Carbon Trends 7 (2022) 100154

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Carbon Trends
journal homepage: www.elsevier.com/locate/cartre

Polyaniline wrapped carbon nanotube/exfoliated MoS2 nanosheet

composite as a promising electrode for high power supercapacitors
M Jasna a,∗, Manoj Muraleedharan Pillai b, A. Abhilash a, P.S. Midhun a, S. Jayalekshmi a,c,
M.K. Jayaraj d
a
Department of Physics, Cochin University of Science and Technology, Kerala 682022, India
b
Department of Applied Physics, University of Eastern Finland, Kuopio FI-70211, Finland
c
Centre of Excellence in Advanced Materials, Cochin University of Science and Technology, Kerala 682022, India
d
University of Calicut, Thenhipalam, Kerala 673635, India

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

Article history: Polyaniline (PANI) wrapped, carbon nanotube (CNT)/and exfoliated MoS2 composite (PANI/CNT/e-MoS2 )
Received 19 August 2021 based electrodes are developed for applications as high-quality supercapacitor electrodes by a facile and
Revised 4 January 2022
effective in-situ oxidative polymerization method. Exfoliation of single/bilayer MoS2 nanosheets via elec-
Accepted 15 January 2022
trochemical method and incorporation of CNT in PANI/e-MoS2 composite are confirmed by scanning and
transmission electron microscopy techniques. Electrochemical properties of PANI/CNT/e-MoS2 electrode
Keywords: are evaluated by cyclic voltammetry and galvanostatic charge-discharge techniques. The incorporation of
Energy storage CNT in PANI/e-MoS2 composite provides maximum utilization of PANI nanowires to achieve maximum ca-
Supercapacitors pacitance. Composite electrode based on PANI/CNT/e-MoS2 shows high specific capacitance of 532 F g−1
2D materials
at a current density of 1 A g−1 as well as good rate capability from 1 A g−1 to 10 A g−1 . Symmetric
MoS2
supercapacitor assembled using PANI/CNT/e-MoS2 composite electrode exhibits good cycling stability and
CNT/Polymer composites
80% capacity retention after 40 0 0 cycles and gives energy density of 11.8 Wh kg−1 and power density of
3785 W kg−1 . Furthermore, electrochemical impedance spectroscopy (EIS) analysis ensures much lower
equivalent series resistance of the PANI/CNT/e-MoS2 electrode. Besides, CNT acts as active electrode ma-
terial in PANI/CNT/e-MoS2 composite and also provides more active sites for insertion and extraction of
ions. This electrode design provides a facile and promising approach for improving the electrochemical
performance of PANI based electrodes.
© 2022 The Authors. Published by Elsevier Ltd.
This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)

1. Introduction terface. Here capacitance mainly depends on the active surface

The rapid development of portable electronic devices, elec-
tric vehicles (EV) and hybrid electric vehicles (HEV) demands
the commercial production of energy storage devices with high
energy density and high power density [1–3]. Supercapacitors
(SCs) are considered to be alternative devices to meet increasing
power demand because of their rapid charge-discharge processes,
high power density and long cycle life [4,5]. Based on the na-
ture of electrode materials and operating mechanism, supercapac-
itors can be classified into three types: (a) electric double-layer
capacitors (EDLCs), (b) pseudo-capacitors (PCs) and (c) hybrid-
capacitors (HCs). In EDLCs, capacitance is generated from the ac-
cumulation of electrostatic charges at the electrode/electrolyte in-
∗ bility than EDLCs and pseudo- capacitors [13–15].
Corresponding author.
E-mail address: jma@cusat.ac.in (M. Jasna).
area of electrodes used, which are generally based on carbon
based materials like CNT, graphene, porous carbon, carbon spheres
and carbon black [6,7]. Energy storage in pseudo-capacitors is
through the redox reactions involved in the electrode materials
made from transition metal dichalcogenides or metal oxides such
as MoS2 , MnO2 and Mn3 O4 or electrochemical conducting poly-
mers such as polyaniline (PANI), polypyrrole (PPy) and poly(3,4-
ethylenedioxythiophene)(PEDOT) [4,8–11]. Due to these redox re-
actions, pseudocapacitors have capacitance far higher than that of
EDLCs. Hybrid supercapacitors work on the basis of both electro-
static and electrochemical storage mechanisms and hence are the
combination of EDLCs and pseudocapacitors [12]. With the involve-
ment of both EDLC and pseudo- capacitive behavior, hybrid capac-
itors have a higher energy density, power density and cycling sta-

