing. An electrode-active material is held
together by a binder, a compound that is electrochemically
inert but has the strength to afford mechanical support.
Binders maintain mechanical integrity between the elec-
trode's active materials and current collectors [17]. Recently,
published papers emphasised the importance of choosing a
suitable binder to enhance the chargingedischarging proper-
ties of supercapacitors by making them more resistant to
volume changes [18e20]. By bridging these separate compo-
nents chemically or physically, the binder ensured the me-
chanical integrity of the electrode without negatively
impacting electronic or ionic conductivity. It is important for
3472 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1

Fig. 2 e SEM images of oxygen-functionalised few-layer graphene on Pt electrodes fabricated at various drying temperatures
(a) 100
C (b) 170
C (c) 190
C. [57], (d) CV plots for 0% CBE, 5% CBE and 5% PBE with 10 mV s¡1 of scan rate (¡0.2 to 0.8 V) (e)
calculated specific capacitances of 0% CBE, 5% CBE and 5% PBE at various scan rate from 5 to 100 mV s¡1 (f) obtained specific
capacitance from the chargeedischarge curves of the 5% CBE and the 5% PBE at 1000 cycles [39], and (g) schematic diagram
for MnO2 with various binder and electron transfers [39].
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1 3473

supercapacitor binder materials to have chemical inertness,
as well as protect the electrolyte or electrode from corrosion
while facilitating ion transport across the interface. In this
way, the active materials and current collector are kept me-
chanically intact.
Currently, several review articles reported materials for
components and design of supercapacitors. Most researchers
focus on active supercapacitor materials [21,22] and are
exceptionally well-informed about carbon-based and metal-
oxide materials [21,22]. However, there is a limited review
regarding binder materials for supercapacitor applications. Up
to now, only one review of graphene and composite polymers
has been available [23]. In this case, polymers like poly-
vinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE)
are integrated with graphene to act as binder material. Note
that most reviews on electrode materials do not cover binder
materials directly [24,25]. The different binders provide
distinct properties like flexibility, toxicity, chemical inertness,

Fig. 3 e SEM images of (a1-3) CuO@MnO2/CMC composite at different magnifications, (b) cyclic retention of CuO@MnO2/CMC
composite [64], SEM image of prepared composite activated carbon and natural cellulose binder (c1) 500£ magnification and
(c2) 10,000£ magnification, and specific capacitance (d1) and capacity retention (d2) EDLCs created from composite materials
with different activated carbon/natural cellulose mass ratios [67].
3474 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1
and solubility, significantly influencing supercapacitor elec-
trode performance. Nonetheless, some reviews focus on
binder materials in batteries [26e29]. As far as we know, no
single review has focused exclusively on polymer binders for
supercapacitors. As such, review articles on binder materials
for supercapacitor applications are hard to find. Herein, our
work expands upon previous research in this field and has not
been substantiated. Besides, understanding the properties of
polymer binder materials in supercapacitors will help readers
see how better electrodes can be produced.
The primary objective is to examine the recent progress in
polymer binders for supercapacitor applications. In addition,
the effect of preparation methods as well as the physical and
electrochemical properties of binder materials on super-
capacitors, are thoroughly analysed.
2. Components of supercapacitors
A supercapacitor is an electrochemical device that stores and
delivers high-voltage electricity quickly and without losing
power for several cycles. It contained two electrodes (positive
and negative) immersed in an electrolyte solution and with a
separator separating the electrodes (Fig. 1a) [3,30]. There are
three types of supercapacitors: EDLC, pseudocapacitors and
hybrid supercapacitors [3]. EDLC involves the non-faradaic
process where coulombic charges adsorb on the
electrodeeelectrolyte interface. Meanwhile, a pseudocapaci-
tor is different from EDLC. Its mechanism involves fast and
reversible redox reactions (intercalation and de-intercalation
of ions into the material's structure) at the electrode surface.
Finally, a hybrid supercapacitor is the involvement of EDLC
and pseudocapacitor mechanism.
To produce supercapacitors that perform well, it is crucial
that supercapacitor electrode materials have substantial
electrical conductivity, outstanding chemical stability, excel-
lent corrosion resistance, large specific surface area, and be
environmentally friendly [3,31]. The electrode system has four
main components, i.e., active materials, conducting mate-
rials, current collector, and binder (Fig. 1b). Activated carbon,
graphene, and carbon nanotube are carbon based-materials,
and transition metal oxides like MnO2 and NiO are utilised
as active materials [32]. These materials have good properties;
for example, smaller pores result in a higher specific capaci-
tance and increased energy density. However, smaller pores
increase equivalent series resistance (ESR), decreasing power
density. Hence, the electrochemical properties of the super-
capacitor were affected by specific surface area, pore size,
homogeneity or distribution of the pore and electrical con-
ductivity of active materials. Other than that, transition metal
oxide-based active materials commonly performed a faradaic
charge transfer compared to carbon-based materials, giving
better performance for supercapacitors [33]. Apart from that,
Nickel (Ni) foam is a common current collector in super-
capacitors. Note that every material in the electrode system
must have excellent characteristics for fabricating the right
electrode.
Three categories of electrolytes are implemented in
supercapacitors: aqueous electrolytes, organic electrolytes,
and ionic liquids [33]. Typically, KOH, NaOH and H2SO4 are
aqueous electrolytes with smaller ions, which can utilise more
surface area [3]. Meanwhile, acid and alkaline solutions have
higher conductivities and lower ESR. Aqueous electrolytes
theoretically decompose at approximately 1.23 V and
1.3e1.4 V in practice [31]. Organic electrolytes are applied to
address this problem. Various organic electrolytes have been
studied in supercapacitors, such as tetraethylammonium
tetrafluoroborate in acetonitrile, which has a relatively high
potential window around 2e2.5 V. Here, the sizeable organic
solvent molecules require a larger pore size in electrodes [34].
A moderate ion size and 4e4.5 V maximum operating voltage
are characteristics of ionic liquid electrolytes [35]. In choosing
between aqueous and organic electrolyte solutions and ionic
liquid solutions, trade-offs must be considered concerning the
working voltage range, specific capacitance, ESR, power den-
sity, corrosion properties, and toxicity.
By isolating the two electrodes, a separator prevents the
formation of ions with opposite charges from the coupling. In
this case, the separator should be a high-resistance insulator.
