Received: 25 February 2019 Revised: 2 April 2019 Accepted: 2 April 2019

DOI: 10.1002/pat.4624

REVIEW

An overview on the recent developments in polyaniline‐based

supercapacitors

Joyita Banerjee1 | Kingshuk Dutta2 | M. Abdul Kader2 | Sanjay K. Nayak3

1
Department of Chemical Engineering,
University of Pittsburgh, Pittsburgh, With the ever‐increasing depletion of nonrenewable fossil fuel reserve, greater atten-
Pennsylvania
tion has been directed towards renewable energy storage devices. One of the most
2
Advanced Research School for Technology
and Product Simulation (ARSTPS), School for important of such devices is the supercapacitor, which exhibits high specific capaci-
Advanced Research in Polymers (SARP), tance. Polyaniline (PAni) is a versatile conducting polymer, which has demonstrated
Central Institute of Plastics Engineering and
Technology (CIPET), Chennai, India excellent electrochemical properties along with good stability and ease of synthesis.
3
Head Office, Central Institute of Plastics Therefore, PAni has been extensively used in the fabrication of supercapacitors. In
Engineering and Technology (CIPET), Chennai,
the last few decades, researchers have studied the effect of morphology, developed
India
during the synthesis of PAni, on its electrochemical properties. It is known that the
Correspondence
electrical conductivity and the electrochemical properties of PAni get influenced by
Kingshuk Dutta, Advanced Research School for
Technology and Product Simulation (ARSTPS), the level and type of dopant used, the method of synthesis adopted, and the surface
School for Advanced Research in Polymers
area and porosity possessed. However, it has been realized that supercapacitors
(SARP), Central Institute of Plastics
Engineering and Technology (CIPET), Guindy, based on PAni suffer from short cycle life. This led to development of PAni compos-
Chennai 600032, India.
ites with carbon‐based materials and transition metal oxides. In this review, focus has
Email: [email protected]
Joyita Banerjee, Department of Chemical
been laid on the achieved performance levels of the recently developed PAni‐based
Engineering, University of Pittsburgh, supercapacitors. In addition, an attempt has been made to study the fundamental
Pittsburgh, PA.
Email: [email protected]
aspects of the conductivity and the electrochemical properties of PAni and their
effect on the supercapacitor performance. Moreover, several new interesting applica-
tions of PAni‐based supercapacitors have also been included in this review.

K E Y W OR D S

capacitance, nanoparticles, polyaniline, pseudocapacitors, supercapacitors

1 | I N T RO D U CT I O N based materials have shown EDLC‐type behavior with high power

density, low cost, and tunable porosity but lacks in energy density.3-5
Supercapacitors, for the last few decades, have accrued immense Pseudocapacitors store charges through fast and reversible reaction,
attention from the scientific society for their unique properties like which can store charges near the surface of the electrode, and thus
long cycle life, wide operating temperature window, high power den- possess high capacitance but low power density. Transition metal
sity, and fast charge‐discharge cycle.1,2 It can store charge in two dif- oxides (TMOs), mixed TMOs,6 and conducting polymers (CPs) exhibit
ferent ways—either by electrostatic way (electrical double layer pseudocapacitance. TMOs exhibit multiple oxidation states with low
capacitors, EDLCs) or by thorough fast and reversible Faradaic reac- activation energy but lack high capacitance and flexibility and suffer
tion (pseudocapacitors). In case of EDLCs, the opposite charges are from instability. In recent years, extensive studies have been done
stored on the surface of the two parallel conductive plates with elec- on TMOs and carbon‐based materials. Another group of fascinating
trolytes between them that help in shuttling of ions between the two. materials is CPs, which show high specific capacitance, flexibility,
EDLCs type of supercapacitors have shown higher power densities and ease of fabrication. The performance of the supercapacitor is
and hence higher rate capabilities. It has been studied that carbon‐ mainly determined by the properties of the materials used. Lots of

Polym Adv Technol. 2019;1–20. wileyonlinelibrary.com/journal/pat © 2019 John Wiley & Sons, Ltd. 1
2 BANERJEE ET AL.

research works had been done on hybrid materials, like CPs/TMOs, considered to show pseudocapacitive behavior. Conway et al18 had
CPs/carbon nanotubes (CNTs), CPs/reduced graphene oxide (rGO), identified several Faradaic mechanisms that may lead to capacitive
and CPs/graphene oxide (GO), which can find potential application behavior. Redox pseudocapacitance involves adsorption of an ion on
as electrode for supercapacitors due to the synergistic effect out of the surface or near the surface of the electrode through Faradaic reac-
the two components. tion and intercalation pseudocapacitance, which involves intercalation
CPs, like polyaniline (PAni), polypyrrole, and polythiophene, have of ions into the tunnels or layer of the active materials through Fara-
also been used as a potential electrode candidate for supercapacitor daic reaction without any change in the crystallographic planes.20
applications, which show pseudocapacitive behavior with high specific Pseudocapacitor provides superior capacitance and energy density,
capacitance.7 However, CPs show short cycle life because of repeti- low equivalent series resistance (ESR), and cost as compared with pure
tive contraction and expansion of polymer chain during charging and carbon active materials.
discharging. Among all the CPs, PAni has been extensively investi- It is to mention here that although for several years nickel oxide/
8-11
gated for its usage in energy storage devices. The extraordinary hydroxide and cobalt oxide/hydroxide have shown CV signature as
properties that help PAni to become unique are its high theoretical that of battery, recently, active materials like MnO2, NiO, Fe3O4 and
capacitance (3407 Fg−1), high hydrogen evolution overpotential, and RuO2 have gained enormous attention for the supercapacitor applica-
wide range of working potential window. It is known to be the most tion and are considered to be the true examples of pseudocapacitive
versatile CPs that find application in energy storage devices like fuel materials.21-25 Among these oxides, RuO2 and MnO2 are the most
cells, supercapacitors, and solar cells and in biomedical engineering widely studied active materials. Both the oxides are conductive in
and can also be used for sensor application.12-16 In this review, the nature along with several distinct oxidation states, and their charge
foremost objective is to focus on the recent developments (last storage mechanism is based on electro‐adsorption of electrolyte cat-
10 y) in the electrode material for supercapacitor application. This ions or protons incorporation on their surface. RuO2 possesses high
piece of work mainly deals with the most extensively studied CP capacitance value (1475 Fg−1), several oxidation states (Ru4+ forms
“PAni,” which has been used as a potential electrode for help in Faradaic charge storage), metallic conductivity, and presence
supercapacitors. Apart from this, the effect of morphology developed of structural water (which helps in proton transfer).26,27 However, high
during synthesis of PAni on the electrochemical behavior has also cost and toxic nature poses challenges to the commercialization of
been addressed. This review presents an overview of the recent RuO2 for supercapacitor application. In contrast, MnO2 showed high
research works that have been done on developing efficient capacitance and low cost and is environment benign, but its low con-
pseudocapacitive electrodes. ductivity limits its application.1,28,29 However, CPs possess high spe-
cific capacitance with high availability and easy of fabrication. CPs
undergo reversible redox reaction to store the charge within the bulk
2 | PSEUDOCAPACITANCE material that improves the energy storage capacity of the
pseudocapacitors and reduces the self‐discharge. However, the
The word “pseudocapacitance” has been coined from the idea that the mechanical stress during reduction‐oxidation on CPs restricts the
electrodes possess the characteristic of tending to or pertaining to cyclic stability of the electrode. In the field of supercapacitors, CPs
behave like a capacitive electrode.17 A battery involves purely Fara- may possess three configurations—(a) symmetric electrodes consisting
daic reaction between the electrodes and the electrolytes using bulk of p‐doped CPs of same material, (b) asymmetric electrodes consisting
active materials, and hence, it imposes a resistance to the ion trans- of p‐doped CPs of different materials with different electroactivities,
portation through the electrolytes. On the other hand, capacitor stores and (c) symmetric electrodes consisting of same CP having p‐doped
electrical charges through electrical double layer formation between form in the positive electrode and n‐doped form in the negative elec-
the oppositely charged electrode and electrolyte. However, trode.30,31 The last type is the most preferred one because of high
“pseudocapacitor” falls in between the above two categories: It stores energy and power.
electrical charges by redox reaction like battery, and the ion transpor- This review focuses on pseudocapacitive behavior of PAni and its
tation takes place through the electrical double layer. It was also pos- recent application in the supercapacitor field. In general, PAni shows
tulated that the capacitive signature in cyclic voltammetry (CV) for three redox peaks in their CV, and these three peaks correspond to
pseudocapacitors is mainly due to the overlap of several redox reac- transition between p‐benzoquinone and hydroquinone, transition
tions that are basically reversible without any changes of phase.18 between the insulating form (leucoemeraldine) and emeraldine salt,
Nowadays, lots of research works have been done on active materials and transition between emeraldine and pernigraniline form.32 Mostly
that undergo Faradaic reaction, but they are used in electrochemical reported results for PAni‐based supercapacitors have shown signifi-
capacitors application. Earlier, the notion “pseudocapacitance” was cant capacitance within the potential window of +0.8 to +1 V. How-
only restricted for materials that undergo Faradaic reaction. However, ever, PAni‐based supercapacitors that show potential as low as
these materials also exhibit capacitive CV signature as it shows +0.6 V are insignificant as energy density becomes very low.33 It
quasirectangular CV response, which is proportional to the scan was found that the electrochemical properties are mainly dependent
19
rate. However, these metal oxides are expensive and scarcely avail- on the morphology developed during the synthesis of PAni, on the
able in nature. CPs, like polypyrrole, PAni, and polythiophene, are also oxidation state of PAni, and also on the quantity and type of doping
BANERJEE ET AL. 3