https://doi.org/10.1016/j.cartre.2022.100154
2667-0569/© 2022 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)
M. Jasna, M. Muraleedharan Pillai, A. Abhilash et al.
Electrochemical conducting polymers (ECPs) have been widely
used for various applications [16–18], especially in energy stor-
age applications because of their good electrical conductivity, large
surface area, a short path for ion transport and superior electro-
chemical activity [19,20]. Among different ECPs, PANI has acquired
broad consideration in energy storage devices because of its cost-
effectiveness, ease of synthesis, high theoretical specific capaci-
tance, good electrical properties, high thermal stability, and envi-
ronmental friendliness [21–23]. Nevertheless, PANI has two signif-
icant drawbacks related to its low practical capacitance and poor
cycling stability because of the fragile backbone of this polymer
which confines its application in supercapacitors. Moreover, volu-
metric change induced during the charge/discharge cycle leads to
the loss of active materials and the resultant structural instabil-
ity leads to poor supercapacitor performance [24,25]. To overcome
these issues, numerous investigations are being carried out on de-
veloping hybrid electrodes in which PANI nanowires are grown
on various nanosheets and nanotubes which can act as templates
and improve the electrochemical performance of PANI electrodes
[26,27]. Manoj et al. have reported the studies on GO/PANI com-
posite electrode in which GO acts as a template for the growth
of PANI nanowires and a specific capacitance of 132 F g−1 at a
current density of 5 A g−1 has been obtained [28]. Ren’s group
has reported the growth of MoS2 /PANI hybrid electrode by in-
situ polymerization of PANI on tubular MoS2 and its symmet-
ric supercapacitors are found to exhibit specific capacitance of
124 F g−1 at a current density of 1 A g−1 [29]. To hinder the in-
herent drawbacks of PANI, carbon based materials including multi-
walled carbon nanotubes (MWCNTs), carbon cloth and graphene
oxide are used to make composites with PANI to make the hy-
brid electrode [30,31]. To commercialize the supercapacitor tech-
nologies for large-scale applications, the developed electrode ma-
terial must have cost-effectiveness, scalability and high stability. To
realize supercapacitors with excellent performance characteristics,
several approaches based on ternary composites of PANI utilizing
carbon-based nanomaterials such as CNT and graphene along with
2D nanosheets have been developed [32]. Among various carbon-
based nanomaterials, MWCNTs constitute a very unique form of
carbon and have gained great attention as supercapacitor elec-
trodes due to the high electrical conductivity, excellent chemical
stability and high electrochemically active surface area possessed
by them. Moreover, the honeycomb structure of CNT with porous
nanostructure provides a good conducting path for fast electro-
chemical kinetic processes during the charge/discharge cycle. The
electrochemical performance of supercapacitors can be improved
by forming a composite structure of PANI and 2D nanosheets with
CNT to serve as the electrode [33]. This type of ternary compos-
ite structure can increase the electrochemical activity by facilitat-
ing more electrochemical active sites within the electrode material.
Only a few studies have been reported on ternary composites for
supercapacitor applications, and the research is still at the initial
stage. Ishaq et al. reported a ternary composite graphene/metal-
doped iron oxide/polypyrrole (rGO/MnFe2 O4 /Ppy) electrode with
specific capacitance of 232 F g−1 [34]. Dubin et al. prepared
MnO2 @MoS2 /Polypyrrole ternary composite through hydrothermal
method and a simple oxidation process using MnO2 @MoS2 sheet
as the substrate and polypyrrole and measured specific capacitance
as 490 F g−1 at a current density of 1 A g−1 with cyclic stability
of 90% after 10 0 0 cycles [35]. Lin et al. synthesized ternary com-
posite nanosheets of MoS2 /WS2 /Graphene via the simple chemical
method and served as a supercapacitor electrode that exhibited
a specific capacitance of 365 F g−1 at 1 A g−1 in 1M KOH elec-
trolytes [36]. The layered, two-dimensional (2D) transition metal
dichalcogenide (TMDC), MoS2 has achieved primary progress as a
substrate in the ternary composite design for developing energy
storage devices [8]. In the present work, MoS2 nanosheets serve as
2
Carbon Trends 7 (2022) 100154
substrates for the efficient growth of PANI nanowires in the design
of the ternary composite electrode and subsequently contribute to-
wards enhancing the performance efficiency of the resulting su-
percapacitor devices. Exfoliated MoS2 nanosheets have been widely
used in the design of composite electrodes for applications in en-
ergy storage devices because of their high electrochemical activity
and good chemical stability. Several methods based on mechanical
and chemical principles have been widely used for the exfoliation
of MoS2 . Mechanical exfoliation based on ultra-sonication is time-
consuming, and also the process causes damages on MoS2 sheets
whose lateral size becomes small [37]. Another well-known tech-
nique is lithium intercalation, in which large-area MoS2 sheets can
be generated through exfoliation. Jing and co-workers[38] have re-
ported the exfoliation of MoS2 by lithium interaction in which n-
butyl lithium was used. The main disadvantage of this method is
that it is time-consuming. Moreover, the restacking tendency of the
