Electrochimica Acta 273 (2018) 379e391

Contents lists available at ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Electrosynthesis of polypyrrole-vanadium oxide composites on

graphite electrode in acetonitrile in the presence of carboxymethyl
cellulose for electrochemical supercapacitors
€
Erhan Karaca a, b, Kadir Pekmez a, Nuran Ozçiçek Pekmez a, *
a
Hacettepe University, Dept. of Chemistry, 06800 Ankara, Turkey
b
Dumlupınar University, Dept. of Chemistry, 43100, Kütahya, Turkey

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

Article history: One-step electrochemical synthesis of polypyrrole-vanadium oxide (PPy-VOx) composites was per-
Received 17 December 2017 formed on the Vanadium-intercalated pencil graphite (PG) surface in an acetonitrile solution with the
Received in revised form presence of carboxymethyl cellulose (CMC). Both intercalated surface and composite coating were
1 April 2018
characterized using SEM-EDX Spectroscopy and X-Ray Diffraction (XRD) techniques. The capacitive
Accepted 8 April 2018
Available online 10 April 2018
properties of the coating were elaborated in an H2SO4/water medium using galvanostatic charge
edischarge, potential cycling, and electrochemical impedance spectroscopy methods in comparison with
the coatings prepared without additives. While V-intercalation provides a significant increase in the
Keywords:
Electrosynthesis
specific capacitance, the carboxymethyl cellulose enhances the cyclic performance of the composite. The
Supercapacitor improvement at the capacitance of the composite may be due to the homogenous distribution as well as
Composite the synergetic effect between PPy and VOx. The capacitive properties were studied in aqueous solutions
Polypyrrole of H2SO4 and Li2SO4, and in an acetonitrile solution of HBF4/TBABF4. The specific capacitance value of the
Vanadium oxide composite coating on the V-intercalated pencil graphite was determined as 204 F g
1 in an acetonitrile
solution of HBF4/TBABF4 for a mass loading of 10.0 mg cm
2 at 2.0 A g
1, when the capacitance of bare
graphite was subtracted. The two-electrode supercapacitors composed of both asymmetric and sym-
metric configurations were also prepared and examined in an acetonitrile/adiponitrile solution of HBF4/
TBABF4. The chargeedischarge results for asymmetric supercapacitor reveal that the PPy-VOx-CMC
composite coating (20 mg cm
2) on V-intercalated graphite paper represents a high energy density of
18 Wh.kg
1 and a high power density of 0.43 kW kg-1 at 0.5 A g
1, as well as a stable cycle life at the
potential range of 1.2 V.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction greater as compared to the activated carbon electrodes, which are

Metal oxides, such as manganese oxide, vanadium oxide, and
cobalt oxide, and conducting polymers such as polyaniline and
polypyrrole (PPy), represent a recently arising topic in super-
capacitor research [1]. PPy is a candidate material for super-
capacitor electrodes with high electrical conductivity, reversible
electrochemical redox property, high charge storage capacity and
good environmental stability. The specific capacitance values of PPy
coated electrodes have been observed at a range of 179 F g
1 to
506 F g
1 at 10.0 mV s
1 scan rate [2e6]. These values are much
* Corresponding author. Fax: þ90 312 299 2163.
€ Pekmez).
E-mail address: npekmez@hacettepe.edu.tr (N.O.
widely available in commercial products. On the other hand, more
expensive and rare metals, such as RuO2 [7,8], Co3O4 [9e11], NiO
[12,13], MnO2 [14e19] show better specific capacitance values.
Transition metal oxides have been subject to detailed research
as an electrode material for electrochemical capacitors. Vanadium
based electrodes exhibit excellent specific capacitance as well as
stable electrochemical reversibility, good conductivity, long cycle
life and typical layered structure [1,20]. Owing to these character-
istics, vanadium oxides are promising active materials for high
power/energy density. VO2 has poor electrical conductivity and
structural stability; therefore, long-term cycling stability is limited.
The typical layered structures and multiple stable oxidation states
(IVeV) of vanadium oxides (VOx) represent critical factors
improving the charge storage capacity when compared to the most