The thickness of the separator can determine the capacitance
value the device can achieve. Ideally, a separator should be
skinny, i.e., in the range of tens of microns [31,36]. Addition-
ally, separators must be porous, and their pores should be
appropriate for the ions freely diffuse across them, lowering
the ESR [37]. Finally, a good separator should be chemically
and mechanically inert so that the electrolyte remains stable
and conductible. In research devices, nonwoven poly-
propylene (PP) membranes with a 40e60% porosity are
employed.
Fabricating high-performance electrodes requires a strong
binding agent. A binder provides adhesion among active ma-
terials and conductive additives by encasing them in an ad-
hesive laminate. Hence, materials used as binder materials
have one or more polymers as components that are electri-
cally non-conductive but can provide mechanical support to
active electrodes [38]. In composite electrodes, binders main-
tain mechanical integrity among the current collector and
active materials.
In chargeedischarge cycles, binders must resist dimen-
sional changes [15]. Furthermore, supercapacitor adhesives
need to be chemically and electrochemically stable and
maintain the low energy density of supercapacitors [19]. In
order to make the slurry efficiently, electrode active materials
and conducting additions must be prepared in a solvent, and
the slurry must have good solubility and homogeneity at room
temperature [18]. Therefore, binders are crucial in electrode
processing.
Binders can be classified as conventional, bio-polymer and
conducting polymer (Fig. 1c). A conventional binder uses
either PVDF [39] or PVA [40]. However, due to the environ-
mental issues of the toxicity effect of the N-Methyl-2-
pyrrolidone (NMP) solution (solvent), a conventional binder
is not recommended. Thus, a bio-polymer-based binder con-
sisting of cellulose-based materials [41], chitosan [17] and
lignin [42] are proposed. Thus, this conducting polymer can
also act as binder material since it can hold other materials
together and exhibits good bonding properties with the cur-
rent collector.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1
3. Conventional binder (PTFE, PVDF and
nafion binder)
Electrodes for supercapacitors are made by mixing active
materials, conductive fillers and binding agents into a homo-
geneous slurry. Subsequently, the current collector is coated
with it. A binder was utilised to bind the active material and
conductive agent to prevent the active electrode from falling
during testing [15,19]. Various binders have been used to
prepare supercapacitor electrode materials, such as PTFE,
Nafion, and PVDF. The best supercapacitor binder material
has traditionally been PTFE due to its insulating properties
and hydrophobicity towards the electrolyte. Due to these
features, the active material has a higher internal resistance
and is less effective [43]. There is a growing demand for eco-
friendly, fluorine-free alternatives to commonly-used fluori-
nated thermoplastic binders like PTFE [44].
Other than that, the Nafion binder has also been developed
as a polymeric binder for supercapacitor electrodes, in addi-
tion to PTFE. Because of its hydrophobicity, the tendency to
improve oxygen solubility, and proton and conducting char-
acteristics, Nafion is frequently applied in supercapacitors
[16,45,46]. The electrode surface absorbs liquid electrolytes to
produce ionic conductivity in the electrodes with Nafion
binders. Its charge and discharge are facilitated by the ionic
transport from the electrolyte to the electrode active mate-
rials. On the other hand, the limited Nafion binder can influ-
ence the supercapacitor electrode's mechanical strength,
proton conductivity, electrochemical stability, and loss of
humidity when the temperature falls or rises above 100
C
[47,48]. As a result, the typical binder, such as PVDF, has been
frequently used in supercapacitors electrodes.
Conventional binders such as PVDF are robust, stable flu-
oropolymers having distinct engineering advantages. PVDF is
one type of semi-crystalline thermoplastic utilised in appli-
cations requiring the highest purity and can withstand harsh
chemicals. Besides that, PVDF has excellent properties such as
good thermal stability, resistance to radiation, and high
dielectric constants [49,50]. Although PVDF has typical fluo-
ropolymer stability, it exhibits polarity differences because of
interactive groups. As a result, this polymer is chemically and
oxidatively resistant but rather hydrophilic and swells
significantly in organic electrolytes [16]. Note that PVDF ma-
terial is one of the popular binders found in supercapacitor
electrode systems. It binds active materials (nanoplates or
nanopowders) to current collectors and provides mechanical
strength and electrode stability. For instance, PVDF is prone to
swell and dissolve in the organic electrolyte at high temper-
ature, leading to a collapse of conductive network and high
interface resistance. Hence, it will affect the electrochemical
performance of the supercapacitor electrode.
Generally, the weight percentage of PVDF binder used in an
electrode system is about 5e10 wt% [39,50,51]. To achieve a
favourable mixing execution, PVDF is normally dissolved in a
solvent and then mixed with active materials into a paste-like
composite. By incorporating organic solvents like NMP, the
viscosity of the slurry can be adjusted. Apart from that, a
supercapacitor electrode is created by coating a composite
slurry on the current collector, drying it, and squeezing it.
3475
Subsequently, various coating techniques can be applied,
such as bar coating, doctor blade coating, drop cast and dip
coating [3,52]. Although there are many methods to fabricate
the supercapacitor electrode using the PVDF binder, the
amount of the PVDF must be optimised.
Controlling the amount of PVDF in the mixture of active
materials is crucial. Insufficient PVDF can result in weak
binding between the active material and the current collector.
In contrast, excessive use of PVDF will lower the electrical
conductivity of the electrode and the power and energy den-
sity of the supercapacitor. Thus, adding conductive fillers such
as acetylene black, carbon nanotube, graphene and carbon
black significantly enhances the conductivity of PVDF [39,51].
Besides mixing and coating, vacuum filtration also pro-
vides an alternative method for creating an electrode for
supercapacitors using active materials or polymers on porous
current collectors such as Ni foam [53]. However, the process's
vacuum pressure, temperature, and duration can affect the
content of active materials.
The access site for the electrolyte to the active materials is
an important issue that needs to be considered. Thus, the
exploration of the accessibility of electrolytes to active mate-
rials is one of the crucial studies that have been reported by
numerous scientists [54e56]. A study was performed to
examine the surface morphology utilising scanning electron
microscope (SEM) images of electrodes dried at distinct tem-
peratures (100, 170 and 190
C) in contrast to other electrodes
(Fig. 2a-c). Agglomeration of the graphene layer was observed
at 100
C, which could interfere with the accessibility of the
electrolyte (Fig. 2a). A great stacking of graphene sheets was
produced when the electrode was dried at 170
C (Fig. 2b).
Moreover, the accelerated evaporation of the solvent occurred
at 190
C and caused the agglomeration of the electrode ma-
terials (Fig. 2c) [57]. It is noted that NMP has a boiling point of
202
C. According to these results, electrodes that dry near the
boiling point of the NMP solution can be harmful and
damaged.