resulting MoS2 nanosheets significantly restricts applications for
developing supercapacitors. The introduction of CNT in the MoS2
based ternary composite can hinder the agglomeration and im-
prove the electronic conductivity of MoS2 . Additionally, CNT help
to increase electrolyte accessibility and facilitate the creation of
more electroactive areas within the composite electrode material.
The ternary composite structure based on PANI wrapped, CNT in-
corporated, MoS2 nanosheets is a 3-dimensional one and helps to
attain maximum utilization of PANI to achieve its highest capaci-
tance.
Furthermore, the current collector plays a vital role in the elec-
trochemical performance of supercapacitors due to its direct im-
pact on fabrication cost, environment, and flexibility of the device.
Commercially available carbon cloth (CC) is one promising alter-
native to traditional electrode material like metal current collec-
tors (aluminum, copper, nickel, etc.) due to its excellent mechani-
cal flexibility, strength, good conductivity, low cost, and lightweight
[39]. Researchers have been widely used CC as current collec-
tors, and its results exhibit excellent electrochemical performance
[40].
The focal theme of the present studies is the in-situ synthe-
sis of PANI wrapped, CNT incorporated MoS2 ternary composite
for applications as supercapacitor electrodes. The effect of CNT in-
tegration with PANI/MoS2 in enhancing the electrolyte accessibil-
ity within the electrode material has been explored in detail. The
electrochemical method is employed for the exfoliation of large-
area MoS2 nanosheets. This is an efficient method since it takes
less time, and also, high-quality nanosheets can be obtained. The
pictorial illustration of the designed PANI/CNT/e-MoS2 composite
formation process is shown in Scheme 1.
This innovative approach for the composite formation gives ex-
cellent electrochemical performance due to the synergistic effect
between individual components. Moreover, the two-electrode sys-
tem adopted in the present work provides device-level results
comparable to practical SC technology. In addition, a 3D flexible
carbon cloth is employed as the current collector, which enables
the development of next-generation flexible SC technology.
2. Experimental Section
2.1. Materials
Aniline, MoS2 flakes (size < 6 μm, purity: 99.995%) and am-
monium persulfate (APS, assay > 98%) were obtained from Merck
and MWCNTs (diameter: 30-50 nm, length: ∼20 μm and purity >
95 wt%) were purchased from Chengdu organic chemical Co. Ltd.
Aniline was purified using vacuum filtration at reduced pressure
before use. Other chemicals were of analytical grade and were used
without any further purification.
M. Jasna, M. Muraleedharan Pillai, A. Abhilash et al.
Scheme 1. The formation process of PANI/CNT/e-MoS2 composite.
Fig. 1. (a) Schematic representation of exfoliation of bulk MoS2 and (b) Galvanostatic discharge curve for Li+ intercalation.
2.2. Exfoliation of MoS2
From bulk MoS2 , exfoliated MoS2 nanosheets were obtained via
Li intercalation by electrochemical method. For this, MoS2 pellets
of 13 mm diameter were prepared using a pelletizer. A Swagelok
type cell was assembled with MoS2 pellet as cathode and Li metal
as anode with LiPF6 in ethylene carbonate: diethyl carbonate (EC:
DEC) (v:v = 1:1) as electrolyte. Electrochemical exfoliation was car-
ried out at a potential of 1.0 V, below which fragmentation of MoS2
layers may occur. The exfoliation process of bulk MoS2 is schemat-
ically shown in Fig. 1a. The Li intercalation process was controlled
by galvanostatic discharge and the discharge curve is shown in
Fig. 1b.
The assembled cell was discharged to 1.0 V at 0.1 C and then
disassembled and washed with hexane to remove excess lithium
and ultra-sonicated in 200 mL deionized water for 30 min. The
mixture was then centrifuged at 30 0 0 rpm for 30 min and the su-
pernatant was collected for making the composite electrode.
2.3. Functionalization of MWCNTs
Normally carbon nanotubes are hydrophobic and hence insolu-
ble in many solvents. Through a suitable functionalization process,
functional groups can be attached to the surfaces of CNT, which
makes them highly dispersible in many solvents. Many strategies
have been utilized to purify MWCNTs using a mixture of acids
[41–44]. In the present work, in a typical functionalization process,
pristine MWCNT (1 g) were dispersed in the mixture of H2 SO4
(6M) and HNO3 (6M) in a 3:1 volume ratio and ultra-sonicated for
1 h. The mixture was then refluxed at 120 °C for 12 h and then
vacuum filtered using polyvinylidene difluoride (PVDF) membrane
with a pore size of 0.2 μm and washed with deionized water until
3
Carbon Trends 7 (2022) 100154
the pH of the solution came to 7 and dried at 60 °C in a vacuum
oven overnight.
2.4. Synthesis of PANI/CNT/e-MoS2 composites
Polyaniline/carbon nanotubes/molybdenum disulfide composite
was synthesized by in-situ oxidative polymerization of monomer
aniline in the presence of the dispersion of acid-functionalized
MWCNT and exfoliated MoS2 in HCl solution using ammonium
persulfate ((NH4 )2 S2 O8 , APS) as the oxidant and the schematic rep-
resentation of the synthesis procedure is given in Fig. 2. Typi-
cally, 2.3 mL aniline was first added to 50 mL 1M HCl solution
and 0.095 g of e-MoS2 and MWCNT was added into the above
solution. The mixture was ultra-sonicated for 1 h and then mag-
netically stirred for another 1 h. APS dissolved in 50 mL 1 M
HCl solution was slowly added dropwise to the mixture which is