https://doi.org/10.1016/j.electacta.2018.04.059
0013-4686/© 2018 Elsevier Ltd. All rights reserved.
380 E. Karaca et al. / Electrochimica Acta 273 (2018) 379e391
of the transition-metal oxides. Vanadium oxides are capable of
storing charge in a broad range of potential windows. There are
several methods successfully utilized to prepare vanadium based
electrodes, including electrodeposition [21e23], sol-gel hydro-
thermal/solvothermal template [24], electrospinning [25], and
atomic layer deposition [24].
Hybridizing the metal oxides with highly conductive materials,
such as graphene, carbon nanotubes, or conductive polymers is an
effective method to improve the electrical conductivity and me-
chanical properties of materials [23,26]. PPy-Vanadium oxide
composites for lithium-ion batteries and supercapacitors have been
subjected to several studies [9,23,27e30]. The energy densities of
the batteries have been reported over a range of 95.2e297 mAh.g
1.
The active materials of these electrodes were prepared chemically
and then were mixed with carbon black using binders. For elec-
trochemical supercapacitors, the composite materials were usually
synthesized chemically, and they have the energy density of
20.0e69.2 Wh kg
1 and the power density of 0.162e0.72 kW kg
1
[28,30e32]. Bai et al. studied the electrochemical synthesis of the
V2O5
PPy composite film on carbon cloth in an aqueous solution.
The composite film was deposited via potentiostatic method at
0.7 V vs SCE from a 100 mM phosphate buffer solution (pH 6.86)
containing 100 mM LiClO4, 100 mM vanadyl sulfate and 30 mM
pyrrole. The specific capacitance, energy density and power density
of three electrode system were found as 412 F g
1, 82 Wh kg
1,
0.8 kW kg-1 at a current density of 4.5 mA cm
2, respectively. 80% of
the specific capacitance was maintained after 5000 galvanostatic
charge
discharge cycles.
This study, for the first time in the literature, presents electro-
chemical codeposition of PPy and VOx as a composite on vanadium
intercalated graphite substrate in one-step in the presence of car-
boxymethyl cellulose. Via this method, VOx can be homogeneously
encapsulated in the conducting PPy coating without using a binder.
The electrochemical synthesis of the coatings on an intercalated
substrate is a new study for supercapacitor research. Moreover, the
electropolymerization medium is a nonaqueous acetonitrile solu-
tion. According to the previous studies, the conductivity (and thus
the specific capacitance) of PPy synthesized in nonaqueous solu-
tions is higher than that of aqueous solutions [33,34]. Both inter-
calated surface and composite coating were characterized by X-Ray
Diffraction (XRD), Raman, SEM-EDX Spectroscopy techniques. The
characteristics of composite film were compared with PPy films
prepared under the same conditions. The capacitive properties of
the coatings were investigated in aqueous H2SO4 solution, utilizing
potential cyclic, galvanostatic chargeedischarge measurements
and electrochemical impedance spectroscopy (EIS) studies. A
detailed electrochemical study for two-electrode supercapacitor
with both asymmetric and symmetric configurations was also
carried out in a non-aqueous electrolyte.
2. Experimental
2.1. Chemicals
Vanadium pentoxide (V2O5, Sigma), tetrabutylammonium tet-
rafluoroborate (TBABF4, Sigma), tetrabutylammonium perchlorate
(TBAClO4, Sigma), lithium sulfate (Li2SO4), Triton X100 (Sigma),
acetonitrile (HPLCegrade, Sigma), adiponitrile (Merk), perchloric
acid (HClO4, Merck), sulfuric acid (H2SO4, Fluka), tetrafluoroboric
acid diethyl ether complex (HBF4$O(CH2CH3)2, Sigma), oxalic acid
(H2C2O4, Sigma) and N-methyl-2-pyrrolidone (Sigma) and Carbon
black (Sigma) were analytical grades and used as received without
further purification. Pyrrole (Py, Fluka) was distilled under the
cover of high purity nitrogen (Linde) and then stored in a refrig-
erator before use. Vanadium pentoxide, oxalic acid (in aqueous
solution) and HBF4$O(CH2CH3)2 or HClO4 were used to extract
vanadyl tetrafluoroborate (VO(BF4)2) or vanadyl perchlorate
(VO(ClO4)2).
2.2. Characterization
The microstructure and morphology were characterized by field
emission scanning electron microscope (FESEM, NOVA NANOSEM
650/FEI, USA), and energy-dispersive X-ray analysis (EDX) and
elemental mapping (AMETEK-EDAX, USA). The coatings were
examined by grazing incidence X-ray diffraction (XRD) analysis
(PANalytical/EMPYREAN, USA) with Cu Kf radiation operating at
45 kV and 40 mA. The Raman measurements were performed using
a DeltaNu Examiner Raman microscope (DeltaNu Inc., Laramie, WY,
USA) with a 785-nm laser source, a motorized microscope stage
sample holder, and a charge-coupled device detector. During the
measurements, a 20 objective was used, and the laser spot
diameter was 3.0 mm. Samples were measured with the laser power
of 140 mW for 10 s acquisition time.
2.3. Electrochemical deposition and tests
Electrochemical measurements were carried out under the ni-
trogen atmosphere in a threeeelectrode cell with separate com-
partments for reference and counter electrodes. Reference
electrodes were Ag/AgCl in acetonitrile and saturated calomel
reference electrode (SCE) in aqueous solutions, whereas counter
electrode was Pt spiral. Pencil graphite electrode (0.0244 cm2),
graphite sheet (2.00 cm2, Ringsdorff-Werke) and graphite paper
(0.196 cm2, SGL Carbon GDL 39 AA) were used as working elec-
trodes. Before the use, working electrodes were rinsed with
acetonitrile and dried at room temperature. PPy was synthesized
using potentiodynamic and galvanostatic methods in an acetoni-
trile solution containing 25 mM Py, 25 mM TBABF4 (or TBAClO4),
100 mM H2O and with and without 25 mM HBF4, (or HClO4). For
comparison of potentiodynamic and galvanostatic methods, the
composite materials were deposited in the above acetonitrile so-
lution, additionally containing 10 mM VO(BF4)2. The effects of ad-
ditives were investigated using the galvanostatic method in the
same acetonitrile solution with and without 25 mM TX100 and
0.5 mg/mL CMC. After the optimum concentrations of the chem-
icals were obtained, in the following sections, composite materials
were galvanostatically deposited on V-intercalated pencil graphite,
graphite sheet or graphite paper electrodes in the acetonitrile so-
lution containing 25 mM Py, 25 mM TBABF4 and 25 mM HBF4,
10 mM VO(BF4)2, 100 mM H2O, 25 mM TX100 and 0.5 mg/mL CMC.
Electrochemical intercalation of vanadium into PG was performed
by scanning the potential between 0.0 and
2.0 V vs. Ag/AgCl with
a scan rate of 100 mV s
1 prior to the electrodeposition of the
composite film in the polymerization solution, containing
25 mM Py, 25 mM TBABF4, 10 mM VO(BF4)2, 100 mM H2O, 25 mM
HBF4, 25 mM TX100 and 0.5 mg/mL CMC. After the deposition
processes, the coatings were cleaned with acetonitrile to remove
unreacted monomer molecules and dried under nitrogen flow at
25OC for approximately 5 min. The electrochemical performances
of coated electrodes were characterized using potential cycling,
galvanostatic chargeedischarge and impedance spectroscopy tests
(EIS) in various electrolytes. In addition to these, analytical mea-
surements were conducted for symmetric and asymmetric super-
capacitor configurations. The galvanostatic measurement of the cell
was characterized at current densities varying from 1 to
20 mA cm
2. The cyclic stability measurement was carried out for
5000 cycles. Electrochemical impedance spectroscopy was
measured at a frequency range varying from 0.01 to 100 kHz at
open circuit potential. ZSimpwin V3.50 software (Scribner
 E. Karaca et al. / Electrochimica Acta 273 (2018) 379e391
Associates Inc., UK), was used to fit impedance data to bring out an
equivalent circuit and its parameters.
The specific capacitance value obtained using the cyclic vol-
tammogram was calculated according to the following equation:
[35,36].
Cm ¼ S = 2 m ðdV=dtÞ DV (1)
where Cm (F g
1) is the specific capacitance of coating; S is the area
calculated from the cyclic voltammetric curve, m (g) is the mass of
active material within the electrode, dV/dt (V s
1) is the scan rate,
and DV is the potential range. The areal capacitance, Cs, (F cm
2), is
calculated by dividing the capacitance by the area of the electrode.
The specific capacitance value obtained using the galvanostatic
chargeedischarge curve was calculated from the following equa-
tion: [37,38].
Cm ¼ I Dt=mDV (2)
where Cm (F g
1) is the capacitance of coating; I is the discharge
current, Dt denotes the discharge time, and DV represents the po-
tential window during the discharge process.
3. Result and discussion
3.1. Electrochemical synthesis of polypyrrole-vanadium oxide
composite and its characterization
3.1.1. Potential cycling synthesis of composite on pencil graphite
surface
In order to combine outstanding specific capacitance and me-
chanical properties, polypyrrole (PPy) and vanadium oxide were
deposited simultaneously on the PG electrode surface instead of
mixing the components prepared separately. By this means, PPy as
intrinsically conducting polymer and vanadium oxide as transition-
metal oxide encapsulate within each other as a mixture during the
electrodeposition of the composite film. The encapsulation of va-
nadium oxide inside the growing polymer provides homogeneous
distribution and mechanical strength of the composite coating.
Polymerization medium is an acetonitrile solution prepared by
primarily adding pyrrole (Py) monomer and vanadyl salt (as BF
4 or
ClO
4 ).
PPy-vanadium oxide composite was electrochemically depos-
ited via potentiodynamic (potential cycling) method on pencil
graphite electrode (PG) in an acetonitrile solution prepared by
adding 25 mM Py monomer, 25 mM TBABF4 (or TBAClO4), 25 mM
HBF4 (or HClO4) and 10 mM VO(BF4)2 (or VO(ClO4)2). Vanadyl salts
are not soluble in acetonitrile, and for this reason, a small amount of
water (100 mM) was added to the acetonitrile solution. Various
potential ranges and scan rates were examined to determine an
optimum condition (Table S1). In all cases, the charge pass during
the electropolymerization was kept constant at 15 mC (0.615C cm