agent. The size of dopant anion is also an important factor that influ-
ences the performance of the PAni‐based supercapacitor. It is impor-
tant to mention that PAni possesses “size memory effect,” which
means that it can retain the memory of the doped anion molecule dur-
ing the electropolymerization.34 Hence, it will show outstanding per-
formance when it is doped with similar or lesser sized anion molecules.
PAni is one of the most widely studied CPs that has a good balance
of desirable properties, like good stability, high electroactivity, high
conductivity (doped state), easy processability, and high specific
capacitance.35 However, it needs a proton to be fully charged or
discharged, so a protic solvent or protic ionic liquid or an acidic solu-
tion is required.30,36 Moreover, it involves slow rate of ion transfer
during redox reaction, which eventually leads to saturation of areal
capacitance with increase in thickness of PAni. In order to overcome
this limitation, different nanostructures have been introduced, such
as nanofibers (NFs),37 nanocones,38 nanowires, and even composites
with graphene and CNTs.
FIGURE 1 Energy associated in a molecular ionization process—EIP‐v
is the vertical ionization process, Erel is the relaxation energy gained in
the ionized state, Edis is the distortion energy paid to be paid in the
3 | E L EC T R O N I C S T R U C T U R E O F TH E
ground state in the order that the molecule adopts the equilibrium
CONDUCTING POLYMERS geometry of the ionized state, and EIP‐d is ionization energy of the
ionized state. Reprinted with permission from previous literature.39
Just like crystal structure, the unit crystals of the CPs interact with © 1985 American Chemical Society
each other to form several electronic bands. The highest occupied
electronic level overlaps to form valence band, and the lowest unoccu- and the LUMO for CPs is controlled by several factors, like deviation
pied band constitutes the conduction band. The intermediate forbid- from planar configurations due to bending of polymer backbone, the
den gap or band gap decides the inherent electronic behavior of nature of substituents present on the backbone, copolymerization,
these organic semiconductors. For most of the CPs, the band gap intermolecular interaction between the polymer chains and even quin-
values are larger than +1.5 eV and hence are considered to be intrin- oid structure. CPs that carry positive charges onto its backbone
sically nonconductive in nature. It has been found that for organic because of its oxidation are mainly doped by counter anion to main-
molecules, the ionized form's equilibrium geometry is completely dif- tain the electrical neutrality of the whole molecule and are better
ferent from its ground state (Figures 1 and 2). Figure 1 shows the known as p‐type CPs. On the other hand, the reduced CPs carrying
Frank‐Condon–like line for ionization from ground to excited state, negative charges on their backbone are also doped by counter cations
which represents the ionization energy (EIP‐v). It is suggested that the to maintain the electrical neutrality and are known as n‐type CPs. It
ground state of the molecule is first allowed to distort to reach the was found that all the CPs possess p‐type behavior. It is to mention
equilibrium state at the excited state that corresponds to distortion here that the degree of doping in case of conventional silicon semi-
energy (Edis). The excited ionized state might prefer to come back to conductor is much higher than that of CPs. Doping of CPs by counter
relax with an energy equal to Erel.39 This distortion leads to transfer ions leads to volume expansion and change in morphology of CPs.
of one electron from highest occupied molecular orbital (HOMO) to
lowest unoccupied molecular orbital (LUMO). In this connection, this
distorted molecule may require energy of EIP‐d. 4 | CO NDU CT I NG MEC H ANISM OF
It was proposed that positive charge formed during doping gets P O L Y A N I LI N E
delocalized along the backbone, and moreover, this hole was found
to be formed on top of the valence band. The localization of charges PAni has a conjugated π‐orbital overlap system, which leads to contin-
formed leads to local disturbance around the defects. This process uous electron transport through the main chain of the polymer back-
lands up with formation of localized band gap between the HOMO bone. This conjugated molecular structure enables effective charge
and the LUMO of CPs due to downshift of LUMO along with upshift transport along the chain provided the charge carriers are available.
of HOMO. It had been observed that the value of conductivity varies from
Like other CPs, PAni consists of delocalized π‐electrons along its 10−10 to 102 Scm−1 depending on the concentration of the dopants
backbone, which can form π‐valence and π*‐conduction band leading used. PAni exhibits various oxidation states: (a) leucoemeraldine—the
to HOMO and LUMO. Usually, the band gap energy (Eg) that exists fully reduced form, (b) pernigraniline, and (c) emeraldine base (EB)
between HOMO and LUMO for the CPs is +1.5 to +3.0 eV, which (doped EB is known as emeraldine salt).40 The two former forms of
can be minimized by doping. In general, the Eg between the HOMO PAni and EB are completely of nonconductive nature, whereas EB
4 BANERJEE ET AL.

FIGURE 2 Schematic representation of one‐

electron energy levels for organic molecules
(biphenyls) in the ground state electronic
configurations: A, the equilibrium geometry of
the ground state and B, the equilibrium
geometry of the first ionized state. Reprinted
with permission from previous literature.39
© 1985 American Chemical Society

can be doped by protonic acid to form emeraldine salt (conductive Coulombic attraction, thereby providing a hydrophobic side chain
form). PAni base shows insulating behavior, and when it is converted compatible with the organic solvents. The complex formed PAni
to its salt form in acidic medium, charge defects in the form of (CSA)0.5 showed higher solubility than the complex formed PAni
polarons get introduced. Mostly used protonated acids are HCl, (DBSA)0.5 in m‐cresol because of availability of more possible sites of
H2SO4, and HI and also organic acids like camphor sulfonic acid association for PAni in case of CSA as compared with DBSA (addi-
(CSA) and dodecylbenzenesulfonic acid (DBSA). Both types of acids tional carbonyl group present in CSA apart from the sulfonic anion).
have shown similar way of activating the conductive behavior of PAni.
The EB has equal proportions of amine (reduced) and quinonoid (oxi-
dized) sites whose oxidized sites get protonated in acidic medium. In 5 | A P P L I C A T I O N OF P O L Y A N I L I N E I N T H E
this case, the lone pair on the nitrogen atom of the quinonoid struc- F I E LD OF S U P E R C A P A C I T O RS
ture plays an important role in conduction mechanism of PAni.41
The EB form of PAni when protonated gets transformed to con- With the rapid development in the field of nanoscience, metal nano-
ductive protonic forms—polaronic and bipolaronic, as seen in particles and even nanoparticles of CPs have also accrued immense
42
Figure 3. However, there exists some debate about the stability of concentration for the application of supercapacitors. The reduction
the two forms. According to some authors, the polaronic form is more in the particles size of the CPs and metal nanoparticles leads to (a)
stable than the bipolaronic form, and for others, it is exactly the oppo- increase in surface area, (b) development of new reaction sites, (c)
site. It was observed that protonation of PAni‐EB with HX acids leads improve in the accommodation of strain within the electrodes during
to a spinless structure known as bipolarons. However, it ultimately electrochemical reaction, and (d) short pathway for charge/mass trans-
undergoes further rearrangement to form delocalized polaron lattice, fer.43 In the next section of the review, we will discuss the several
better known as polysemiquinone radical cation site. novel PAni‐based supercapacitors that have evolved with time.
PAni possesses semiconducting behavior; and hence, it requires Although only PAni‐based supercapacitors show exceptional
doping with certain protic molecules to achieve high conductivity. pseudocapacitive behavior, but it has short cycle life. In order to
DBSA and CSA are mostly used as doping agents for whom the nega- improve the cyclability, several carbon‐based nanoparticles, like CNTs
tively charged sulfonate group of the dopant acid gets attached with and graphene, are used. However, we could also evidence that in
the positively charged backbone of the emeraldine salt through order to improve the interaction between PAni and CNTs, a multi‐

FIGURE 3 Schematic representation of

polaronic and bipolaronic state of polyaniline
(PAni). Reproduced from previous literature42
with permission from The Royal Society of
Chemistry [Colour figure can be viewed at
wileyonlinelibrary.com]
BANERJEE ET AL. 5

amino dendrimer (PAMAM) was used. The fabricated electrode com- CP‐based composites have been considered to be active at posi-
posed of PAni‐PAMAM‐CNT composite (568 Fg−1) exhibited much tive potential as they behave like p‐type semiconductor and holes
higher specific capacitance than PAni and PAni/CNT–based are the major charge carrier. However, recent research works have
supercapacitors. 44
proved that highly ordered α‐Fe2O3@PAni core‐shell nanowire arrays
Vertically grown PAni nanorods were synthesized by using a nano might be used as a potential negative electrode for supercapacitors.50
template based on a supramolecular assembly of copolymer of 2‐4′‐ This novel electrode coupled with PAni nanowires grown on carbon
hydroxybenzeneazo benzoic acid (HABA) and polystyrene‐b‐poly(4‐ cloth (as cathode) to form a full cell has shown a significantly high vol-
vinyl pyridine) (PS‐P4VP) as scaffold material. 45
These highly dense umetric capacitance of 2.02 mFcm−3 and energy density of
array of PAni, possessing a diameter of 10 nm and a height of around 0.35 mWhcm−3 at a power density of 120.51 mWcm−3 along with
27 nm grown on transparent indium tin oxide (ITO) substrate, have good cycling stability with capacitance retention of 95.77% after
shown an electrochemical capacitance value of 3407 Fg−1. 10 000 cycles. Transition metals were also used as a doping agent
Electro‐co‐deposition of tungsten oxide (WO3) and PAni with car- for PAni for enhancing its electrochemical properties. It was studied
bon electrode and sodium dodecylbenzene sulfonate (SDBS) surfac- that Mn‐doped PAni/single‐walled carbon nanotubes (SWCNTs) com-
tant as the template was performed. This nanostructured PAni/WO3 posites exhibited a higher specific capacitance value as compared with
composite has shown a capacitance of 201 Fg−1 at 1.28 mAcm−2 in Mn‐doped PAni (475 Fg−1) and pure PAni (395 Fg−1) at a 10 mVs−1
46
large potential window with 78% retention of capacitance. Earlier, scan rate.51 The high surface area possessed by the composite in the
47
Sopčić et al had observed that PAni/RuO2 composites with binder presence of SWCNTs, coordination between Mn2+ ion and a lone pair
poly(vinylidene fluoride) (PVdF) display an electrochemical capacitance or one‐electron donation from the nitrogen atom of PAni, uniform
of 526 Fg−1. However, it was postulated that this particular composite coating of Mn‐doped PAni layer on SWCNTs, and most importantly,
is able to show more potential, but because of the presence of PVdF good interaction between π‐bonded SWCNTs surface with the conju-
as binder, its conductivity gets restricted. Recently, Kwon et al48 have gated structure of the PAni was considered to be the reason behind
studied that the electrochemical properties of three‐dimensional (3D) the improved electrochemical properties of the electrode. Ternary
1‐arrayed hollow PAni nanospheres when encaged RuO2 nanoparti- composites of PAni/GO with 70 wt% of MnO2 prepared by quick
−1
cles and its capacitance (1570 Fg ) reach close to the theoretical and two‐step facile method had shown a high capacitance value of
capacitance of PAni. 512 Fg−1 at 0.25 Ag−1 current density with retention of 97% of its ini-
Tetragonal prism array of TiO2, grown on fluorine‐doped tin oxide tial capacitance after 5000 cycles.52 Figure 5 depicts the CV curves for
(FTO) that was synthesized by hydrothermal reaction followed by PAni/GO/MnO2 composites at different scan rates. It is evident from
PAni coating, had proven to be an efficient electrode material for Figure 5 that PAni/GO/MnO2 composites showed pseudocapacitance
supercapacitor. Figure 4 shows the schematic diagram of the synthesis behavior. However, the combined effect of double layer capacitance
route of TiO2 grown on FTO and the process of coating of PAni on it. as well as redox behavior was expected to contribute to the total
The electrode composed of PAni/TiO2/FTO composites had exhibited capacitance of the electrode. It was observed that PAni/GO/MnO2
−1 −1 49
a specific capacitance of 78 Fg at a current density of 1 Ag . composites with 46 wt% of MnO2 exhibited highest capacitance value

FIGURE 4 A, Formation of tetragonal prism array of TiO2 grown on fluorine‐doped tin oxide (FTO), followed by polyaniline (PAni) coating, B,
formation of TiO2 array by hydrolysis, and C, optical images of TiO2/FTO and PAni/TiO2/FTO.49 Reproduced with permission from Elsevier
[Colour figure can be viewed at wileyonlinelibrary.com]
6 BANERJEE ET AL.