continuously stirred in an ice bath. During the in-situ polymer-
ization of aniline, the color was found to change to dark green
and the mixture was stirred for 6 h. The obtained precipitate was
collected by vacuum filtration, washed with deionized water, and
dried in a vacuum oven at 60 °C for 12 h to get the final product,
PANI/CNT/e-MoS2 composite material. For comparison, PANI/bulk
MoS2 and PANI/exfoliated MoS2 composites were also prepared,
using the same procedure, which was denoted as PANI/MoS2 and
PANI/e-MoS2 , respectively.
3. Characterization
Field emission scanning microscope (FESEM) images were ob-
tained using Supra 40 VP Carl Zeiss, Germany machine, with an
accelerating voltage of 5 kV, the working distance of 4.9 mm, and
the emission current of 100 pA. Transmission electron microscope
M. Jasna, M. Muraleedharan Pillai, A. Abhilash et al.
Fig. 2. The synthesis scheme of PANI/CNT/e-MoS2 composite.
(TEM) images were recorded using Jeol/JEM 2100 microscope with
accelerating voltage of 200 kV, emission current of 103 μA, and
spot size of 1 nm. Samples were prepared for TEM measurements
using ultrasonication of materials in isopropyl alcohol and drop
cast on the TEM grid (200 mesh carbon-coated Cu). Micro-Raman
spectroscopy measurements were done using Lab RAM HR spec-
trophotometer (HORIBA Jobin Yvon) with argon-ion laser as the ex-
citation source of wavelength 514.5 nm with laser power of 1 mW,
number of accumulation of 1, and exposure time of 10 s. The
electrochemical performance of the synthesized electrode materi-
als was assessed using SP300 electrochemical workstation (Biologic
Science Instruments) at room temperature.
4. Electrochemical measurement
The electrochemical performance of the prepared samples was
analyzed using the techniques of cyclic voltammetry (CV), galvano-
static charge−discharge (GCD) test and electrochemical impedance
spectroscopy (EIS). Electrodes were prepared by mixing electro-
active materials, acetylene black and polyvinylidene difluoride
(PVDF) in N-methyl-2-pyrrolidone (NMP) in a mass ratio of
80:10:10, respectively, to form a homogeneous slurry. The slurry
was then coated on a carbon cloth (CC) current collector. Finally,
the coated carbon cloth was dried at 70 °C in the oven for 12 h.
After drying, it was cut into circular discs to form working elec-
trodes. The mass loading of the active material was about 1.2 mg.
Two electrode Swagelok supercapacitor test cells were assembled
using PANI/MoS2 , PANI/e-MoS2 and PANI/CNT/e-MoS2 composites
as working electrodes and aqueous 1M H2 SO4 as electrolyte. Elec-
trochemical studies were carried out over a potential range from 0
to 0.8 V and EIS measurements were carried out in the frequency
range of 200 kHz–10 mHz at open circuit potential with an ampli-
tude of 10 mV.
The specific capacitance of the assembled supercapacitors was
calculated from the GCD curve using Eq. 1[32]:
C = It/MV
where I is the applied current, t, the discharge time during the
discharge process, M (mg), the total mass of active material in both
the electrodes and V , the voltage window. The specific capaci-
Carbon Trends 7 (2022) 100154
tance of a single electrode was calculated using CS = 4C. The en-
ergy density (E) and power density (P) are two substantial param-
eters that determine the performance of a supercapacitor. These
parameters are calculated using equations 2 and 3 [32]:
E = (1/2 × 3.6 )C ∗ V 2 (2)
P = (E/t ) × 3600 (3)
where C in F g-1
is the specific capacitance of SC, ࢞V, the potential
window in volts and t, the discharging time in seconds.
5. Results and discussion
Lithium intercalation is a widely used process to exfoliate lay-
ered materials into 2D nanosheets. In this technique, lithium metal
serves as a Li-ion source. During discharging of the assembled
device, Li ions penetrate in between the MoS2 layers leading to
an increase in the interfacial spacing, as shown in Fig. 1. During
water-assisted ultrasonication, the expanded material undergoes
exfoliation and finally, nanosheets are obtained. The FESEM im-
ages of pristine MoS2 and exfoliated MoS2 nanosheets are shown
in Figs. 3a and 3b, respectively. In Figs. 3c and 3d, TEM images of
pristine MoS2 and exfoliated MoS2 nanosheets are shown, respec-
tively, and the corresponding SAED pattern is shown as an inset
image. The analysis reveals the presence of large area exfoliated
mono- or bi-layer MoS2 nanosheets. The retention of the SAED pat-
tern in exfoliated MoS2 confirms exfoliation has not changed the
structural integrity of MoS2 .
The XRD patterns of PANI/MoS2 , PANI/e-MoS2, and PANI/CNT/e-
MoS2 composites are shown in Fig. 4. In the PANI/MoS2 and
PANI/e-MoS2 composites, peaks at 2θ = 14.4° (002), 32.7° (100),
33.6° (101), 35.8° (102), 39.6° (103), 44.2° (006), 49.8° (105),
58.3°(110), 60.4° (008) representing the crystalline structure of
MoS2 [45]. Additional peaks at 2θ = 12.9°, 25.3°, 20.4° indicate the
semicrystalline nature of PANI [46]. In PANI/CNT/e-MoS2 compos-
ites, the peak at 2θ = 25.5° has broadened, which points out that
(1)
this peak is a combination of PANI and CNT. Raman scattering
technique was used to confirm the composite formation of PANI,
CNT and MoS2 . Raman spectra of PANI/MoS2 , PANI/e-MoS2 , and
PANI/CNT/e-MoS2 composites are shown in Fig. 5. For PANI/MoS2
4
M. Jasna, M. Muraleedharan Pillai, A. Abhilash et al.
Fig. 3. FESEM (a) and TEM (c) images of pristine MoS2 . FESEM(b) and TEM (d) ex-
foliated MoS2 nanosheets. Inset images of c and d display SAED patterns.
Fig. 4. XRD patterns of PANI/MoS2 , PANI/e-MoS2 and PANI/CNT/e-MoS2 composites.