The calendaring method can reduce the agglomeration of
the binder and active material [58,59]. As a result of such a
method, an electrode structure with a smoother surface and a
more compact structure is created, which reduces macropore
gaps and increases conductivity. Besides calendaring,
compaction of electrodes is also shown to reduce agglomer-
ation between PVDF binder and active materials [15]. How-
ever, in carbon electrodes, a PVDF binder causes pore blockage
[59], in which supercapacitors can be severely affected by this
phenomenon due to reduced electrode surface area.
As a method for characterising the capacitive properties of
any active material, cyclic voltammetry (CV) is considered
suitable for supercapacitor testing [50]. When 5 wt.% PVDF,
PTFE, and Nafion binder are utilised in an activated carbon
electrode, the PVDF binder is observed to have the highest
specific capacitance (160.6 F g1) [16]. This is because a higher
specific capacitance results from PVDF interacted with the
active materials. For example, maximum specific capacitance
(203 F g1) can be obtained for a 5% composite binder electrode
(CBE) compared to 0% CBE (183 F g1) and 5% PVDF binder
electrode (192 F g1) (Fig. 2d and e) [39]. Note that too much
binder reduces the surface area of active materials as well as
the ability of the former to store charges by adsorbing or
3476 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1

desorbing electrolyte ions at the electrolyte/electrode inter-
face, causing a lower specific capacitance [15].
An electrode fabricated from PVDF is thermally and elec-
trochemically stable, resulting in excellent adhesion between
the electrode film and collector [52,57]. Thus, achieving good
adhesion properties that can increase the life span and energy
density of the supercapacitor's electrode. Due to the chemical
resistance of PVDF, longevity in such harsh conditions is
guaranteed [15]. The cycling performance of the binder is
another important aspect of its suitability for electrode use.
For example, the charge/discharge cycling was tested at
1 A g1 for the 5% CBE and the 5% PBE (Fig. 2f). The results
presented both electrodes retained between 90.07% and 83.3%
of their maximum capacitance after 1000 cycles. Due to the
interaction between PVDF and active materials, the electrode
has excellent cycle stability. Such an outcome can be proved
by the mechanism of the MnO2 employing different binders
and electron transfers (Fig. 2g) [39].
The electrical conductivity of the composite electrode with
polymer binder can be improved by adding conductive fillers
like activated carbon, acetylene black, graphene, and carbon
nanotube [60]. The binder provides benefits through the
secure network and contact area among the current collector
and active materials of the electrode. Alternatively, estab-
lishing an electrical connection quickens the electron trans-
fers to the active material electrodes. This can improve the
system's electrical conductivity, rate capability and cycle sta-
bility for a longer time [39,49]. A binder with conductive filler
can increases its conductivity. However, too much conductive
filler can decrease electrode properties, such as the surface
area. Consequently, the CBE must contain enough conductive
filler to increase the performance of the supercapacitor.

Fig. 4 e (a1-a4) Digital images of polypyrrole@cobalt oxyhydroxide/cellulose fibre (PCC-11) electrode curved into various
states, (b) CV plots of PCC-11 electrode under distinct bending angles and (supplementary [71]). (c) specific capacitance plots
vs. scan rate of rGO with various binders in 2 M KOH electrolyte [56].
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1
4. Cellulose-based binders
Linear polysaccharide cellulose contained numerous D-
glucose units linked through b (1e4) glycosidic bonds [61].
Cellulose is a microfibril structure built of parallel chains and
latticework sheets that can be stacked to form three-
dimensional (3D) polypro crystal structures that can range in
diameter and length. Besides its abundance, natural cellulose
also boosts mechanical robustness, hydrophilic, biocompat-
ible, biodegradable, and affordable price. This cellulose is a
natural resource derived from biological materials such as
jute, wood, corn, flasks, hemp and cotton. Many products in
the market use cellulose as a binder, for instance, in cos-
metics, fibre, clothes, foods and pharmaceuticals. In addition,
cellulose's excellent mechanical properties and sustainability
have sparked an interest in the electronic industry, covering
the printed electronics sector. Two types of cellulose are uti-
lised as a binder: natural and derivative (carboxymethyl cel-
lulose and ethyl cellulose).
Preparing cellulose as a slurry is the first step in making
cellulose as a binder for supercapacitors. First, cellulose types
need to be dissolved in a solvent (water or ionic liquid); for
example, CMC is dissolved in water. Consequently, the stir-
ring process (1 h, room temperature) is followed by the addi-
tion of active material and conducting material. Subsequently,
the mixture is blended for 1 h to achieve homogeneity using a
magnetic stirrer. Finally, after coating on the current collector,
the mixture is dried overnight at 80
C [49,62,63].
A cellulose derivative known as CMC is a water-soluble
polymer in which carboxymethyl groups bond part of the
hydroxyl groups of cellulose. Due to its sustainability and ease
of processing in water, CMC has drawn much attention as a
supercapacitor binder substitute for the recently utilised
PVDF. Note that CMC is a biodegradable polymer. Therefore,
once the supercapacitor's useful life is up, the electrode may
be taken out. The residual electrode active material, which
contains CMC, can be more safely buried in the soil. CMC of-
fers high water solubility, biocompatibility, nontoxicity, and
superior chemical stability for various material applications.
Furthermore, the materials are exceptional for developing
conductive networks due to the CMC's strong coordination
behaviour with metal oxides. The morphological characteristics
were employed to explore the crucial function of CMC for the
supercapacitor qualities when CMC was employed as a com-
posite material and directly acted as a binder in CuO@MnO2 in
the supercapacitor electrode (Fig. 3a1-a3). The CuO@MnO2/CMC
nanocomposite was shown to have many nanoplates and a
porous structure, as well as MnO2 nanorods, ornamented on the
CuO plates [64]. The MnO2 nanorods were created to cross one
another to provide a significant surface area that might increase
the contact area between the electrode and electrolyte. Subse-
quently, the specific capacitance of the active materials can be
increased [65,66]. The cyclic retention test for the CuO@MnO2/
CMC nanocomposite was performed for 5000 galvanostatic
chargeedischarge (GCD) cycles at 0.5e4 A g1 to demonstrate
the improvement in specific capacitance. The results indicated
that the cyclic retention is 96.2, demonstrating that the com-
posite electrodes were well-suitable for supercapacitors due to
their pseudocapacitance properties.