FIGURE 5 A, Cyclic voltammetry (CV) curves of GOPM‐46 at scan rate of 10, 20, 30, 40, 50, and 100 mVs−1. B, CV curves of graphene oxide
(GO), MnO2, GO‐PAni, GO‐MnO2, and GOPM‐46 at scan rate of 50 mVs−1.52 Reproduced with permission from Springer Nature [Colour figure
can be viewed at wileyonlinelibrary.com]

because of its unique hybrid porous structure as compared with elec- had been utilized that to some extent reduces the conductivity of
trodes of pure GO and PAni (owing to self‐aggregation). PAni‐coated the active material that in turn affects the performance of the elec-
MnO2 nanorods that were intercalated within GO sheets facilitated trode. In situ polymerized PAni with GO to form close‐knit matrix
conductive pathway as well as high surface area to interact with the along with deposition of MnO2 was synthesized by hydrothermal
electrolyte. reaction to form 3D network hydrogel system.54 This hydrogel‐based
Graphene/MnO2/PAni nanorod arrays were synthesized using electrode had shown a good synergized electrochemical property of
highly ordered MnO2/PAni coaxial nanorod arrays grown on pseudocapacitance of PAni and double layer capacitance of GO. It
graphene‐coated glassy carbon piece that finds application as an elec- showed a power density of 4500 Wkg−1 and energy density of
trode for supercapacitor.53 It was observed that this ternary compos- 61.2 Whkg−1 with good cycle stability. It has been mentioned earlier
−1 −1
ite showed capacitance of 755 Fg at a current density of 0.5 Ag that electrodes based on PAni synthesized by in situ polymerization
with 87% retention after 1000 cycles. However, in this work, binder in the presence of CNTs have shown excellent performance because

FIGURE 6 Field emission scanning electron microscopy images of electrode surfaces containing A, pristine polyaniline (PAni), B, PAni/Ni (OH)2
nanocomposite electrodeposited for 10 min, C, PAni/Ni (OH)2 nanocomposite electrodeposited for 20 min, and D, pristine Ni (OH)2.57
Reproduced under Creative Commons Attribution License (CC BY) [Colour figure can be viewed at wileyonlinelibrary.com]
BANERJEE ET AL. 7

of good adhesion between PAni and CNTs. It was further studied that presence of higher dominant charge as compared with other
PAni/multiwalled carbon nanotubes (MWCNTs) doped with transition electrodes.
metal ions like Cu2+ and Ni2+ during polymerization reaction have It was studied that the morphology developed during hydrothermal
−1 −1 55
shown better performance (1337 Fg at 5 mVs ). This was due synthesis of PAni composite depends on the reaction condition
to good coordination between these ions and the nitrogen atoms of parameters. Direct hydrothermal reaction involving synthesis of
PAni that facilitates effective delocalization throughout PAni chain. PAni/graphene nanosheet (GNS) composites has led to formation of
In another study, it was found that PAni doped with zirconium had fiber‐like PAni/GNS composites, whereas hydrothermal‐assistant
−1
demonstrated a higher specific capacitance value of 323 Fg , as com- chemical oxidation polymerization generates nanosheets of
pared with the values produced by HCl‐doped PAni (ie, 160 Fg−1) and PAni/GNS composites.58 Moreover, it has been noted that the elec-
pristine PAni (ie, 160 Fg−1), when measured at a scan rate of 2 mVs−1 trochemical properties of the PAni/GNS composites electrodes
in 6M KOH solution. It was realized that pseudoprotonation of PAni depend on the temperature. Figure 7 depicts the PAni/GNS compos-
4+
by Zr ions led to higher capacitance and intercalation of metallic ions ites prepared by hydrothermal synthesis process at different reaction
into PAni layers. The energy and power density of the Zr‐doped PAni temperatures. It was observed that the composites prepared by direct
composite were observed to be 114.8 Whkg−1 at 2 mVs−1 scan rate synthesis method had shown high agglomeration as compared with
and 703.5 Wkg−1 at 10 mVs−1 scan rate, respectively.56 other compositions. Two‐step hydrothermal‐assistant chemical oxida-
Hybrid nanocomposites of PAni/Ni (OH)2, formed by single‐ or tion polymerization process leading to PAni layers with total thickness
two‐step electrodeposition on stainless steel (SS) at various time, have of 10 to 20 nm was uniformly composited with GNS, whereas PAni
shown excellent electrochemical properties in basic medium.57 The NFs prepared by a one‐step direct hydrothermal process exhibited a
corresponding morphologies obtained at different durations of elec- diameter of 50 to 100 nm. Among different reaction temperatures
trodeposition have been presented in Figure 6. It was observed that (120°C, 150°C, and 180°C), the electrodes prepared from PAni/GNS
Ni (OH)2 deposited for longer time exhibited the highest capacitance composites using hydrothermal process with reaction temperature at
value (ie, 113.8 Fg−1) among all other nanocomposites, owing to the 120°C have shown best electrochemical properties.

FIGURE 7 Transmission electron microscopy (TEM) images of sample A 120 A,B, A 150 C, and A 180 D, by direct hydrothermal treatment.58
Reproduced under Creative Commons Attribution 4.0 International License
8 BANERJEE ET AL.

PAni/GO or rGO composites (231.2 Sm−1) have shown higher con- Carbon nanofiber (CNF)‐CNTs‐PAni composite NFs using acid
ductivity as compared with pure PAni (10.6 Sm−1), which was attrib- functionalized MWCNTs had been appeared as a promising electrode
uted to the π‐π stacking between the PAni backbone and graphene‐ material for supercapacitor.64 This ternary composite showed higher
59
based sheet. It was observed that the obtained PAni/GO composites capacitance than either any of the composites—CNF‐PAni (794 Fg
exhibited lower specific capacitance than fibrous PAni NFs (420 Fg−1) −1
), CNF‐CNT (320 Fg−1), and CNF (278 Fg−1). In this work, CNF‐CNTs
because of the presence of insulating GO sheets in the composites composites were prepared by using polyacrylonitrile (PAN) as the pre-
that contribute little to the total specific capacitance of the compos- cursor followed by incorporation of PAni by in situ polymerization of
ites. Three‐dimensional graphene‐PAni‐CNTs composites also exhibit aniline. It was observed that addition of CNTs increases the diameter
excellent specific capacitance of 920 Fg−1 at a specific current of of CNF‐CNTs‐PAni composite NFs because of the introduction of
0.8 Ag−1 as compared with PAni/graphene foam. In another work, entanglements. However, the diameter of CNF‐CNTs‐PAni composite
Phokaratkul et al60 had fabricated graphene foam by chemical vapor NFs reduced to a range of 279 to 433 nm after carbonization owing to
deposition (CVD) on Ni foam using acetylene carbon source and release of CO, NH3, CO2, H2O, and other small molecules. It has been
hydrogen gas carrier at high temperature. Electrodes composed of reported that metal (copper and nickel)–doped PAni synthesized by
coaxial electrospun fibers have also shown excellent electrochemical seeding approach has shown high specific capacitance (three electrode
performance. system) and long cycle life with a capacitance loss of only 5% after
61
Bharadiya et al had studied the electrochemical properties of 1000 charge/discharge cycles.65 PAni/CNT/rGO nanocomposites
GO‐wrapped PAni composites (Figure 8). They observed that the have been studied to act as an efficient electrode for supercapacitors
wrapping of monolayer (1) and multilayer (2 to 10) of GO sheets on with a high specific capacitance of 312 Fg−1. In this case, CNTs form
PAni nanorods led to an increase in the d‐spacing of the GO sheets the conductive pathways connecting the rGO islands that are present
from 12.76 Å for PAni/GO1 to 13.46 Å for PAni/GO10. The compos- in the ternary nanocomposites.66 Chang et al67 had reported a novel
ite of PAni/GO10 had demonstrated a specific capacitance value of electrode based on biomimetic hierarchical structure of
276 Fg−1. PAni/MWCNTs composites on using fresh plant leaves as a template
One such example is the ternary MnO2/PAni/MWCNT coaxial through the nanocasting technique, which had shown much higher
composites fibers that have shown high specific capacitance of specific capacitance than PAni‐3D (420 Fg−1). MWCNTs facilitate in
−1 −1
431.3 Fg at 0.5 Ag with a retention of 88.2% of initial capacity formation of 3D network within PAni phase, and the value of specific
after 2000 cycles.62 Microglobules of PAni, grown on commercial steel capacitance was observed to be dependent on amount of CNTs used.
plate (which was further used as a catalyst for the hydrothermal syn- It can be observed from Figure 9 that the CV curve of PAni‐3D and
thesize of WO3 nanoparticles), have been reported to be used as an PAni/MWCNTs composites had shown three pair redox peaks—(a)
electrode for supercapacitors.63 This fabricated electrode has shown A/A′ and C/C′ represent the redox reaction associated by
an area specific capacitance of 294 mFcm−2 in the presence of leucoemeraldine and pernigraniline species of PAni and (b) the weak
LiClO4/propylene carbonate (PC) electrolyte. It was inferred that B/B′ peak designates the redox reaction involving double electron
WO3 emerged as a potential catalyst and it also provides firmness to transition between hydroquinone and benzoquinone via hydrolysis
the electrode. reaction of PAni.

FIGURE 8 A schematic diagram depicting

the preparation of graphene oxide (GO)–
wrapped polyaniline (PAni) nanorods.61
Reproduced with permission from Wiley
[Colour figure can be viewed at
wileyonlinelibrary.com]
BANERJEE ET AL. 9

FIGURE 9 Scanning electron microscopy (SEM) B,C and atomic force microscopy D, images and cyclic voltammetry (CV) curves E, of biomimetic
hierarchical structure of polyaniline/multiwalled carbon nanotubes (PAni/MWCNTs) composites on using fresh plant leaves as a template.
Reproduced from previous literature67 with permission from The Royal Society of Chemistry [Colour figure can be viewed at wileyonlinelibrary.
com]

Binder‐free PAni/MWCNTs/poly(ethylene oxide) (PEO) compos- method. The resulting working electrode had shown good cycle stabil-
ites prepared by electrospinning method showed higher capacitance ity with 65% retention of capacitance even after 5000 cycles. The mor-
of 385 Fg−1 as compared with PAni/PEO composites fibers phology of the active materials plays an important role in deciding the
−1 −1 68
(308 Fg ) at a current density of 0.50 Ag . PAni due to its aromatic electrochemical properties of the electrode. It was studied that PAni‐
(rigid) structure considered being insoluble in most of the solvents; NFs web formed by electrospinning exhibited higher specific capaci-
hence, PEO was used as carrier to ease the electrospinning process. It tance at 0.35 Ag−1 current density as compared with PAni powder at
was also studied that azobenzene functionalized CNTs composited various solvent like 1M H2SO4, Na2SO4, and LiClO4 in propylene chlo-
with PAni exhibited good electrochemical properties owing to grafting ride.70 The interconnected fibers like structure in case of PAni‐NF web
69
of PAni onto CNTs via azobenzene. This grafting phenomenon as allow efficient penetration of electrolyte within the pores of web,
well as covalent linkage resulted in better electron transport between whereas PAni powder forms agglomerated structure that inhibits the
PAni and CNTs. In this work, acid functionalized CNTs were used and easy percolation of electrolyte within the agglomerates that resulted
PAni was grafted onto it via azobenzene using emulsion polymerization in comparatively poor electrochemical properties of the electrodes.
10 BANERJEE ET AL.