composite, the band observed at 1556 cm−1 corresponds to the
deformed bond vibration in C=C stretching related to the quinoid
structure and the one at 1367 cm−1 can be assigned to the C – N+
stretching vibration associated with a polaronic structure [47,48].
A small shift (in the band position of pure PANI, shown in Fig. S1,
from 1356 cm−1 to 1367 cm−1 ) is observed in the characteristic
peak positions of PANI in the composite which is a clear indica-
tion of the composite formation of PANI with MoS2 . Moreover, in
PANI/e-MoS2 composite, Raman shift is observed for MoS2 peaks,
as shown in Fig. 5d, which confirms that the exfoliation results
in the interaction of MoS2 nanosheets with PANI. In PANI/CNT/e-
MoS2 composite, the peak at 1352 cm−1 (peak shift from pure
CNT, shown in Fig. S2, 1344 cm−1 to 1352 cm−1 ) assigned to
sp3 hybridized carbon vibrational band and referred to as the D
band originating from the vacancies, edge defects, grain bound-
aries and disordered carbon species in the CNT [45], shows a small
shift from that of the D band in pure CNT, generally observed at
1344 cm−1 (shown in Fig. S2). The ID /IG ratio of carbon nanotubes
determines its quality [49] and is found to be 1.05 for functional-
ized CNT (Fig. S2) even after the functionalization process, which
5
Carbon Trends 7 (2022) 100154
indicates the structural integrity of CNT after the acid treatment
process. The characteristic Raman peaks of PANI/CNT/e-MoS2 com-
posite detected at 385 cm−1 and 411 cm−1 are ascribed to the E21g
and A1g modes of MoS2 [50]. Moreover, in PANI/CNT/e-MoS2 com-
posite, the intensity of characteristic peaks of MoS2 decreases and
the peaks become broadened, whereas the intensity of the charac-
teristic peaks of PANI increases as well. This is mainly because of
the interesting situation that the exfoliated MoS2 nanosheets act as
templates for the growth of PANI nanowires. For understanding the
morphological details of PANI/MoS2, PANI/e-MoS2, and PANI/CNT/e-
MoS2 composites, FESEM and TEM images are recorded and are
shown in Figs. 6(a-f) and 7(a-b), respectively. From Figs. 5a and 5b,
it is observed that fiber-like PANI nanowires are anchored from the
side surface of bulk MoS2 .
But in the FESEM images of PANI/e-MoS2 composite, (Figs. 5c
and 5d) PANI nanowires are found to be grown over the sur-
faces on both sides of exfoliated MoS2 nanosheets. It is observed
that PANI nanowires are also anchored randomly from the MoS2
nanosheets.
The FESEM images of PANI/CNT/e-MoS2 composite at different
magnifications show PANI coated CNT and PANI nanowires are ran-
domly attached on the surfaces of nanosheets. The EDX elemental
mapping indicates the presence of the elements Mo (0.12 at%), S (1
at%), C (70.4 at%) and N (14.4 at%) in the PANI/CNT/e-MoS2 com-
posite (Figs. 6g-6j). The incorporation of CNT between exfoliated
MoS2 nanosheets provides 3D structure to the PANI/CNT/e-MoS2
composite. These types of nanosheets are extremely suitable for
the PANI nanowires to get connected to them, consequently hin-
dering the agglomeration of PANI nanowires and hence enhancing
the active surface area for ion motion from PANI.
Moreover, the introduction of CNT inhibits the restacking of ex-
foliated MoS2 nanosheets and thus, providing a more active area
for ion adsorption during the charge/discharge cycle. This 3D struc-
ture improves the electrochemical performance of the composite
electrode. The TEM and HRTEM images of the PANI/CNT/e-MoS2
composite are shown in Figs. 7a and 7b. The fibrillary structure of
PANI is observed in PANI/CNT/e-MoS2 composite and the dark re-
gion shows MoS2 nanosheets and CNT are found to cling between
them. In the HRTEM image, CNT can be identified and the lattice
spacing estimated as 0.3 nm corresponds to that of CNT.
For analyzing the electrochemical performance of the elec-
trodes, a three-electrode configuration is generally used, which
provides the material characterization data. To explore the prac-
tical application of the electrodes, a two-electrode configuration
must be employed. Two electrode configuration is used for device-
level testing, which provides the electrochemical performance data
of the assembled supercapacitor. Hence, to explore the potential
applications of the synthesized composites as electrode materials
in energy storage devices, the electrochemical properties of the su-
percapacitors assembled using PANI/MoS2 , PANI/e-MoS2 and PANI/
CNT/e-MoS2 composite materials as electrodes are investigated by
cyclic voltammetry and galvanostatic charge-discharge tests in the
form of two-electrode cells in 1 M H2 SO4 electrolyte with the
applied potential in the range of 0 to 0.8 V. The CV curves of
the symmetric supercapacitor cells based on PANI/MoS2 , PANI/e-
MoS2 and PANI/CNT/e-MoS2 composite materials at a scan rate of
50 mVs -1 are shown in Fig. 8a. All cells are found to exhibit the
characteristics CV curves of electrochemical Faradaic response con-
sisting of two noticeable groups of the redox peaks which origi-
nate from the doping state changes of PANI [51]. In the case of
PANI/CNT/e-MoS2 based cell, it can be observed that the CV loop
has a larger area under the redox curve compared to the situation
of the cells based on binary PANI/MoS2 and PANI/e-MoS2 compos-
ites, which indicates higher capacitance of the cell based on the
ternary composite electrode. Moreover, the CV profile of this de-
vice exhibits a more rectangular shape than that of other devices,
M. Jasna, M. Muraleedharan Pillai, A. Abhilash et al. Carbon Trends 7 (2022) 100154