3477
The conductivity of CMC is 162 S m1 due to its cellulose-
based composition [4]. Moreover, graphene and CMC binder
interact excellently, which allows for high electrical conduc-
tivity of CMC binders. According to CV analysis, binders cause
slightly different responses, currents, and capacitances [4].
Using SBR/CMC in active material such as reduced graphene
oxide (rGO), the specific capacitance can be measured at
10 mV s1 (95 F g1), and capacitance retention increases as
scan rates increase (Fig. 3b) [56]. Other than that, the elec-
trodes fabricated using the hydrophilic CMC/SBR binder
exhibit advanced wetting properties on the surface compared
to those made using other binders in aqueous electrolytes. It
leads to enhanced capacitive behaviour. Notably, active ma-
terials slightly lose conductivity when an insulating binder is
added. However, the absence of enough binder can result in
poor adhesion, which makes it difficult to form an electrode
that can stand on its own [56,68]. The excess of a binder can
increase the internal resistance of an electrode and clog the
accessible pores for ionic transport. Other than that, it can
also reduce the electrochemical performance of that elec-
trode. When making a large-scale film, it is essential to select
excellent binders to reduce electrical insulating properties.
Moreover, as CMC is water soluble, using aqueous slurries
to fabricate the electrode is made possible by this binder,
increasing the overall safety of the EDLC manufacturing pro-
cess. Recent research has shown that the capacitance and
cycle stability of electrodes based on CMC is equivalent to
those based on traditional and fluorinated binders, as well as
various electrolytes. These electrodes, however, cannot be
used with aqueous electrolytes due to the solubility of CMC in
water. Hence, the supercapacitor electrode uses a natural
cellulose binder to address this issue.
Natural cellulose is derived from organic resources (such as
jute, wood, hemp, corn and cotton) and has a low cost of
manufacture. In light of these qualities, using natural cellu-
lose as a binder of supercapacitor electrodes would signifi-
cantly contribute to the development of affordable and
ecologically friendly technology. Nevertheless, natural cellu-
lose is not soluble in practically all organic solvents. This in-
cludes water and some ionic liquids, such as 1-ethyl-3-
methylimidazolium acetate (EMIM Ac), which can dissolve
the natural cellulose. Thus, natural cellulose can be used as a
binder material in supercapacitor electrodes.
Recent research has demonstrated that compound elec-
trodes with natural cellulose as a binder exhibit homogeneous
shapes and have good thermal stabilities that are on par with
traditional electrodes. Other researchers concur that elec-
trodes made of natural cellulose exhibit excellent long-range
uniformity [49,67]. A deeper examination reveals that, in
certain instances, the allocation of the nano-sized activated
carbon appears to be enhanced by applying the natural cel-
lulose binder (Fig. 3c1-2), leading to a better connection
network among the comparatively big activated carbon
[67,69].
The amount of binder used in an electrode is only about
5e10 wt.% [49,70]. So, in the electrode system, the optimum
amount of binder can optimising the electrochemical perfor-
mance, adhesion strength, and mechanical flexibility of the
electrodes [18]. The excess of a binder can increase an elec-
trode's internal resistance and clog the accessible area for
3478 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1

ionic transport, reducing the electrochemical properties of
that electrode. When making a large-scale thin film, it is
essential to pick out the most favourable binders to increase
their electrical insulating properties.
Other than that, CV was implemented to evaluate the
prepared electrode's electrochemical performance. The ratios
between active materials and natural cellulose binder will
produce different results in specific capacitance and capacity
retention (Fig. 3d1-2) [67]. It was demonstrated by the mea-
surement of the specific capacitance of various activated
carbon/natural cellulose mass ratios that a higher percentage
of activated carbon improves capacity retention and the value
of specific capacitance. Nevertheless, it was shown that there
is an optimum concentration value after which a further in-
crease of the active material concentration does not impact
the further improvement of the electrochemical characteris-
tics of the composite material [67]. It presented that the binder
and active materials' composition needs to be optimised to get
the maximum results of the specific capacitance. The mass
ratio between active material and binder will affect the

Fig. 5 e (a) Structure of chitosan: SEM images of (b) chitosan powder (c) prepared graphite electrode with chitosan binder [80].
(d) chitosan hydrogels. [81], (e) the changes of resistance of graphene@cotton-10 during bending [77], (f) the CV curves of
graphene@cotton-10 with chitosan binder at 50 mV s¡1, (g) durability of the graphene@ cotton with chitosan binder at
5 mA cm¡2. [77], and (h) schematic diagram of charge storage mechanism in CNF-Chitosan/Co nanocomposite [79].
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1
electrode's surface area and porosity. Therefore, the optimal
ratio of the active material and binder will give a larger specific
surface area and further the reaction sites between electrode
and electrolyte ions [12].
Several experiments are proposed to learn more about the
composite electrode made of cellulose (Fig. 4a). The composite
of polypyrrole @ cobalt oxyhydroxide/cellulose fibre compos-
ite displayed it could be folded into various shapes [71].
Furthermore, the cellulose fibres appear very soft and flexible
[72]. This includes carbon-chopped fibres (CCFs) in the cellu-
lose fibre-based paper resulting in superior mechanical
properties, such as 42 MPa tensile strength at 5.7% strain for
the rGO/PPY CCFs paper. Note that active electrode materials
can transfer electrons through the interpenetrating con-
ducting networks of CCFs [73].
The composite electrode's CV plots were almost unaffected
after bending into different angles, revealing excellent flexi-
bility. For cyclic stability, the GCD test was performed. The
cellulose electrode as a binder demonstrated a capacitance of
93% after 1000 to 80% after 5000 cycles (Fig. 4b) [68,71].
During the fabrication of supercapacitor electrodes, a
cellulose-based binder has several advantages since it has
great binding properties. However, owing to its high resis-
tance, it must be mixed with another conductive filler to
improve the supercapacitor performance. The carboxylate
groups in cellulose make it more hydrophilic, which boosts
component conductivity and improves electrolyte wettability.
Due to its elastic properties, which reduce volume change,
composite cellulose (rGO-CMC/SBR) has long cycling stability
during charge/discharge cycles (Fig. 4c) [56]. In order to meet
the demands of high-performance electrodes for energy
storage devices, novel binder formulations must have
extraordinary adhesion strength, structural flexibility, and
electrical conductivity.