Another binder‐free electrode is based on sponge‐like 1.56 mAcm−2. The symmetric supercapacitor composed of PAni/N‐
phosphorus‐doped GO@PAni, which showed a specific capacitance doped CNTs electrodes and poly(vinyl alcohol) (PVA)/H2SO4 hydrogel
value of 588 Fg−1 at a current density of 1 Ag−1 in 6M KOH solution.71 as separator exhibited a specific capacitance of 128 Fg−1 at 2.47 Ag−1
The asymmetric supercapacitor device composed of phosphorus‐ current density and also showed 92% retention even after
doped GO@PAni as the anode and activated carbon as the cathode 1000 cycles.73
−1
exhibited a high energy density of 7.91 Whkg and a power density In general, electrodes for supercapacitors are prepared by assem-
of 7826.22 Wkg−1. Figure 10 shows the schematic diagram of all‐ bling or mixing active materials, conductive materials, and binder
solid‐state supercapacitor that used 3D network–based Fe3O4‐deco- particles. A binder helps in adhering the active materials with the
rated rGO‐doped PAni as the electrode.72 It was suggested that the conductive materials as well as with the substrate material in order
combined effect of double layer capacitance from rGO and to prevent falling off of the active materials. Hence, binders play
pseudocapacitance from Fe3O4 and PAni helped in the enhancement an important role in enhancing the performance of the electrodes of
of the overall capacitance of the all‐solid‐state supercapacitor. This the supercapacitors. The mostly used binder materials are
ternary composite exhibited a specific capacitance of 283.4 Fg−1 at polytetrafluoroethylene (PTFE), PVdF, Nafion, polyvinylchloride
1.0 Ag−1 current density, with maximum power and energy densities (PVC), and PAN. Even mixture of polyvinylpyrrolidone/
of 550 Wkg−1 and 47.7 Whkg−1, respectively. Three‐dimensional polyvinylbutyral (PVP/PVB) has been shown to be an efficient binder
nanostructured CNTs (N‐doped) sheet grown in an array, formed using for supercapacitor applications.74 Table 1 summarizes the perfor-
dry drawing process from spinnable CNTs, was used as a support on mance of supercapacitors in the presence and absence of binder.
which electropolymerization of PAni (50 wt% of polymer content) Nowadays, aerogel and hydrogel of carbon‐based materials like
was done (Figure 11). This free‐standing flexible electrode showed a CNTs and graphene have been used as a support material for the
gravimetric capacitance of 359 Fg−1 at a current density of active materials. The major advantages for utilizing these active mate-

FIGURE 10 A schematic illustration of binder‐free all‐solid‐state supercapacitor.72 Reprinted with permission from previous literature.72 © 2017
American Chemical Society. PAni, polyaniline; rGO, reduced graphene oxide [Colour figure can be viewed at wileyonlinelibrary.com]

FIGURE 11 A schematic diagram of the formation of polyaniline (PAni)/N‐doped carbon nanotube (CNT) sheet.73 Reproduced with permission
from Elsevier [Colour figure can be viewed at wileyonlinelibrary.com]
BANERJEE ET AL. 11

TABLE 1 Summary of the performance of supercapacitors in the presence and absence of binder

Materials Used Binder or Binder Free Performance References

−1 95
PAni interconnected with metal(II) hexacyanoferrate(III) Binder free Specific capacitance of 725 Fg at a current
nanocomposites (M = Ni, Co) on flexible carbon fibers density of 1 Ag−1
96
PAni/carbon NFs Binder free Retention of 74% of capacitance after
4500 cycles
MoS2/PAni Binder free Specific capacitance of 485 Fg−1 at a current 97

density of 1 Ag−1
PAni/graphene Binder free Specific capacitance of 255 Fg−1 98

−1 99
Functional acetylene black–doped PAni PVdF as binder Specific capacitance of 132 Fg at a current
density of 0.3 Ag−1
PAni/graphene/CNTs CNTs as binder Energy density of 188.4 Whkg−1 and maximum 100

power density of 200.5 kWkg−1

RuO2/PAni Nafion as binder Specific capacitance of 155 Fg−1 47

Abbreviations: CNTs, carbon nanotubes; NF, nanofiber; PAni, polyaniline; PVdF, poly(vinylidene fluoride).

rials are as follows—(a) provides interconnected macroscopic network the electrodes, and (d) acts as strong and scaffold to relieve stress
system for easy accessibility for ions and electrolytes, (b) ensures developed because of repetitive cycling of the polymeric phase.
higher surface area for depositing higher loading of active materials, Gao et al75 had reported an extraordinary electrode based on
(c) contributes EDL capacitance to the overall capacitance value of PAni/graphene composites synthesized by electro‐depositing thin

FIGURE 12 A, Photo of V2O5·nH2O dispersions and the corresponding lyophilized monolith. B, Scanning electron microscopy (SEM) image of
the lyophilized V2O5 dispersions. C, Photo of polyaniline (PAni) suspensions prepared by mixing an aniline acidic solution with an ammonium
persulfate one. D, SEM image of the lyophilized PAni suspension in C. Reprinted with permission from previous literature.79 © 2018 American
Chemical Society [Colour figure can be viewed at wileyonlinelibrary.com]
12 BANERJEE ET AL.

PAni layer on 3D‐based graphene framework. This electrode had capacitance of 424 Fg−1 and retains 96% even at 90% compressive
−1
exhibited a maximum of energy density of 24 Whkg and power den- strain and a volumetric capacitance 65.5 Fcm−3.
sity of 30 kWkg−1 with a good cycling stability. Reports revealed that Recently, porous PAni ultrathin nanowires have been reported by
the compressible graphene aerogels exhibited specific capacitances of Zhou et al,79 where V2O5 was used as a sacrificial template to form
−1
37 and 90 Fg , which is quite low owing to double layer storage the PAni hydrogel. In this case, V2O5 was not only used as sacrificial
mechanism of carbonaceous materials.76,77 Hence, graphene aerogels template (by converting into soluble salts) but also used as oxidant
are combined with pseudocapacitors materials to enhance the perfor- for in situ polymerization of aniline. V2O5 nanowires play an important
mance of the electrodes. Compressible PAni/graphene electrodes with role for the synthesis of hydrogel of PAni nanowires through 3D net-
63% of PAni had shown excellent specific capacitance with a high work because of its long aspect ratio and hydrophilicity (retards aggre-
recoverable compressive strain of 90%.78 It showed a gravimetric gation of nanowires). It was observed that this highly porous ultrathin

FIGURE 13 Top: A, Cyclic voltammogram and B, galvanostatic charge‐discharge of several hydrogels, and Bottom: Schematic representations of
the structures of a, PAni hydrogel, b, graphene/PAni hydrogel and c, N‐doped graphene/PAni hydrogel. Reproduced from [86] with permission
from The Royal Society of Chemistry [Colour figure can be viewed at wileyonlinelibrary.com]
BANERJEE ET AL. 13

PAni NF–based electrodes exhibited a specific capacitance of 636 Fg of active materials on flexible materials.81 Sarker and Hong82 had
−1 −1 −1 −1
(at 2.0 Ag ) and 626 Fg (at 25.0 Ag ) along with 83% retention explored the plastic‐based supercapacitor composed of thin
of its capacitance even after 10 000 cycles. Figure 12 presents the PAni/rGO films using layer‐by‐layer (LBL) deposition method. In this
scanning electron microscopy (SEM) images of the V2O5‐based PAni work, polyethylene terephthalate (PET) had been used as a flexible
hydrogel that showed porous structure with high surface area substrate as well as current collector. It was also studied that the
whereas PAni particles obtained by using ammonium persulfate as oxi- nature of the substrate also played an important role on the electro-
dant had showed an aggregated morphology with irregular shaped chemical properties of the electrode. PAni/GO was deposited by
structures. Nowadays, CPs have been extensively investigated for LBL process on both PET and ITO substrate, and it was observed that
their application in flexible devices used in wearable electronics. ITO‐based PAni/GO electrode (956 Fcm−3) exhibited higher volumet-
Zou et al 80
had recently reported about the excellent electrochem- ric capacitance than PET‐based PAni/GO electrode (529 Fcm−3) at
ical properties of soluble PAni hydrogel synthesized by hydrothermal 3 Acm−3 owing to higher conductivity of ITO. Electrodes formed by
process. It was observed that PAni hydrogel had shown extremely layer‐bilayer multilayer deposition of PAni/rGO on fused silica had
robust areal capacitance of 484 mFcm−2 at 1 mAcm−2 with good bend- shown excellent electrochemical properties.83 It has been observed
ing cycles. Introduction of GO led to increase the surface area of that PAni and GO interact through electrostatic force, hydrogen bond,
PAni/GO (100.7 m2 g−1) and PAni/m‐phenylenediamine (mPD)/GO and π‐π bond. It had a volumetric capacitance of 584 Fcm−3 at a cur-
−1 −1
2
(76.1 m g ) hydrogel composites from PAni hydrogel (21.1 m g ). 2
rent density of 3.0 Acm−3, which decreased 170 Fcm−3 at higher cur-
Figure 13 depicts the CV and galvanostatic charge‐discharge of rent density of 100 Acm−3. It has been recently reported that even
PAni/GO, PAni/mPD/GO, and PAni hydrogel and also the possible PAni nanowires grown in the internal surfaces of the macroporous
mechanism proposed for the interaction between PAni and GO. It carbon (MC) derived from luffa sponge fibers have shown high capac-
was postulated that during hydrothermal reaction, phenazine‐like seg- itance with excellent cyclability.84 The main reason behind this excel-
ments were obtained by crosslinking between quinoid rings of PAni lent performance of this electrode was attributed to large pores that
whereas in case of PAni/GO hydrogel, the benzenoid amine section allowed the electrolyte to interact with the whole active material that
of PAni formed epoxy bond with oxygen functionalized graphene. It had been grown in the internal surface of the MC. The symmetric full
was further observed from RAMAN and XPS analysis that in case of cell composed of MC/PAni materials displayed a high energy density
PAni/mPD/GO hydrogel, the interaction between PAni and GO was of 19 Whkg−1 at 0.5 kWkg−1 and 83% retention of its initial capaci-
disturbed by mPD and also acts as a dopant for graphene, which helps tance after 7000 cycles. Flexible electrodes produced by drop casting
to keep the electronic structure of graphene intact. method on ITO‐coated PET substrate (22‐25 Ωcm−2) had shown quite
Another approach that is gaining enormous attention is the fabri- high capacitance of approximately 120 Fg−1 (0.08 g of PAni) along
cation of PAni‐based flexible supercapacitors. Recent upsurge in with a retention of 70.51% after 100 charge‐discharge using 0.5M
research of flexible electronics led to focus on the idea of deposition LiClO4 and polypropylene carbonate as electrolyte.85

FIGURE 14 A schematic depiction of the synthesis of sandwich structure of carbonized Zn‐metal‐organic framework/polyaniline (MOF/PAni)
composites.89 Reproduced with permission from Elsevier [Colour figure can be viewed at wileyonlinelibrary.com]
14 BANERJEE ET AL.