Fig. 5. Raman spectra of (a) and (b) PANI/MoS2 , (c) and (d) PANI/e-MoS2 and (e) and (f) PANI/CNT/e-MoS2 composites.

indicating the contribution of electric double-layer capacitance. Table 1

Electrochemical parameters of the symmetric supercapacitor test cells.
The GCD curves of PANI/MoS2 , PANI/e-MoS2 and PANI/CNT/e-MoS2
composites based supercapacitors at the current density of 1 A g-1 Specific capacitance (F/g)@1Ag-1 Cycling stability
Composite material at 5Ag-1 after
are shown in Fig. 8b and PANI/CNT/e-MoS2 based cell shows the Supercapacitor Composite 10 0 0 cycles
highest discharge time at the current density of 1 A g-1 . Electro- cell electrode
chemical parameters of PANI/MoS2 , PANI/e-MoS2 and PANI/CNT/e-
PANI/MoS2 68.5 274 42%
MoS2 based SCs are given in Table 1. The specific capacitance of PANI/e-MoS2 91 364 72%
the symmetric SCs (based on the total mass of the two electrodes) PANI/CNT/e-MoS2 133 532 83%
assembled using PANI/MoS2 , PANI/e-MoS2 and PANI/CNT/e-MoS2
composite electrodes are found to be 68.5 F g-1 , 91 F g-1 and
133 F g-1 , respectively, at a current density of 1 A g-1 . For a sin- [52]. The specific capacitance of PANI has increased with the incor-
gle electrode, corresponding specific capacitance of the PANI/MoS2 , poration of exfoliated MoS2 , compared to that of PANI incorporated
PANI/e-MoS2 and PANI/CNT/e-MoS2 composite electrodes is ob- with pristine MoS2 . Exfoliation may result in the creation of more
tained as 274 F g-1 , 364 F g-1 and 532 F g-1 , respectively, at a active sites for redox kinetics. More importantly, PANI/CNT/e-MoS2
current density of 1 A g-1 , calculated by multiplying the device ca- composite can offer more active sites for the adsorption of ions
pacitance by a factor of 4 as described by Ruoff and his co-workers because of the 3D structure formation of the electrode material by

6
M. Jasna, M. Muraleedharan Pillai, A. Abhilash et al.
Fig. 6. FESEM images of (a and b) PANI/MoS2 , (c and d) PANI/e-MoS2 and (e and f) PANI/CNT/e-MoS2 composites with different magnifications and (g-j) elemental mapping
of PANI/CNT/e-MoS2 composites.
Fig. 7. (a)TEM and (b) HRTEM images of PANI/CNT/e-MoS2 composite.
the incorporation of CNTs. Scheme 2 represents the role of CNT for
the enhancement of ion adsorption in the electrode material. Usu-
ally, CNTs are formed in bundles which limit their applications in
supercapacitors due to the limited surface area. Only the outermost
7
Carbon Trends 7 (2022) 100154
surface of the CNT can be availed by electrolyte ions (Scheme 2a).
Exfoliated MoS2 sheets are likely to be restacked through Van der
Waals interactions and hence it is difficult for the electrolyte ions
to access sites on the inner surfaces of the sheets (Scheme 2b).
In CNT/exfoliated MoS2 composite, CNT can serve as a spacer be-
tween the MoS2 nanosheets to increase ion adsorption sites and
provide rapid diffusion pathways for the electrolyte ions. Moreover,
the overall electrical conductivity can also be enhanced by pres-
ence of CNT. (Scheme 2c).
The cycle performance of PANI/MoS2 , PANI/e-MoS2 and
PANI/CNT/e-MoS2 based symmetric SCs is investigated by consecu-
tive charge/discharge technique at a current density of 5 A g-1 for
10 0 0 cycles (Fig. 8c). For PANI/MoS2 electrode-based SC, specific
capacitance has an obvious decay after 500 cycles and only 42%
of its initial capacitance is retained after 10 0 0 cycles. For PANI/e-
MoS2 based SC, no obvious decay is observed up to 800 cycles
while a decreasing trend in capacitance is observed at the end
of cycles and 72% of its initial capacitance is retained after 10 0 0
M. Jasna, M. Muraleedharan Pillai, A. Abhilash et al. Carbon Trends 7 (2022) 100154

Fig. 8. Electrochemical performance of PANI/MoS2 , PANI/e-MoS2 and PANI/CNT/e-MoS2 based symmetric supercapacitors in 1 M H2 SO4 electrolyte–a) CV profiles at 50 mVs-1 ,
b) GCD profiles at 1 A g-1 , c) cycle performance at 5 A g-1 and d) Nyquist plots.