5. Chitosan binder
As a natural polymer, chitosan is known to have a high degree
of N-deacetylated form of chitin. Linear polysaccharides like
chitosan are mainly made up of inconstantly dispersed b-
(1e4)-linked D-glucosamine (deacetylated unit) and N-acetyl-
D-glucosamine (acetylated unit). This chitosan was created by
deacetylating chitin from the exoskeleton of shrimp, insects,
crabs, fungi and lobster (Fig. 5a). Note that chitosan is the most
common polymer alternative after cellulose [17,74,75]. The
mild alkalinity of chitosan makes it soluble in weak acids such
as acetic acid or lactic acid. It is soluble when chitosan's
glucosamine unit (ReNH2) is converted into its protonated
form (ReNHþ 3 ). The protonation of chitosan in acetic acid
promotes ionic conductivity due to protons in the acetic acid
solution [20,76]. Thus, chitosan is suitable for the electrode
system as a binder. Due to its high retention capacity, envi-
ronmentally friendly, great ionic conductivity, and efficient
adsorption of ions onto its matrix, chitosan offers many
benefits to the supercapacitor, displaying superior electro-
chemical performance [77e79].
The use of chitosan as a supercapacitor binder is limited
due to its lack of electrical and mechanical performance. The
tensile strength of pure chitosan is 6.99 ± 0.95 MPa.
3479
Meanwhile, the tensile strength of a composite film of chito-
san/graphene is 15.32 ± 2.47 MPa [76]. The tensile strength of
chitosan is quite significant. Hence, it can be utilised as a
binder in electrode systems. As an electrode binder in a
lithium-ion battery and fuel cell, chitosan indicates excellent
properties [80,82]. Compared to polyvinyl alcohol, chitosan
has better water retention capability as it is far more hydro-
philic. Due to its exceptional achievement in fuel cells, chi-
tosan has been applied as an electrode binder material in a
supercapacitor [17,74,77].
Chitosan powder has a smooth surface and well-defined
compact grain (Fig. 5b). To create a functional and uniform
binder without agglomeration, a chitosan binder was pre-
pared by dissolving it in acetic acid (1, 2, 4 and 10%), followed
by mixing it with the active material and conductive material
to form a slurry solution [75,79,83,84]. Consequently, the
dissolution of the chitosan powder in the acetic acid produced
ionic conductivity that transported the ions [76]. Due to ionic
conductivity, there is no problem if the chitosan slurry covers
the surface of the active materials. The chitosan binder could
bind the active material uniformly with a smooth surface
without agglomeration [80]. Furthermore, these features help
the active and conductive materials bind properly. Having no
agglomeration or aggregation of the binder in the electrode
can increase specific capacitance by reducing the blocking on
the surface of the electrode's active materials. For example, in
the graphite electrode, the chitosan binder is attached to the
graphite uniformly and smoothly (Fig. 5c) [80].
The distribution and homogeneity of the composite are
important to increase the electrochemical performance to
form a composite electrode (active materials and binder). Note
that cross-linking reactions create a loose 3D network struc-
ture in chitosan hydrogels. In the presence of graphene oxide,
among the functioning groups of a cross-linking factor and
the two oxygen-containing groups of graphene oxide and
amino groups of chitosan, a 3D covalent-bonding network was
created [81]. The 3D morphology of chitosan reveals larger
surfaceearea properties like huge porosity and functional
groups via hydroxyl groups, which commit to the approach
and attachment of graphene [85]. Moreover, the SEM image
clearly presents that the graphene oxide-chitosan hydrogels
have a flexible microporous structure varying from 100 to
50 mm (Fig. 5d). This microporous structure helps to maintain
mechanical stability [86].
The flexibility of the electrode is the key requirement for
wearable supercapacitors [1]. It is seen that electrodes are
prone to malfunction [87]. Hence, an investigation regarding
the resistance of different binding states of a
graphene@cotton-10 electrode has been studied (Fig. 5e) [77].
When the bending angle increased to 40
, resistance hardly
changed. However, as resistance increased gradually, it
reached 2.26 U at the bending angle of 180
[19].
Chitosan was mixed with other conducting polymers to
build up its electrical and mechanical properties for a binder
electrode. Due to its high ability to generate hydrogen bonds
with amino and hydroxyl groups, chitosan helps the elec-
trode materials to exhibit greater hydrophilicity and con-
ductivity [79]. Here, 1% aqueous acetic acid solution revealed
huge porosity (2e7 mm diameter pores), good thermal (up to
250
C), chemical (in 1 M H2SO4), electrochemical (up to
3480 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1

Fig. 6 e (a) Chemical structure of lignin [28], (b) preparation process of PANi/lignin composite by oxidation polymerisation
[88], and (c) N2 adsorption/desorption measurement of PPL-Zn at different percentages [91].
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1
1.21 V) and mechanical stability (up to 39 MPa under tensile
loading).
The working electrode was early tested in a three-electrode
system to gauge the capacitive capabilities of the chitosan
binder. Thus, the CV curves of graphene/chitosan cloth elec-
trodes were analysed at different dipping times (Fig. 5f). The
quasi-rectangular CV curves on the graphene/chitosan cloth
electrode show a normal double-layer capacitance. It is due to
graphene electrostatic ion adsorption and desorption. At long
cycling cycles, the stability of the chitosan binder was tested
(Fig. 5g). Apart from that, the chitosan binder in the graphene
electrode demonstrated good electrochemical durability,
which after 5000 cycles (5 mA cm2), the capacity retention is
94.2% [77].
The performance of the supercapacitor when the chitosan
binder is blended with another polymer, activated carbon
reaches 135.2 F g1 (at 1 A g1) [78]. Chitosan is also utilised
with carbon nanofibre (CNF) mixed with mild oxidation using
acetic acid to form the CNF-chitosan matrix. Besides that,
adding cobalt into this matrix boosted the electrical properties
of the electrode [79]. According to its electrochemical char-
acterisation, the composite's ability to store charge was
improved. After the oxidation, the CNF surface became more
hydrophilic and wettable. Additionally, the chitosan com-
posite creation improved the conductivity and stability of the
chitosan in the composite.
The storage mechanism of the active material, CNF,
conductive filler (Co), and chitosan binder nanocomposite
(Fig. 5h) enhanced the electrochemical performance of the
electrode. The storage capacity of the active material signifi-
cantly increased when chitosan was combined with the active
material [78,79]. The oxidation process significantly improved
the hydrophilic nature of the active material. The active ma-
terial formed a composite with chitosan nanoparticles via
HeH bonding using functional groups on both molecules [75].