TABLE 2 Summary of some recent developments in PAni‐based supercapacitors

Materials Used Electrochemical Performance References

−1 101
Unzipped CNT (UCNT)/PAni Specific capacitance of 762 Fg with 20% capacity fade after 1000 cycles
−1 102
PAni Specific capacitance of 890 Fg with 89% retention after 1000 cycles in PVA/
H3PO4 electrolyte
PAni/CNT Specific capacitance of 7926 Fg−1 with 4% capacity loss after 1000 cycles 103

−1 −1 104
Ag/MnO2/PAni Specific capacitance of 800 Fg at 1 mAg in 0.5M LiClO4 (in PC)
CoMoO4/PAni Specific capacitance of 380 Fg−1 at 1 mAg−1 in 1M Na2SO4 with 90% 105

retention in initial capacitance after 1000 cycles

Cellulose/CNT/PAni Specific capacitance of 495.2 Fg−1 with 19% capacity fade after 1000 cycles 106

Stretchable isotropic buckled Specific capacitance of 1147.12 Fg−1 107

CNT/PAni
CNT/PAni cotton–shaped fiber Specific capacitance of 144 Fg−1 with 15.5% capacity fade after 200 cycles 108

RuO2/PAni/C Specific capacitance of 531 Fg−1 in 1M H2SO4 109

−1 110
G/PAni/MCM‐41 Specific capacitance of 405 Fg with 91.4% retention after 1000 cycles in 1M
KOH
H/Ni co‐doped PAni/CNT Specific capacitance of 781 Fg−1 at 0.5 Ag−1 with 92% retention after 111

700 cycles in 1M H2SO4

PAni/NiCo2O4 Specific capacitance of 781 Fg−1 at 1 Ag−1 with 91% retention after 112

3000 cycles in 1M H2SO4

CNT/CB/GNSs PAni Specific capacitance of 450 Fg−1 with 16% capacity fade after 1000 cycles 113

PAni‐g‐MWCNT/TiO2NTs/Ti Specific capacitance of 708 Fg−1 with 12% capacity fade after 1000 cycles 114

−1 115
PAni/CNT array Specific capacitance of 1030 Fg with 23% capacity fade after 100 cycles
PAni/MoS2 Specific capacitance of 575 Fg−1 at 1 Ag−1 with 98% retention after 500 cycles 116

in 1M H2SO4
MoS2/PAni/G Specific capacitance of 618 Fg−1 at 1 Ag−1 with 78% retention after 117

2000 cycles in 1M Na2SO4

PAni/C/Ni Specific capacitance of 725 Fg−1 at 0.5 Ag−1 in 1M Na2SO4 118

Self‐doped PAni Specific capacitance of 408 Fg−1 at 1 Ag−1 in 0.5M Na2SO4 119

3D PAni on pillared rGO Specific capacitance of 652 Fg−1 at 1 Ag−1 with 90% retention after 120

4000 cycles in 0.5M H2SO4

PAni nanorods on rGO sponges Specific capacitance of 662 Fg−1 at 1 Ag−1 with 93% retention after 121

5000 cycles in 1M H2SO4

PAni/B‐doped rGO Specific capacitance of 406 Fg−1 at 1 Ag−1 with 90% retention after 122

10 000 cycles in 1M H2SO4

rGO hydrogel films embedded Specific capacitance of 921 Fg−1 at 1 Ag−1 with 100% retention after 123

with PAni NFs 2000 cycles in 1M H2SO4

PAni nanowire on rGO/ZrO2 Specific capacitance of 1360 Fg−1 at 1 Ag−1 with 93% retention after 124

1000 cycles in 1M H2SO4

Bamboo carbon/PAni Specific capacitance of 244 Fg−1 at 0.5 Ag−1 with 92% retention after 125

1000 cycles in 1M H2SO4

PAni NFs/N‐doped rGO Specific capacitance of 610 Fg−1 at 1 Ag−1 with 94% retention after 126

hydrogels 1000 cycles in 1M H2SO4

Hydrogel‐assisted PAni microfiber Specific capacitance of 709 Fg−1 at 10 mVs−1 in 1M methane sulfonic acid 127

PAni nanowhiskers Specific capacitance of 470 Fg−1 at 1 Ag−1 with 90% retention after 128

1000 cycles in 1M H2SO4

PAni/GO on SS Specific capacitance of 1136 Fg−1 at 1 Ag−1 with 89% retention after 129

1000 cycles in 1M H2SO4

PAni/OMC Specific capacitance of 146 Fg−1 at 6 Ag−1 in 1M LiPF6 130

−1 −1 131
PAni/MnO2/TiN Specific capacitance of 674 Fg at 1 Ag in 1M Na2SO4

(Continues)
BANERJEE ET AL. 15

TABLE 2 (Continued)

Materials Used Electrochemical Performance References

−1 −1 132
PAni/TiO2/GO Specific capacitance of 430 Fg at 1 Ag in 1M H2SO4
PAni‐coupled Co3O4 and rGO Specific capacitance of 1063 Fg−1 at 1 Ag−1 with 95% retention after 133

2500 cycles in 6M KOH

PAni on rGO paper Specific capacitance of 233 Fg−1 at 2 mVs−1 with 100% retention after 134

1500 cycles in 1M H2SO4

PAni NF–wrapped graphene‐PAni Specific capacitance of 578 Fg−1 at 1 Ag−1 with 93% retention after 135

nanorod 10 000 cycles

PAni coated on nanoporous gold Areal capacitance of 6.54 mFcm−2 136

support
PAni/V3O7/rGO Specific capacitance of 579 Fg−1 at 0.2 Ag−1 with 94% retention after 137

2500 cycles in 1M H2SO4

PAni/2D host nanosheets from Specific capacitance of 592.5 Fg−1 at current density of 2 Ag−1 with 87% 138

the MgFe layered double retention after 500 cycles

hydroxide (MgFe‐LDH)
Porous PAni/graphene on carbon Mass capacitance of 55.1 Fg−1 under 0.5 Ag−1 139

paper
PAni‐coated graphene paper Areal capacitance of 123 mFcm−2 at current density of 0.2 mAcm−2 140

rGO@‐c‐PAni/CNT‐SS Specific capacitance of 465 mFcm−2 at current density of 1 mAcm−2 with 84% 141

retention after 1000 GCD cycles

PAni/activated carbon/Ni Specific capacitance of 1661 Fg−1 at 1 Ag−1 with 93% retention after 142

2000 cycles in 1M aqueous Na2SO4 solution

Abbreviations: CNT, carbon nanotube; GCD, galvanostatic charge‐discharge; GNS, graphene nanosheet; GO, graphene oxide; MWCNT, multiwalled carbon
nanotube; NF, nanofiber; OMC, ordered macroporous carbon; PAni, polyaniline; PC, propylene carbonate; PVA, poly(vinyl alcohol); rGO, reduced graphene
oxide; SS, stainless steel.

PAni/MnO2 composites prepared by one‐pot deposition process Guo et al89 had studied the electrochemical performance of
that involves simultaneous electropolymerization of aniline and electro- carbonized Zn‐(metal‐organic framework) MOF/PAni–based
deposition of MnO2 from aqueous medium on ITO‐coated glass/PET supercapacitor. In this work, the MOF had been derived from 8‐
substrate had shown excellent electrochromic properties along with hydroxyquinoline and zinc acetate via calcination process. Figure 14
86
good cycle stability. In this arrangement, MnO2 and PAni act as n‐type shows a schematic diagram of the preparation and structure of car-
and p‐type semiconductor that improves the electron transference bonized Zn‐MOF/PAni composites. Zn‐MOF/PAni composites had
between the two entities. It was postulated that the unique properties been reported to exhibit a specific capacitance of 477 Fg−1 at a cur-
of these electrodes were due to its porous morphology, smaller inter- rent density of 1 Ag−1.
particle distance between the nanoparticles, and more importantly, An asymmetric supercapacitor, composed of PAni deposited elec-
the donor‐acceptor relationship between PAni and MnO2. Flexible trochemically on interdigital finger gold electrode as positive electrode
paper–like electrodes produced from aqueous dispersion of chemically and graphene quantum dots as negative electrodes, has exhibited a
converted graphene and PAni NFs by vacuum filtration have showed good electrochemical behavior in Na2SO4 and H3PO4‐PVA gel as elec-
87
promising electrochemical properties. In this case, PAni NFs are incor- trolytes.90 In another study, Tian et al91 had studied the performance
porated between the graphene layers, and it observed to contain 44% of a supercapacitor device composed of PAni and W18O49, both oper-
chemical converted graphene to improve the mechanical properties of ating at different potential ranges, ie, 0 to +0.8 V and −0.5 to 0 V,
the electrodes. The conductivity of this paper electrode exhibited respectively. The authors observed excellent cycling behavior and high
2 −1
5.5 × 10 Sm , and the resultant symmetric supercapacitor device capacitance value. Apart from the studies discussed above, PAni has
had shown a high capacitance of 210 Fg−1 at 0.3 Ag−1 with 94% reten- found use as electrolytic capacitors in other supercapacitor applica-
tion in capacitance when the charging current increased to 3 Ag−1. tions as well.92-94 Table 2 depicts the summary of some recent devel-
In this context, it is also important to mention the performance of opments in PAni‐based supercapacitors.
supercapacitors based on perovskite/PAni composites. Recently, it
was reported that KCa2Nb3O10 perovskite/PAni composite–based
supercapacitor had shown a specific capacitance of 250 Fg−1.88 These 6 | CO NC LUSIO N
new class of materials are economically viable but lag behind tradi-
tional carbon‐based materials in terms of conductivity and metal In summary, this review narrates the recent advances in the electrode
oxides in terms of pseudocapacitance. materials along with their design, synthesis, and application in
16 BANERJEE ET AL.

supercapacitors. PAni has shown high specific capacitance value but 11. Dutta K, Das S, Kundu PP. Effect of the presence of partially
exhibits short cycle life. In order to overcome this shortcoming, PAni sulfonated polyaniline on the proton and methanol transport behavior
of partially sulfonated PVdF membrane. Polym J. 2016;48(3):301‐309.
was composited with either carbon‐based or TMO nanomaterials.
PAni‐based asymmetric supercapacitors have shown excellent electro- 12. Das S, Dutta K, Kundu PP. Nickel nanocatalysts supported on
sulfonated polyaniline: potential toward methanol oxidation and as
chemical capacitance along with high cycle stability and mechanical
anode materials for DMFCs. J Mater Chem A. 2015;3(21):
strength. For these types of supercapacitors, the working potential 11349‐11357.
voltage remains high, which led to high charge storage. Nevertheless, 13. Dutta K, Das S, Kundu PP. Synthesis, preparation, and performance of
further works on PAni‐based supercapacitors are required to blends and composites of π‐conjugated polymers and their copoly-
advance the application of these unique materials in the field of mers in DMFCs. Polym Rev. 2015;55(4):630‐677.
supercapacitors. In addition, future works should also focus on design- 14. Dutta K, Das S, Rana D, Kundu PP. Enhancements of catalyst distribu-
ing tailor‐made derivatives of PAni and functionalized PAni in order to tion and functioning upon utilization of conducting polymers as
supporting matrices in DMFCs: a review. Polym Rev. 2015;55(1):1‐56.
achieve high level of performance. Moreover, since nanostructured
PAni has exhibited better properties compared with their larger coun- 15. Dutta K, Kundu PP. A review on aromatic conducting polymers‐based
catalyst supporting matrices for application in microbial fuel cells.
terparts, therefore, focus should be laid on development of unique
Polym Rev. 2014;54(3):401‐435.
nanostructures of PAni with higher surface areas and conductivities
16. Pramanik N, Dutta K, Basu RK, Kundu PP. Aromatic π‐conjugated
for such applications. Furthermore, other CPs, most notably polypyr-
curcumin on surface modified polyaniline/polyhydroxyalkanoate
role and polythiophene, in conjunction with PAni should be tested based 3D porous scaffolds for tissue engineering applications. ACS
for their application potential in supercapacitors. Biomater Sci Eng. 2016;2(12):2365‐2377.
17. Brousse T, Bélanger D, Long JW. To be or not to be
ORCID pseudocapacitive? J Electrochem Soc. 2015;162(5):A5185‐A5189.