Scheme 2. Comparison of (a) CNTs, (b) MoS2 and (c) CNT/e-MoS2 composite as electrode materials.

cycles. Nevertheless, PANI/CNT/e-MoS2 composite electrode based
SCs exhibit excellent performance over large cycles and 83% of ini-
tial capacitance remain after 10 0 0 cycles.
For a better understanding of the electrochemical reaction ki-
netics of the composite materials, the electrode performance has
been analyzed using electrochemical impedance spectroscopy mea-
surements. The Nyquist plots of PANI/MoS2 , PANI/e-MoS2 and
PANI/CNT/e-MoS2 electrodes are shown in Fig. 8d. The plots con-
tain a semicircle at the high-frequency region and a straight line
at the lower frequency region. The radius of semicircle on the
real axis at high-frequency region of all plots corresponds to the
interfacial charge transfer resistance (Rct) [50]. For the plots of
PANI/MoS2 and PANI/e-MoS2 , the diameter of the semicircle is
higher than that of the semicircle of the plot of PANI/CNT/e-
MoS2 . This means the lowest interfacial charge transfer resistance
for this ternary composite, which indicates that PANI/CNT/e-MoS2
has good electrical conductivity. In other words, a semicircle of
larger diameter for PANI/MoS2 and PANI/e-MoS2 composites indi-
cates slower charge transfer and lesser conductivity of the elec-
trodes. Moreover, among all the composites, PANI/CNT/e-MoS2 has
smaller Rct, and its plot is found to be more vertical at lower fre-
quencies along the imaginary axis, showing lower resistance and
better capacitive behavior as compared to PANI/MoS2 and PANI/e-
MoS2 composites. Here the tubular nature of CNT makes the com-

8
M. Jasna, M. Muraleedharan Pillai, A. Abhilash et al. Carbon Trends 7 (2022) 100154

Fig. 9. Capacitive performance of PANI/CNT/e-MoS2 based symmetric supercapacitor in 1 M H2 SO4 electrolyte–a) CV profiles from 10 mVs-1 to 200 mVs-1 , b) GCD profiles
from 1 A g-1 to 10 A g-1 , c) specific capacitance at different current densities, d) coulombic efficiency and cyclic performance at 5 A g-1 for 40 0 0 cycles, e) GCD curves at 1st ,
10 0 0th and 40 0 0th cycles and f) Ragone plot.

posite a 3D structure. Consequently, PANI/CNT/e-MoS2 composite
has conductive pathways as well as a favorable porosity for ion ad-
sorption from the electrolyte to the electrode. Moreover, this elec-
trode structure can also maximize the utilization of PANI, which
contributes to the enhanced capacitance behavior of PANI/CNT/e-
MoS2 electrode. CV curves of the PANI/CNT/e-MoS2 composite-
based cells at different scan rates are shown in Fig. 9a and it is ob-
served that redox peaks shift to a higher potential. The area of CV
curves increases with the increase of sweep rates from 10 mVs-1
to 200 mVs-1 . The redox peaks of CV profiles are still maintained
even at high scan rates, which indicates the stability of the device.
It is observed that the specific capacitance decreases with an in-
crease in current density, as shown in Fig. 9b.
Usually, at high current density, the ion diffusivity in the elec-
trolyte, adsorption of ions on the electrode surface and charge
transfer in the electrode material are relatively slow due to the fast
charge/ discharge process, resulting in a relatively lower specific
capacitance. At lower current density, ion diffusivity is high and
there is sufficient time to complete the above processes, which re-
sults in much higher specific capacitance. Electrochemical param-
eters of PANI/CNT/e-MoS2 based SCs are given in Table 2. For the
PANI/CNT/e-MoS2 composite based symmetric supercapacitor, spe-
cific capacitance decreases from 133 F g-1 to 92.5 F g-1 as the
current density increases from 1 A g-1 to 10 A g-1 (Fig. 9c) and
70% rate capability is obtained. This result indicates that the syn-
thesized PANI/CNT/e-MoS2 ternary composite electrode possesses

9
M. Jasna, M. Muraleedharan Pillai, A. Abhilash et al. Carbon Trends 7 (2022) 100154

Table 2
Electrochemical performance of PANI/CNT/e-MoS2 composite based supercapacitor cells.

Current density (A g-1 ) Specific capacitance (F g-1 ) Energy density (Wh kg-1 ) Power density (W kg-1 )

1 133 11.8 457

2 125 11.1 928
5 113.6 10.09 2228
10 93 8.22 3785

Table 3
Comparison of electrochemical performance of some similar PANI composite based supercapacitors.

Voltage Specific capacitance (F/g) Capacity retention(cycle

Material Electrolyte window (V) Composite electrode Supercapacitor cell number) Ref.
−2
PANI/CNT 1M Na2 SO4 0 – 0.9 0.016 F cm (0.25 mA - 63% (500) [53]
cm−2 )
MoS2 /PANI 1 M H2 SO4 - 552 F/g(0.5 A/g-1 ) 124 Fg -1 -1
(1A g ) 79%(6000) [29]
PANI/CNT/MoS2 1 M H2 SO4 0 – 0.8 350F/g (1A g-1 ) - 68%(2000) [45]
PANI/GO/CNT 1 M H2 SO4 0 – 0.7 589 F/g(0.2A g-1 ) - 81%(1000) [54]
MoS2 /RGO@PANI 1 M H2 SO4 0 – 0.8 - 160 F g-1 (1A g-1 ) 82.5%(3000) [32]
MoS2 /PANI 1 M H2 SO4 0 -1 390 F/g (0.8 A g-1 ) - 86% (1000) [55]
MoS2 /PANI 1 M H2 SO4 - - 133 F g-1 (0.5 A g-1 ) - [56]
PANI/CNT/e-MoS2 (this work) 1 MH2 SO4 0 – 0.8 532 F g-1 (1A g-1 ) 133 F g-1 (1A g-1 ) 80%(4000)