2
, 0.19 mg cm
2) for comparison. An aqueous H2SO4 solution is
used as the electrolyte for evaluating the capacitive properties of
the coatings. The cyclic voltammograms of the coatings were
recorded in the 100 mM H2SO4 solution by scanning the potential
between
0.30 V and 0.65 V vs. SCE at a 100 mV s
1 scan rate. The
specific capacitance values were calculated from Eq. (1) using the
cyclic voltammograms. According to the results (Table S1), the
highest capacitance value, 499 F g
1 in the presence of BF
4 and
394 F g
1 in the presence of ClO
4 , is obtained by scanning the po-
tential between
0.20 V and 1.2 V vs. Ag/AgCl at a 100 mV s
1 scan
rate in the presence of TBABF4, HBF4, and VO(BF4)2. Fig. S1 shows
the multi-sweep cyclic voltammogram recorded during the elec-
trodeposition of the composite coating and its cyclic
381
voltammogram obtained in the 100 mM H2SO4 solution. Potential
values exceeding the limits are not appropriate for the synthesis of
the films. The polymer film may be incurred over-oxidation quickly
due to the VOþ 2 ion when the upper potential limit is more positive
than 1.20 V [39]. In case, the applied potential is more negative
than
0.20 V, vanadium ion is reduced to vanadium species in
lower valence during the electrosynthesis (see Section 3.2 for
details).
In order to investigate the effect of the acids and vanadyl salts on
the capacitance, the coatings were again produced under the op-
timum conditions without using HBF4 acid (or HClO4) and VO(BF4)2
salt (or VO(ClO4)2). The specific capacitance values of the coatings,
presented in Table 1, increase in the presence of only acids, and also
in the presence of both acids and vanadyl salt in the polymerization
solution. It is well known that the acidic medium provides stability
of existing cation radicals during the formation of the conductive
polymers [40]. The resulting higher capacitance values in the
presence of vanadyl salt also indicate that vanadium oxide can be
deposited into the polymer matrix in every solution.
From Table 1, the PPy film with BF
4 counter ion exhibited a
higher capacitance behavior in cases the polymerization solution is
with and without vanadyl salts and/or acids. This may be due to the
presence of smaller and more polar counter ion. Yamaura et al. also
showed that the polarity and steric effect of the counter ion on the
mechanical properties and conductivity of PPy films were observed
when compared to the ClO