Each electrochemical surface was fully utilised by incorpo-
rating chitosan into the active material matrix of charge
storage. A consequence of the adsorption properties of the
active material, chitosan, is that the Co is deposited homo-
geneously on the matrix, resulting in less agglomeration of the
filler. A significant improvement in the mechanical, electrical,
and fast ion transport properties has been achieved during
this process [79].
It has been demonstrated that chitosan can be employed as
an electrode binder without impairing supercapacitor perfor-
mance. Chitosan can bind active materials uniformly and
without agglomeration. Furthermore, chitosan is environ-
mentally benign because no toxic solvent is needed. Chitosan
binder/graphene electrodes demonstrated exceptional elec-
trochemical durability and excellent capacitance retention.
6. Lignin-based binder
Lignin is a complex aromatic heteropolymer, which includes
sinapyl alcohol (S), coniferyl alcohol (G) and p-Coumaryl
alcohol (H). Note that all three are distinct in the number of
methoxy groups hooked to the phenol ring in the ortho posi-
tion (Fig. 6a) [28,88,89]. The application of lignin as a binder in
a supercapacitor electrode is very limited. Despite its lack of
3481
direct use as a binder, lignin has been applied as a derivative
for generating active materials such as carbon or composite
electrodes [89,90]. For example, carbon fibre mats are utilised
as active components in supercapacitors and are produced
from pure eucalyptus kraft lignin. Fibres are believed to form
through hydrogen bonding and stacking between individual
lignin macromolecules in response to low molecular weight
lignin molecules. It leads to the formation of association
complexes in an electrospinning solution [88]. As a result,
lignin provides a structure for the electrodes of super-
capacitors while simultaneously forming a bond between the
active materials [88]. A composite of PANi/lignin containing a
fibrous network of interpenetrating bands has been prepared
by oxidising aniline with reticulated lignin and then poly-
merising it (Fig. 6b).
Transition metal oxide has a high capacitance via redox
reactions. Nevertheless, the oxide has some problems, such as
lower electrical conductivity, low-rate performance, poor
cycle stability, and higher price. This can narrow their appli-
cation for high-performance supercapacitors [92]. Therefore,
an effective technique to enhance the conductive matrix is
adding transition metal oxides with nanostructure charac-
teristics. For this purpose, lignin-based carbon material, for
instance, can provide a good conductive matrix that is not
expansive [93,94]. It was proved that the substitutions of lignin
on PANi were observed to enhance conductivity to 3.22 S cm1
compared with PANi alone, which is 1.43 S cm1 [88].
By one-step electrospinning using PANi, pitch, lignin and
zinc acetate solution, the PANi/Pitch/lignin-Zn (PPL-Zn) com-
posites were produced. According to the findings, the PPL-Zn
(5) electrode has a high porosity and many functional
groups. Other than that, PPL-Zn (5) exhibits excellent capaci-
tive behaviour, including high capacitance, increased energy
and power efficiency, constant improvement in capacity
retention, and improved cycling performance. It is a result of
the benefits of double-layer capacitance and pseudocapaci-
tance. Furthermore, lignin considerably increased the specific
surface area of the composite nanofibres, demonstrating that
lignin generates porosity on the surface of the fibres by py-
rolysis (Fig. 6b) [91,95,96].
Reducing the number of functional groups (carboxylic,
carbonyl, ketones, hydroxyl) in the simple heat process of
oxygen-rich lignin can create porosity on the fibre surface.
Lignin is a perfect precursor for CNF composites because of its
high carbon content, aromatic components, and low glass
transition temperature [91], as another material was added to
the CNF, making the process easier. In this instance, the cost
of the CNFs is decreased, their carbon yield is increased, and
their electrical conductivity is improved using pitch as a pre-
cursor with lignin. Apart from that, these discoveries
improved the potential for turning biomass into high-
performance carbon compounds for energy storage applica-
tions. It is capable of fast rates, high energy/power efficiency,
and high capacitance.
7. Conducting polymer-based binders
Commonly used binders, i.e., CMC-SBR, chitosan, and lignin,
are intrinsically insulators. Excessive use of these binders
3482 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1

Fig. 7 e (a) Schematic diagram of the composite formation of PEDOT-PSS:EG/rGO composite formation with secondary
doping. [110], SEM images of composites (b) PEDOT-PSS:EG/rGO [110], (c) PEDOT-TiO2 [111], (d) CV curve of
graphene þ PEDOT:PSS [109] (e) the cycling performance of PEDOT-TiO2 at the current density of 0.5 A g¡1 [111].
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1 3483

Fig. 8 e SEM images of (a) mesoporous MnO2, and (b) PANI/mesoporous MnO2 [99], CV curves of (c) PANi/MnO2 and MnO2
[99], (d) TiO2, MneTiO2, PANi/MneTiO2 and Pure PANi at 5 mV s¡1, and (e) specific capacitance of TiO2, MneTiO2 and PANi/
MneTiO2 at different current densities [116].
3484 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1
adversely affects the electrode's conductivity and the perfor-
mance of devices. The introduction of conducting polymers as
binders can solve this issue. Recently, PEDOT [97,98] and PANi
[99,100] are two conducting polymers utilised as binders in
supercapacitor applications. PEDOT and PANi have many ad-
vantages as binders, such as flexibility, high electrical con-
ductivity, thermal stability, good pseudocapacitance and low
cost [101e103]. These conducting polymers (PEDOT and PANi)
can act as active materials in supercapacitors and, at the same
time, can also function as an electrode binder.
The great conductivity, electroactivity, specific capaci-
tance, and stability of PANi make it an ideal electrode material
for supercapacitors [104e106]. In addition, PANi is a binding
agent and active material to create a composite electrode
when used in hybrid supercapacitors. Therefore, it is essential
to charge and discharge PANi properly before applying it in
supercapacitor applications. To dissolve the PANi, a protic
solvent, an acidic solution or a protic ionic liquid is required
[107].
The common method used to fabricate this electrode is
vapour phase polymerisation, oxidative chemical vapour
deposition, and polymerisation via spin coating/annealing
[55,108]. However, the most efficient way to make a PEDOT
hybrid supercapacitor is via flow-directed self-assembly
[97,109]. Other than that, polymeric binders simulate the
PEDOT structure for casting electrodes in aqueous slurries and
improve binding efficiency while relying on lower-cost binder
production methods.