Kingshuk Dutta https://orcid.org/0000-0001-8971-4621 18. Conway BE, Birss V, Wojtowicz J. The role and utilization of
pseudocapacitance for energy storage by supercapacitors. J Power
Sources. 1997;66(1‐2):1‐14.
RE FE R ENC E S
19. Costentin C, Porter TR, Savéant J‐M. How do pseudocapacitors store
1. Simon P, Gogotsi Y. Materials for electrochemical capacitors. Nat energy? Theoretical analysis and experimental illustration. ACS Appl
Mater. 2008;7(11):845‐854. Mater Interfaces. 2017;9(10):8649‐8658.
2. Yu G, Xie X, Pan L, Bao Z, Cui Y. Hybrid nanostructured materials for 20. Augustyn V, Simon P, Dunn B. Pseudocapacitive oxide materials for
high‐performance electrochemical capacitors. Nano Energy. 2013;2(2): high‐rate electrochemical energy storage. Energ Environ Sci.
213‐234. 2014;7(5):1597‐1614.

3. El‐Kady MF, Strong V, Dubin S, Kaner RB. Laser scribing of high‐ 21. Ghodbane O, Pascal J‐L, Favier F. Microstructural effects on charge‐
performance and flexible graphene‐based electrochemical capacitors. storage properties in MnO2‐based electrochemical supercapacitors.
Science. 2012;335(6074):1326‐1330. ACS Appl Mater Interfaces. 2009;1(5):1130‐1139.

4. Stoller MD, Park S, Zhu Y, An J, Ruoff RS. Graphene‐based 22. Wei W, Cui X, Chen W, Ivey DG. Manganese oxide‐based materials
ultracapacitors. Nano Lett. 2008;8(10):3498‐3502. as electrochemical supercapacitor electrodes. Chem Soc Rev. 2011;
40(3):1697‐1721.
5. Xia J, Chen F, Li J, Tao N. Measurement of the quantum capacitance
23. Roy A, Ray A, Saha S, et al. NiO‐CNT composite for high performance
of graphene. Nat Nanotechnol. 2009;4(8):505‐509.
supercapacitor electrode and oxygen evolution reaction. Electrochim
6. Yuan C, Wu HB, Xie Y, Lou XW. Mixed transition‐metal oxides: Acta. 2018;283:327‐337.
design, synthesis, and energy‐related applications. Angew Chem Int 24. Li T, Yu H, Zhi L, et al. Facile electrochemical fabrication of porous
Ed. 2014;53(6):1488‐1504. Fe2O3 nanosheets for flexible asymmetric supercapacitors. J Phys
7. Banerjee J, Dutta K, Rana D. Carbon nanomaterials in renewable Chem C. 2017;121(35):18982‐18991.
energy production and storage applications. In: Saravanan R, Mu N, 25. Ahn YR, Park CR. Enhanced charge‐discharge characteristics of RuO2
Raju K, Boukherroub R, eds. Emerging Nanostructured Materials for supercapacitors on heat‐treated TiO2 nanorods. Appl Phys Lett. 2007;
Energy and Environmental Science. Switzerland: Springer Nature; 90(12):122106.
2019:51‐104, DOI: 10.1007/978‐3‐030‐04474‐9_2.
26. Trasatti S, Buzzanca G. Ruthenium dioxide: a new interesting elec-
8. Das S, Dutta K, Kundu PP, Bhattacharya SK. Nanostructured trode material. Solid state structure and electrochemical behaviour.
polyaniline: an efficient support matrix for platinum‐ruthenium anode J Electroanal Chem Interfacial Electrochem. 1971;29(2):A1‐A5.
catalyst in direct methanol fuel cell. Fuel Cells. 2018;18(4):369‐378.
27. Zheng JP, Cygan PJ, Jow TR. Hydrous ruthenium oxide as an elec-
9. Dutta K, Das S, Kundu PP. Polyaniline nanowhiskers induced low trode material for electrochemical capacitors. J Electrochem Soc.
methanol permeability and high membrane selectivity in partially 1995;142(8):2699‐2703.
sulfonated PVdF‐co‐HFP membranes. RSC Adv. 2016;6(109): 28. Bélanger D, Brousse T, Long JW. Manganese oxides: battery materials
107960‐107969. make the leap to electrochemical capacitors. Electrochem Soc Inter-
face. 2008;17:49‐52.
10. Dutta K, Das S, Kundu PP. Highly methanol resistant and selective
ternary blend membrane composed of sulfonated PVdF‐co‐HFP, 29. Wu Z‐S, Ren W, Wang D‐W, Li F, Liu B, Cheng H‐M. High‐energy
sulfonated polyaniline and nafion. J Appl Polym Sci. 2016;133(15): MnO2 nanowire/graphene and graphene asymmetric electrochemical
43294. https://doi.org/10.1002/app.43294 capacitors. ACS Nano. 2010;4(10):5835‐5842.
BANERJEE ET AL. 17

30. Ryu KS, Kim KM, Park YJ, Park N‐G, Kang MG, Chang SH. Redox 48. Kwon H, Hong D, Ryu I, Yim S. Supercapacitive properties of 3D‐
supercapacitor using polyaniline doped with Li salt as electrode. Solid arrayed polyaniline hollow nanospheres encaging RuO2 nanoparticles.
State Ion. 2002;152‐153:861‐866. ACS Appl Mater Interfaces. 2017;9(8):7412‐7423.
31. Villers D, Jobin D, Soucy C, et al. The influence of the range of 49. Chen S, Liu B, Zhang X, et al. Growth of polyaniline on TiO2 tetragonal
electroactivity and capacitance of conducting polymers on the perfor- prism arrays as electrode materials for supercapacitor. Electrochim
mance of carbon conducting polymer hybrid supercapacitor. J Acta. 2019;300:373‐379.
Electrochem Soc. 2003;150(6):A747‐A752. 50. Lu X‐F, Chen X‐Y, Zhou W, Tong Y‐X, Li G‐R. α‐Fe2O3@PANI core‐
32. Huang W‐S, Humphrey BD, MacDiarmid AG. Polyaniline, a novel shell nanowire arrays as negative electrodes for asymmetric
conducting polymer. Morphology and chemistry of its oxidation and supercapacitors. ACS Appl Mater Interfaces. 2015;7(27):14843‐14850.
reduction in aqueous electrolytes. J Chem Soc, Faraday Trans 1. 51. Dhibar S, Bhattacharya P, Hatui G, Sahoo S, Das CK. Transition metal‐
1986;82:2385‐2400. doped polyaniline/single‐walled carbon nanotubes nanocomposites:
33. Gobal F, Faraji M. Electrodeposited polyaniline on Pd‐loaded TiO2 efficient electrode material for high performance supercapacitors.
nanotubes as active material for electrochemical supercapacitor. ACS Sustain Chem Eng. 2014;2(5):1114‐1127.
J Electroanal Chem. 2013;691:51‐56. 52. Han G, Liu Y, Zhang L, et al. MnO2 nanorods intercalating graphene
34. Xing J, Liao M, Zhang C, Yin M, Li D, Song Y. The effect of anions on oxide/polyaniline ternary composites for robust high‐performance
the electrochemical properties of polyaniline for supercapacitors. supercapacitors. Sci Rep. 2014;4(1–7):4824.
Phys Chem Chem Phys. 2017;19(21):14030‐14041. 53. Yu L, Gan M, Ma L, et al. Facile synthesis of MnO2/polyaniline nano-
35. Ryu KS, Kim KM, Park N‐G, Park YJ, Chang SH. Symmetric redox rod arrays based on graphene and its electrochemical performance.
supercapacitor with conducting polyaniline electrodes. J Power Synth Met. 2014;198:167‐174.
Sources. 2002;103(2):305‐309. 54. Jayakumar A, Yoon Y‐J, Wang R, Lee J‐M. Novel
36. Talbi H, Just P‐E, Dao LH. Electropolymerization of aniline on carbon- graphene/polyaniline/MnOx 3D hydrogels obtained by controlled
ized polyacrylonitrile aerogel electrodes: applications for morphology of MnOx in the graphene/polyaniline matrix for high per-
supercapacitors. J Appl Electrochem. 2003;33(6):465‐473. formance binder‐free supercapacitor electrodes. RSC Adv.
2015;5(114):94388‐94396.
37. Wang J, Xian H, Peng T, Sun H, Zheng F. Three‐dimensional
55. Sharma AK, Chaudhary G, Bhardwaj P, Kaushal I, Duhan S. Studies on
graphene‐wrapped PANI nanofiber composite as electrode material
metal doped polyaniline‐carbon nanotubes composites for high per-
for supercapacitors. RSC Adv. 2015;5(18):13607‐13612.
formance supercapacitor. Curr Anal Chem. 2017;13:277‐284.
38. Yu M, Ma Y, Liu J, Li S. Polyaniline nanocone arrays synthesized on
56. Giri S, Ghosh D, Mandal A, Das CK. Preparation and characterization
three‐dimensional graphene network by electro‐deposition for
of Zr (IV) doped polyaniline for supercapacitor application. Macromol
supercapacitor electrodes. Carbon. 2015;87:98‐105.
Symp. 2013;327(1):54‐63.
39. Brédas JL, Street GB. Polarons, bipolarons, and solitons in conducting
57. Shendkar JH, Jadhav VV, Shinde PV, Mane RS, O'Dwyer C. Hybrid
polymers. Acc Chem Res. 1985;18(10):309‐315.
composite polyaniline‐nickel hydroxide electrode materials for
40. Dutta K, Kumar P, Das S, Kundu PP. Utilization of conducting poly- supercapacitor applications. Heliyon. 2018;4(9):e00801.
mers in fabricating polymer electrolyte membranes for application in
58. Wang R, Han M, Zhao Q, et al. Hydrothermal synthesis of nanostruc-
direct methanol fuel cells. Polym Rev. 2014;54(1):1‐32.
tured graphene/polyaniline composites as high‐capacitance electrode
41. Stafström S, Brédas JL, Epstein AJ, et al. Polaron lattice in highly materials for supercapacitors. Sci Rep. 2017;7(1–9):44562.
conducting polyaniline: theoretical and optical studies. Phys Rev Lett. 59. Zhang K, Zhang LL, Zhao XS, Wu J. Graphene/polyaniline nanofiber
1987;59(13):1464‐1467. composites as supercapacitor electrodes. Chem Mater. 2010;22(4):
42. Silva CHB, Ferreira AMDC, Constantino VRL, Temperini MLA. Hybrid 1392‐1401.
materials of polyaniline and acidic hexaniobate nanoscrolls: high 60. Phokaratkul D, Mensing JPh, Jaruwongrangsee K, Lomas T,
polaron formation and improved thermal properties. J Mater Chem Tuantranont A, Wisitsoraat A. Novel 3D graphene foam‐polyaniline‐
A. 2014;2(22):8205‐8214. carbon nanotubes supercapacitor prepared by electropolymerization.
43. Aricò AS, Bruce P, Scrosati B, Tarascon J‐M, van Schalkwijk W. Nano- Proceedings of the 15th IEEE international conference on nanotech-
structured materials for advanced energy conversion and storage nology July 27‐30, 2015, Rome, Italy.
devices. Nat Mater. 2005;4(5):366‐377. 61. Bharadiya P, Jain R, Chaudhari V, Mishra S. Graphene oxide‐wrapped
44. Jin L, Jiang Y, Zhang M, et al. Oriented polyaniline nanowire arrays polyaniline nanorods for supercapacitor applications. Polym Compos.
grown on dendrimer (PAMAM) functionalized multiwalled carbon 2019;40(S2):E1716‐E1724.
nanotubes as supercapacitor electrode materials. Sci Rep. 2018; 62. Liu W, Wang S, Wu Q, et al. Fabrication of ternary hierarchical nano-
8(1):6268. fibers MnO2/PANI/CNT and their application in electrochemical
45. Kuila BK, Nandan B, Böhme M, Janke A, Stamm M. Vertically oriented supercapacitors. Chem Eng Sci. 2016;156:178‐185.
arrays of polyaniline nanorods and their super electrochemical prop- 63. Kadam AV, Patil SB. Polyaniline globules as a catalyst for WO3 nano-
erties. Chem Commun. 2009;0(38):5749‐5751. https://pubs.rsc.org/ particles for supercapacitor application. Mater Res Express. 2018;5(8):
en/content/articlelanding/2009/cc/b912513b#!divAbstract 085036.
46. Zou B, Gong S, Wang Y, Liu X. Tungsten oxide and polyaniline com- 64. Agyemang FO, Tomboc GM, Kwofie S, Kim H. Electrospun carbon
posite fabricated by surfactant‐templated electrodeposition and its nanofiber‐carbon nanotubes coated polyaniline composites with
use in supercapacitors. J Nanomater. 2014;2014(1–9):3. https://doi. improved electrochemical properties for supercapacitors. Electrochim
org/10.1155/2014/813120 Acta. 2018;259:1110‐1119.
47. Sopčić S, Roković MK, Mandić Z. Preparation and characterization of 65. Kazemi SH, Kiani MA, Mohamadi R, Eskandarian L. Metal‐polyaniline
RuO2/polyaniline/polymer binder composite electrodes for nanofibre composite for supercapacitor applications. Bull Mater Sci.
supercapacitor applications. J Electrochem Sci Eng. 2012;2:41‐52. 2014;37(5):1001‐1006.
18 BANERJEE ET AL.