good rate capability. Moreover, the discharge/charge profiles retain
the same shape and show no significant IR drops even at higher
current density. The cycling stability of the PANI/CNT/e-MoS2 com-
posite based cell was also evaluated for large cycles (Fig. 9d). After
40 0 0 cycles of constant charge/discharge processes at 5 A g-1 , the
capacitance retention is about 80%. The specific capacitance and
cyclic stability of the electrode are comparatively high when com-
pared to the early reports on PANI/CNT ternary composites based
supercapacitors [45]. The coulombic efficiency is also close to 100%
for all cycles and this indicates that the PANI/CNT/e-MoS2 compos-
ite based SC has high stability (Fig. 9d). From Fig. 9e, which shows
the charge/discharge curves at different cycling stages at 5 A g-1 ,
it is observed that there are no significant IR drops during dif-
ferent cycling stages which indicate lesser equivalent series resis-
tance (ESR) for PANI/CNT/e-MoS2 based symmetric SC due to the
3D structure of the composite electrode. The energy density and
power density of the PANI/CNT/e-MoS2 based symmetric SC are
calculated for the current density from 1 A g-1 to 10 A g-1 using
Eqs 2 and 3 and found to be 11.8 Wh kg-1 and 3785 W kg-1 , re-
spectively (Figs. 9c and 9f). To the best of our knowledge, the elec-
trochemical performance of devices of the present study is supe-
rior to that of previously reported PANI-based SCs, as evident from
Table 3. The combination of exfoliated MoS2 , PANI and CNT im-
proves the electrochemical properties of the corresponding devices
significantly because of the synergistic effect of the component
materials. Consequently, this electrode design offers a promising
approach for enhancing the capacitive performance of the PANI-
based symmetric SCs. Even though this innovative electrode design
gives an excellent electrochemical performance, it has a limitation
of the presence of inactive materials due to the adoption of the
conventional slurry method, which affects the overall performance
of the SC. The use of binder-free electrodes can overcome this lim-
itation and can contribute 100 percent participation of active ma-
terials in the electrochemical performance of the device.
6. Conclusion
With the incorporation of CNT, and exfoliated MoS2 , 3D struc-
tured PANI/CNT/e-MoS2 ternary composite has been synthesized
by facile and effective in-situ oxidative polymerization method and
SC electrode is developed on the fiber-like structure of the carbon
cloth which serves as the current collector. The introduction of CNT
in the PANI/e-MoS2 composite improves the electrochemical per-
formance of the composite due to its 3D structure. The obvious
synergistic effect between tubular CNT and exfoliated MoS2 thin
sheets plays an important role in better ion transport and stor-
age, as well as maximum utilization of PANI nanowires and resists
the volume change on cycling, which makes this type of electrode
design unique, with remarkable rate performance and excellent
capacitive behavior. The ternary composite based on PANI/CNT/e-
MoS2 shows a maximum specific capacitance of 532 F g-1 , which is
relatively higher than that of PANI/MoS2 and PANI/e-MoS2 compos-
ites. Moreover, it has been found that the specific capacitance re-
tention of the PANI/CNT/e-MoS2 ternary composite based superca-
pacitor is about 80% after 40 0 0 charge/discharge cycles at a current
density of 5 A g-1 . Energy density and power density of 11.8 Wh
kg-1 and 3785 W kg-1 , respectively, are achieved for the assembled
PANI/CNT/e-MoS2 based symmetric supercapacitor cells. All these
results highlight the potential of the prepared ternary composite as
an auspicious electrode material for realizing next-generation high-
performance supercapacitors. Moreover, the unique electrode de-
sign adopted in the present work can be utilized as an efficient de-
sign strategy to improve the electrochemical performance of PANI
as well as other conducting polymers-based electrodes for devel-
oping the next generation high power supercapacitors.
Declaration of Competing Interests
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
CRediT authorship contribution statement
M Jasna: Conceptualization, Methodology, Data curation, Inves-
tigation, Formal analysis, Writing – original draft, Writing – review
& editing. Manoj Muraleedharan Pillai: Data curation, Validation,
Writing – review & editing. A. Abhilash: Conceptualization, For-
mal analysis. P.S. Midhun: Conceptualization, Writing – review &
editing. S. Jayalekshmi: Validation, Conceptualization, Supervision,
Writing – review & editing. M.K. Jayaraj: Supervision, Conceptual-
ization, Validation, Writing – review & editing.
Acknowledgments
Author Jasna is thankful to the university grants commission
for awarding BSRRFSMS fellowship and A. Abhilash thank the min-
istry of new and renewable energy for the national renewable en-

10
M. Jasna, M. Muraleedharan Pillai, A. Abhilash et al.
ergy fellowship. The authors acknowledge the financial support ex-
tended by DST-FIST scheme, Government of India, for the FE-SEM
facility.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.cartre.2022.100154.
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