For example, the low-cost preparation of composite
PEDOT-PSS was achieved by the mixing or secondary doping
process with other materials (Fig. 7a). Moreover, PEDOT-PSS
has unique characteristics, which can act as active materials
and function as a binding agent to bind the conductive filler
simultaneously. In the PEDOT-PSS matrix, rGO particles had a
homogeneous distribution (average particle size) according to
SEM images (Fig. 7b). A PEDOT-PSS:EG coating completely
covers rGO nanoparticles. In order to minimise electro-
chemical reactions, ethylene glycol (EG) is employed to pre-
vent restacking of rGO [110]. Note that vapour-phase
polymerisation is also used to fabricate composite PEDOT
[111,112]. As a result, a significant amount of this material
grew on top of the active material (TiO2) rather than blending
with it (Fig. 7c) [111]. This close combination benefited the
capacitive behaviour. The formation of interconnected net-
works and macropores improved nanocomposites’ electrical
conductivity and electrochemical performance [110,111].
Other than that, PANi is most often synthesised via oxidative
polymerisation or electrochemical polymerisation
[100,113,114].
It is observed that the electrochemical properties of the
composite with PEDOT: PSS have increased. The area of CV
plots of the graphene with PEDOT:PSS was improved due to
the conductivity of PEDOT compared to the pristine graphene
alone (Fig. 7d) [109]. Apart from that, most of the research
involves PVA and PVDF. It insulates properties that make
them ideal for electrode binders. Adding additional con-
ducting materials like carbon black and graphene to this
polymer increases its conductivity. Additionally, PEDOT: PSS
enhances the supercapacitor's performance and acts as a
binder.
Conductive polymers are typically applied as efficient
supercapacitor electrodes because of their long-term stability.
However, composite TiO2 fibres fabricated by polymerisation
of PEDOT (50
C) have the best specific capacitance and best
cycling performance (0.5 A g1) [111]. The capacitance reten-
tion after 1000 cycles was 90.2%, demonstrating good cycling
stability (Fig. 7e). Furthermore, the specific capacitance
retention of PEDOT electrodes was almost comparable to that
of other PEDOT electrodes, viz ~86, 85, 83 and 80%
[36,97,101,112]. Therefore, this work demonstrates that PEDOT
is an inexpensive material with good electrochemical prop-
erties, excellent cycling stability, and excellent for
supercapacitors.
Recently, a mixture of PANi and other metal oxides was
utilised to prepare composite electrodes for supercapacitors in
an acidic solution, hydrochloric acid (HCl) [99,115]. The com-
posites of PANi and MnO2 still maintain similar graininess,
despite some particles agglomerating together (Fig. 8a and b).
By synthesising PANi on the surface of MnO2, MnO2 can easily
be wrapped within PANi, and a chemical reaction occurs. Due
to the transfer of electrons, PANi and MnO2 have a better
specific capacity [99].
The good contact of PANi and other metal oxides has
resulted in excellent electrochemical performances. The CV
curves showed the comparison between MnO2 and PANI/
MnO2. The analysis displayed that this composite involves
more current area than MnO2 (Fig. 8c), contributed by the good
contact of the inter-molecule between PANi and MnO [117].
This result is attributable to the matrix of nanocomposite
polymer being distributed with good homogeneity. Addition-
ally, it provides a simple way of transferring electrons and
charges between the [118]. In addition to providing a greater
surface area for the dispersion of MnO2, PANi also provides a
larger surface area for redox processing due to its larger active
surface area. As a result, the MnO2 interlinks the polymer
chains to maximise the redox cycling efficiency and stability
of PANi [119]. The PANi/MneTiO2 composite showed
increased CV areas with TiO2 electrodes to MneTiO2 and
PANi/MneTiO2, causing an increase in specific capacitance
(Fig. 8d). Note that PANi/MneTiO2 presented a much smaller
anodic and cathodic peak separation. PANi/MneTiO2 has a
high capacity attributed to faster kinetic reversibility [116].
Hence, as the CV area increased, the specific capacitance
increased from TiO2, MneTiO2 to PANi/MneTiO2 (Fig. 8e).
The specific capacitance of the as-prepared electrode was
635.87 F g1 (1 A g1), which is bigger than PANi (135.55 F g1),
MneTiO2 (326.69 F g1), and TiO2 (162.22 F g1), at the same
current density [116]. Due to the well-developed cooperation
among the electrode's active materials, the capacity was
improved. The smaller band gap of the final composite caused
the best capacitance of all three electrode materials. Here, an
excellent supercapacitor's performance is facilitated by a low
band gap energy and faster charge transport [99,117]. Thus,
the composite possesses high specific capacitance, as the
polymer used in the composite acts as a binder and prevents
the dissolution of metal oxide (TiO2) in the electrolyte.
Table 1 e Summary of different binder in Supercapacitor.
Properties
Materials
Polyvinyllidene difluoride (PVDF) - A semi-crystalline thermoplastic
- Good electrochemical stability
- Good binding capability
Setup/experimental
- Conventional binder in supercapacitor
- 5e20 wt% used in the electrode system
depend on the active materials
- N-Methyl-2-pyrrolidone (NMP) as a
solvent to form a slurry
Highlight Ref.
- Low content of PVDF- low adhesion 12,37,42,43,52
- Higher content of PVDF- reduce the
conductivity, power density, and energy
density of supercapacitor
- 5% (160.6 F g1) and 10% (142.9 F g1) in
activated carbon electrode.

j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1
- Excellent resistance to creep and fatigue - Coating technique - doctor blade - Excellent long-term cycle stability (90.07
coating, bar coating, dip coating and e83.3% capacity retention) in the
drop cast graphene-MnO2- PVDF electrode
- Good thermal stability - Suitable for aqueous, organic and solid-
state electrolyte
- High dielectric constant - Drying temperature at 60e70
C for
- Volatile overnight
- Flammable
- Need organic solvent (NMP)
- Sensitive to humidity
Cellulose - Biodegradable - 5 to 10 wt% as a binder in - Uniform coating on the current collector 4,15,41,49,55,56,
supercapacitor electrode 60,63,64,113
- Biocompatibility - Water as a solvent to form a slurry - Spread out and adhere over their edges
and plane over active material and
conductive material
- Hydrophilicity - Drying process at 80
C overnight - Excessive cellulose binder can increase
internal resistance and block the open
pores for ionic transport
- Abundant - Coating technique: doctor blade coating, - Carboxyl-methyl cellulose (CM) con-
dipping coating and drop cast ductivity 162 S m1
- Water soluble polymer - Have been folded at certain shape to - The CV curves of the electrode with
investigate the flexibility cellulose binder almost unchanged after
bending into different angles (excellent
flexibility)
- The structure is maintain after long - The capacitance retained between 93
cycles and 80% after 1000 until 5000 cycles
- Form homogenous surface and uniform
distribution
- Exhibit higher reversible capacity after
long cycle
- Low capacity losses
- Weak polyacid
- Stiff
- Have small elongation break
(continued on next page)

3485
 3486
Table 1 e (continued )
Properties Setup/experimental Highlight Ref.