66. Kumar MS, Yasoda KY, Batabyal SK, Kothurkar NK. Carbon‐ 84. Li J, Ren Y, Ren Z, Wang S, Qiu Y, Yu J. Aligned polyaniline nanowires
polyaniline nanocomposites as supercapacitor materials. Mater Res grown on the internal surface of macroporous carbon for
Express. 2018;5(4):045505. supercapacitors. J Mater Chem A. 2015;3(46):23307‐23315.
67. Chang C‐M, Weng C‐J, Chien C‐M, et al. Polyaniline/carbon nanotube 85. Kim J, Sohn J, Jo Y, et al. Drop‐casted polyaniline thin films on flexible
nanocomposite electrodes with biomimetic hierarchical structure for substrates for supercapacitor applications. J Korean Phys Soc.
supercapacitors. J Mater Chem A. 2013;1(46):14719‐14728. 2014;65:L1320‐L1323.
68. Simotwo SK, DelRe C, Kalra V. Supercapacitor electrodes based on 86. Zhou D, Che B, Lu X. Rapid one‐pot electrodeposition of
high‐purity electrospun polyaniline and polyaniline‐carbon nanotube polyaniline/manganese dioxide hybrids: a facile approach to stable
nanofibers. ACS Appl Mater Interfaces. 2016;8(33):21261‐21269. high‐performance anodic electrochromic materials. J Mater Chem C.
69. Male U, Shin BK, Huh DS. Synthesis and characterization of 2017;5(7):1758‐1766.
polyaniline‐grafted CNT as electrode materials for supercapacitors. 87. Wu Q, Xu Y, Yao Z, Liu A, Shi G. Supercapacitors based on flexible
Macromol Res. 2017;25(11):1121‐1128. graphene/polyaniline nanofiber composite films. ACS Nano.
70. Chaudhari S, Sharma Y, Archana PS, et al. Electrospun polyaniline 2010;4(4):1963‐1970.
nanofibers web electrodes for supercapacitors. J Appl Polym Sci. 88. Takei T, Muraki N, Xu N, Miura A, Kumada N. Anodic hybridization of
2013;4:1660‐1668. fluorinated layered perovskite nanosheet with polyaniline for electro-
71. Bigdeli H, Moradi M, Borhani S, Jafari EA, Hajati S, Kiani MA. One‐pot chemical capacitor. Colloids Surf A Physicochem Eng Asp.
electrochemical growth of sponge‐like polyaniline‐intercalated 2014;459:186‐193.
phosphorous‐doped graphene oxide on nickel foam as binder‐free 89. Guo SN, Zhu Y, Yan YY, et al. (Metal‐organic framework)‐polyaniline
electrode material of supercapacitor. Physica E. 2018;100:45‐53. sandwich structure composites as novel hybrid electrode materials
72. Mondal S, Rana U, Malik S. Reduced graphene oxide/Fe3O4/ for high‐performance supercapacitor. J Power Sources. 2016;316:
polyaniline nanostructures as electrode materials for an all‐solid‐ 176‐182.
state hybrid supercapacitor. J Phys Chem C. 2017;121(14):7573‐7583. 90. Liu W, Yan X, Chen J, Feng Y, Xue Q. Novel and high‐performance
73. Malik R, Zhang L, McConnell C, et al. Three‐dimensional, free‐ asymmetric micro‐supercapacitors based on graphene quantum dots
standing polyaniline/carbon nanotube composite‐based electrode and polyaniline nanofibers. Nanoscale. 2013;5(13):6053‐6062.
for high‐performance supercapacitors. Carbon. 2017;116:579‐590.
91. Tian Y, Cong S, Su W, et al. Synergy of W18O49 and polyaniline for
74. Aslan M, Weingarth D, Herbeck‐Engel P, Grobelsek I, Presser V. Poly- smart supercapacitor electrode integrated with energy level indicating
vinylpyrrolidone/polyvinyl butyral composite as a stable binder for functionality. Nano Lett. 2014;14(4):2150‐2156.
castable supercapacitor electrodes in aqueous electrolytes. J Power
92. Song Y, Jiang L, Qi W, Lu C, Zhu X. Fabrication of solid aluminium
Sources. 2015;279:323‐333.
electrolytic capacitors utilizing conductive polyaniline solutions. Synth
75. Gao S, Zhang L, Qiao Y, Dong P, Shi J, Cao S. Electrodeposition of Met. 2012;162(3‐4):368‐374.
polyaniline on three‐dimensional graphene hydrogel as a binder‐free
93. Yamamoto H, Oshima M, Hosaka T, Isa I. Solid electrolytic capacitors
supercapacitor electrode with high power and energy densities. RSC
using an aluminum alloy electrode and conducting polymers. Synth
Adv. 2016;6(64):58854‐58861.
Met. 1999;104(1):33‐38.
76. Wilson E, Islam MF. Ultracompressible, high‐rate supercapacitors
94. Xiao F, Yang S, Zhang Z, et al. Scalable synthesis of freestanding
from graphene‐coated carbon nanotube aerogels. ACS Appl Mater
sandwich‐structured graphene/polyaniline/graphene nanocomposite
Interfaces. 2015;7(9):5612‐5618.
paper for flexible all‐solid‐state supercapacitor. Sci Rep. 2015;5(1):
77. Hong J‐Y, Bak BM, Wie JJ, Kong J, Park HS. Reversibly compressible, 9359.
highly elastic, and durable graphene aerogels for energy storage
devices under limiting conditions. Adv Funct Mater. 2015;25(7): 95. Maier MA, Babu RS, Sampaio DM, de Barros ALF. Binder‐free
1053‐1062. polyaniline interconnected metal hexacyanoferrates nanocomposites
(Metal = Ni, Co) on carbon fibers for flexible supercapacitors. J Mater
78. Lv P, Tang X, Zheng R, Ma X, Yu K, Wei W. Graphene/polyaniline Sci Mater Electron. 2017;28:17405‐17413.
aerogel with superelasticity and high capacitance as highly
compression‐tolerant supercapacitor electrode. Nanoscale Res Lett. 96. Simotwo SK, Kalra V. Polyaniline‐carbon based binder‐free asymmet-
2017;12(1):630. ric supercapacitor in neutral aqueous electrolyte. Electrochim Acta.
2018;268:131‐138.
79. Zhou K, He Y, Xu Q, et al. A hydrogel of ultrathin pure polyaniline
nanofibers: oxidant‐templating preparation and supercapacitor appli- 97. Nam MS, Patil U, Park B, Sim HB, Jun SC. A binder free synthesis of
cation. ACS Nano. 2018;12(6):5888‐5894. 1D PANI and 2D MoS2 nanostructured hybrid composite electrodes
by the electrophoretic deposition (EPD) method for supercapacitor
80. Zou Y, Zhang Z, Zhong W, Yang W. Hydrothermal direct synthesis of
application. RSC Adv. 2016;6(103):101592‐101601.
polyaniline, graphene/polyaniline and N‐doped graphene/polyaniline
hydrogels for high performance flexible supercapacitors. J Mater 98. Wang L, Lv S, Zhang J, et al. Low‐cost, flexible graphene/polyaniline
Chem A. 2018;6(19):9245‐9256. nanocomposite paper as binder‐free high‐performance supercapaci-
tor electrode. Funct Mater Lett. 2014;07:1440010(06).
81. Dawouda HD, Altahtamounia TM, Zaghoa MM, Bensalahb N. A brief
overview of flexible CNT/PANI super capacitors. Mater Sci 99. Ajit S, Palaniappan S, Gopukumar S. Polyaniline binder for functional-
Nanotechnol. 2017;1:23‐36. ized acetylene black: a hybrid material for supercapacitor. Synth Met.
2013;180:43‐48.
82. Sarker AK, Hong J‐D. Flexible and transparent plastic electrodes com-
posed of reduced graphene oxide/polyaniline films for supercapacitor 100. Cheng Q, Tang J, Shinya N, Qin L‐C. Polyaniline modified graphene and
application. Bull Kor Chem Soc. 2014;35(6):1799‐1805. carbon nanotube composite electrode for asymmetric supercapacitors
of high energy density. J Power Sources. 2013;241:423‐428.
83. Sarker AK, Hong J‐D. Layer‐by‐layer self‐assembled multilayer films
composed of graphene/polyaniline bilayers: high‐energy electrode 101. Fathi M, Saghafi M, Mahboubi F, Mohajerzadeh S. Synthesis and elec-
materials for supercapacitors. Langmuir. 2012;28(34):12637‐12646. trochemical investigation of polyaniline/unzipped carbon nanotube
BANERJEE ET AL. 19