Materials
Chitosan - Insoluble in water but can dissolved in - As a binder material in supercapacitor - Bind the active material and conductive 14,68,67,70-73,75,76
acid solution electrode system material uniformly, smooth and
homogenous
- Resulting high electrochemical - Dissolve in acetic acid and ascorbic acid - Mechanical stability (up to 39 MPa under
performance to form a slurry tensile loading)
- Possesses excellent viscosity - 1e10 wt% amount as binder - Show excellent electrochemical dura-

j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1
bility with 94.2% capacitance retention
after 5000 cycles in graphene electrode
- Excellent adsorption of ions into its - As a composite material in super- - Have long cycle stability
matrix capacitor electrode
- Non-toxicity - Suitable for aqueous, organic and solid
state electrolyte
- Low cost - Technique coating- doctor blade coating
and dipping coating
- Can form well distribution over the - Drying temperature at 60e70
C for
active materials overnight
Lignin - Abundant - Not directly/directly used as binder - Increase the specific capacitance and 82e84,87-89
good stability for supercapacitor
electrode
- Eco-friendly - As a derivative to form active materials - Good capacitance retention until 94%
such as carbon fibre mat after 6000 cycles
- Can withstand high temperature - Form a composite with electrospinning - The as synthesized lignin have favour-
method able electrochemical performance due
- Exhibits tuneable electrochemical per- - Can be dissolved in methanol and to high surface area, high porous struc-
formance, suitable for both high power dioxane ture, hydrophilic surface and superior
and high energy application conductivity
- Highly cost for post-production - Drying temperature at 60e70
C for
processing (thermal and chemical overnight
treatment)
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 3 : 3 4 7 0 e3 4 9 1
8. Conclusion and outlook
Evidently, the polymer-based binder is one of the crucial
components of a supercapacitor. It is also clear that polymer
binders like PVDF, cellulose, chitosan, PEDOT etc., are efficient
binders and widely used (Table 1). However, conducting poly-
mers like PEDOT and PANi can have two roles in the electrode
system: active material and binder. Ideally, supercapacitors
should use electrodes made from polymer-based materials
since they are lightweight, inexpensive, and recyclable.
The following are the most critical considerations for this
particular polymer binder.
i. PVDF: electrodes having a homogeneous distribution of
active materials and a large specific surface area can be
made by regulating the amount of PVDF. The inclusion
of PVDF binder, on the other hand, increases the resis-
tance of the electrodes. PVDF, in particular, requires a
specialised solvent to form a slurry solution.
ii. Cellulose: cellulose has great binding properties, but its
high resistance must be mixed with another conductive
filler to enhance supercapacitor performance. Two types of
cellulose are utilised as a binder in supercapacitor elec-
trodes. It is a derivative of cellulose and natural cellulose.
iii. Chitosan: chitosan can bind active materials uniformly
and without agglomeration. Notably, chitosan is eco-
friendly because no toxic solvent is required.
iv. Lignin: lignin is typically used as a framework in electrode
supercapacitors, but it also serves as a binder holding
active materials and conductive fillers. Due to their high
surface area, porous structure, hydrophilic surface, and
superior conductivity, the as-synthesised lignin dis-
played favourable electrochemical performance.
v. Conducting polymers: conducting polymers can serve
as both an active material and a binder. The electrical
conductivity of the composite electrode with con-
ducting polymer can be improved. Metal oxide alone
has a lower specific capacitance than composite metal
oxide with a conductive polymer.
In addition, polymer binders offer a promising field for more
extensive research. It has been observed that polymer binder
materials can improve supercapacitors' performance and help
develop wearable and flexible supercapacitors. Note that wear-
able and flexible supercapacitors are not only used in electronic
devices but also in medical devices. The best examples of flexible
supercapacitors are self-powered sensors for wearable medical,
wellness and sports applications and biomedical energy har-
vesting devices. When supercapacitors are integrated into medi-
cal devices, a high demand for eco-friendly, safe and cost-
effective materials will arise. In this context, polymer binders in
supercapacitor applications provide flexibility and can also help
the safety concern. The usage of polymer binders such as PVDF,
cellulose, chitosan, lignin and conductive polymer is beneficial.
Other than that, the best electrodes for flexible and portable
supercapacitors are light in weight, low in cost, and easily recy-
clable. This review aimed to view the recent trends in polymer
materials’ applications in the supercapacitors field as important
components of supercapacitor-like binders. It is evident from the
3487
research that polymer binders are efficient binders for not only
widely employed carbon and metal oxide electrodes but also for
emerging electrodes.
Finally, the conductivity and surface characteristics of the
binder need to be further adjusted from a standpoint or
outlook. When the polymer binder is employed, the elec-
trode's surface characteristics and conductivity will be
affected. Therefore, by adding functional groups to the back-
bone or side chains of conductive polymers, the chemical
structure can be altered to overcome these difficulties while
fine-tuning the electrical properties. Furthermore, creating
ternary hybrid structures utilising highly conductive and
flexible materials may also improve the electrode's conduc-
tivity properties. Polymer binders can chemically modify
surface passivation to improve surface characteristics and
prevent unwanted reactions.
Credit author statement
Nor Azmira Salleh: Writing-Original draft, Investigation,
Visualization, Project administration.
Soorathep Kheawhom: Writing -review and editing,
Validation.
Noor Ashrina A Hamid: Writing -review and editing,
Validation.
Wan Rahiman: Writing -review and editing, Validation.
Ahmad Azmin Mohamad: Supervision, conceptualization,
Writing -review and editing.
Declaration of Competing interest
The authors declare the following financial interests/personal
relationships which may be considered as potential
competing interests: Ahmad Azmin Mohamad reports finan-
cial support was provided by Nippon Sheet Glass Foundation
2021. no confilict of interest.
Acknowledgements
The authors would like to thank the Universiti Sains Malaysia
and appreciate the financial support provided from Graduated
Fellowships USM 2022 and the Nippon Sheet Glass Foundation
2021 (NSG 2021) grant (Ref: 304.PBAHAN.6050464.N120). S.K.
acknowledge the Program Unit for Human Resources & Insti-
tutional Development, Research and Innovation, Thailand.
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