composites as electrode material in supercapacitors. Synth Met. 119. Bian L, Luan F, Liu S, Liu X. Self‐doped polyaniline on functionalized
2014;198:345‐356. carbon cloth as electroactive materials for supercapacitor. Electrochim
Acta. 2012;64:17‐22.
102. Liu M, Miao Y, Zhang C, et al. Hierarchical composites of polyaniline‐
graphene nanoribbons‐carbon nanotubes as electrode materials in all‐ 120. Zang X, Li X, Zhu M, et al. Graphene/polyaniline woven fabric com-
solid‐state supercapacitors. Nanoscale. 2013;5(16):7312‐7320. posite films as flexible supercapacitor electrodes. Nanoscale.
2015;7(16):7318‐7322.
103. Zhang Y, Cui X, Zu L, et al. New supercapacitors based on the syner-
getic redox effect between electrode and electrolyte. Materials. 121. Iessa KHS, Zhang Y, Zhang G, Xiao F, Wang S. Conductive porous
2016;9(9):734. sponge‐like ionic liquid‐graphene assembly decorated with nanosized
polyaniline as active electrode material for supercapacitor. J Power
104. Kim J, Ju H, Inamdar AI, et al. Synthesis and enhanced electrochemi-
Sources. 2016;302:92‐97.
cal supercapacitor properties of Ag‐MnO2‐polyaniline nanocomposite
electrodes. Energy. 2014;70:473‐477. 122. Pedros J, Bosca A, Martinez J, et al. Polyaniline nanofiber sponge
filled graphene foam as high gravimetric and volumetric capacitance
105. Mandal M, Ghosh D, Giri S, Shakir I, Das CK. Polyaniline‐wrapped 1D
electrode. J Power Sources. 2016;317:35‐42.
CoMoO4.0.75H2O nanorods as electrode materials for
supercapacitor energy storage applications. RSC Adv. 2014;4(58): 123. Hu N, Zhang L, Yang C, et al. Three‐dimensional skeleton networks of
30832‐30839. graphene wrapped polyaniline nanofibers: an excellent structure for
high‐performance flexible solid‐state supercapacitors. Sci Rep.
106. Shi X, Hu Y, Li M, et al. Highly specific capacitance materials con- 2016;6(1):19777.
structed via in situ synthesis of polyaniline in a cellulose matrix for
supercapacitors. Cellul. 2014;21(4):2337‐2347. 124. Giri S, Ghosh D, Das CK. Growth of vertically aligned tunable
polyaniline on graphene/ZrO2 nanocomposites for supercapacitor
107. Yu J, Lu W, Pei S, et al. Omnidirectionally stretchable high‐ energy‐storage application. Adv Funct Mater. 2014;24(9):1312‐1324.
performance supercapacitor based on isotropic buckled carbon nano-
tube films. ACS Nano. 2016;10(5):5204‐5211. 125. Zhou X, Li L, Dong S, et al. A renewable bamboo carbon/polyaniline
composite for a high‐performance supercapacitor electrode material.
108. Xie D, Jiang Q, Fu G, et al. Preparation of cotton‐shaped CNT/PANI J Solid State Electrochem. 2011;16:877‐882.
composite and its electrochemical performances. Rare Metals.
126. Luo J, Zhong W, Zou Y, Xiong C, Yang W. Preparation of morphology‐
2011;30(S1):94‐97.
controllable polyaniline and polyaniline/graphene hydrogels for high
109. Zhao D, Guo X, Gao Y, Gao F. An electrochemical capacitor electrode performance binder‐free supercapacitor electrodes. J Power Sources.
based on porous carbon spheres hybrided with polyaniline and nano- 2016;319:73‐81.
scale ruthenium oxide. ACS Appl Mater Interfaces. 2012;4(10):
127. Ismail YA, Chang J, Shin SR, Mane RS, Han S, Kim SJ. Hydrogel‐assisted
5583‐5589.
polyaniline microfiber as controllable electrochemical actuatable
110. Feng X, Yan Z, Chen N, et al. Synthesis of a graphene/polyaniline/ supercapacitor. J Electrochem Soc. 2009;156(4):A313‐A317.
MCM‐41 nanocomposite and its application as a supercapacitor.
128. Yan Y, Cheng Q, Wang G, Li C. Growth of polyaniline nanowhiskers
New J Chem. 2013;37(7):2203‐2209.
on mesoporous carbon for supercapacitor application. J Power
111. Ghosh D, Giri S, Mandal A, Das CK. Supercapacitor based on Hþ and Sources. 2011;196(18):7835‐7840.
Ni 2þ Co‐doped polyaniline‐MWCNTs nanocomposite: synthesis and
129. Zhang Q, Li Y, Feng Y, Feng W. Electropolymerization of graphene
electrochemical characterization. RSC Adv. 2013;3(29):11676‐11685.
oxide/polyaniline composite for high‐performance supercapacitor.
112. Jabeen N, Xia Q, Yang M, Xia H. Unique core‐shell nanorod arrays Electrochim Acta. 2013;90:95‐100.
with polyaniline deposited into mesoporous NiCo2O4 support for 130. Woo S, Dokko K, Nakano H, Kanamura K. Incorporation of
high‐performance supercapacitor electrodes. ACS Appl Mater Inter- polyaniline into macropores of three‐dimensionally ordered
faces. 2016;8(9):6093‐6100. macroporous carbon electrode for electrochemical capacitors. J
113. G‐m Z, Wang D‐w, Li F, Zhang L‐L, Weng Z, Cheng H‐M. The effect Power Sources. 2009;190(2):596‐600.
of carbon particle morphology on the electrochemical properties of 131. Xia C, Xie Y, Du H, Wang W. Ternary nanocomposite of
nanocarbon/polyaniline composites in supercapacitors. New Carbon polyaniline/manganese dioxide/titanium nitride nanowire array for
Mater. 2011;26:180‐186. supercapacitor electrode. J Nanopart Res. 2015;17(1–12):30.
114. Faraji M, Najafi Moghadam P, Hasanzadeh R. Fabrication of binder‐ 132. Su H, Wang T, Zhang S, et al. Facile synthesis of polyaniline/TiO2/
free polyaniline grafted multi‐walled carbon nanotube/TiO2 graphene oxide composite for high performance supercapacitors.
nanotubes/Ti as a novel energy storage electrode for supercapacitor Solid State Sci. 2012;14(6):677‐681.
applications. Chem Eng J. 2016;304:841‐851.
133. Li S, Wu D, Cheng C, et al. Polyaniline‐coupled multifunctional 2D
115. Zhang H, Cao G, Wang W, et al. Influence of microstructure on the metal oxide/hydroxide graphene nanohybrids. Angew Chem Int Ed.
capacitive performance of polyaniline/carbon nanotube array com- 2013;52(46):12105‐12109.
posite electrodes. Electrochim Acta. 2009;54(4):1153‐1159.
134. Wang D‐W, Li F, Zhao J, et al. Fabrication of graphene/polyaniline
116. Zhou S, Mo S, Zou W, Jiang F, Zhou T, Yuan D. Preparation of composite paper via in situ anodic electropolymerization for high‐
polyaniline/2‐dimensional hexagonal mesoporous carbon composite performance flexible electrode. ACS Nano. 2009;3(7):1745‐1752.
for supercapacitor. Synth Met. 2011;161(15‐16):1623‐1628.
135. Li J, Xiao D, Ren Y, Liu H, Chen Z, Xiao J. Bridging of adjacent
117. Sha C, Lu B, Mao H, et al. 3D ternary nanocomposites of molybde- graphene/polyaniline layers with polyaniline nanofibers for
num disulfide/polyaniline/reduced graphene oxide aerogel for high supercapacitor electrode materials. Electrochim Acta. 2019;300:
performance supercapacitors. Carbon. 2016;99:26‐34. 193‐201.
118. Li Y, Fang Y, Liu H, Wu X, Lu Y. Free‐standing 3D polyaniline‐CNT/ 136. Lee K‐U, Byun JY, Shin HJ, Kim SH. A high‐performance
Ni‐fiber hybrid electrodes for high‐performance supercapacitors. supercapacitor based on polyaniline‐nanoporous gold. J Alloys Compd.
Nanoscale. 2012;4(9):2867‐2869. 2019;779:74‐80.
20 BANERJEE ET AL.

137. Yasoda KY, Mikhaylov AA, Medvedev AG, et al. Brush like polyaniline 141. Vedhanarayanan B, Huang T‐H, Lin T‐W. Fabrication of 3D hierarchi-
on vanadium oxide decorated reduced graphene oxide: efficient cally structured carbon electrode for supercapacitors by
electrode materials for supercapacitor. J Energy Storage. 2019;22: carbonization of polyaniline/carbon nanotube/graphene composites.
188‐193. Inorg Chim Acta. 2019;489:217‐223.
142. Elanthamilan E, Sathiyan A, Rajkumar S, Sheryl EJ, Merlin JP.
138. Cao X, Zeng H‐Y, Xu S, Yuan J, Han J, Xiao G‐F. Facile fabrication of
Polyaniline based charcoal/Ni nanocomposite material for high perfor-
the polyaniline/layered double hydroxide nanosheet composite for
mance supercapacitors. Sustain Energy and Fuels. 2018;2(4):811‐819.
supercapacitors. Appl Clay Sci. 2019;168:175‐183.

139. He Y, Wang X, Huang H, Zhang P, Chen B, Guo Z. In‐situ

electropolymerization of porous conducting polyaniline fibrous net- How to cite this article: Banerjee J, Dutta K, Kader MA,
work for solid‐state supercapacitor. Appl Surf Sci. 2019;469:446‐455. Nayak SK. An overview on the recent developments in
140. Li K, Liu X, Chen S, Pan W, Zhang J. A flexible solid‐state polyaniline‐based supercapacitors. Polym Adv Technol.
supercapacitor based on graphene/polyaniline paper electrodes. J 2019;1–20. https://doi.org/10.1002/pat.4624
Energy Chem. 2019;32:166‐173.