4 and BF4 counter ions [34]. As a
consequence, the following experiments were carried out to syn-
thesize the composite film on PG surface using TBABF4, HBF4, and
VO(BF4)2.
3.1.2. Galvanostatic synthesis of the composite on pencil graphite
surface
Electrosynthesis of PPy containing vanadium oxide was also
carried out in an acetonitrile solution by applying various current
values at a number of steps (1e4) using the galvanostatic deposi-
tion technique. The solution was prepared by the addition of
25 mM Py monomer, 25 mM TBABF4, 25 mM HBF4, 10 mM VO(BF4)2
and 100 mM H2O. In all cases, the charge pass during the electro-
deposition was kept constant at 0.615 C cm
2 to compare with the
results obtained via potential cycling. According to the results
(Table S2), the maximum Cm value was 522 F g-1 at total current
density of 12.3 mA cm
2 by the deposition condition involving step
I: 20 s at 500 mA, step II: 20 s at 300 mA and step III: 20 s at 200 mA.
Using the deposition procedure with the three galvanostatic stage,
the amount of the composite was obtained as 0.19 mg cm
2. The
chronopotentiometric curves recorded during the electrodeposi-
tion of the coatings in the regular solution (composite) and also
with the absence of VO(BF4)2 (PPy) are presented in Fig. 1Ab and a,
respectively. Their cyclic voltammograms attained in
100 mM H2SO4 solution are given in Fig. 1Bc and d, in the same
order.
For comparison, the coatings were obtained by the galvanostatic
method under optimum conditions in the absence of HBF4 and/or
VO(BF4)2. The resulting specific capacitance values are also
included in Table 1. Although the amount of charge consumed
during the electrodeposition at each solution is identical for both
methods, the PPy-vanadium oxide coatings produced by the gal-
vanostatic method have better capacitive behavior than those
produced via potential cycling method. The coating could have
yielded a more porous surface structure. It is known that galva-
nostatic deposition can provide control over physical-chemical
properties of materials such as morphology, porosity, adhesion,
compound content, and electrical conductivity via modification of
galvanostatic parameters [3,41,42]. While the highest value ob-
tained using galvanostatic method is 522 F g
1, the potential cycling
382 E. Karaca et al. / Electrochimica Acta 273 (2018) 379e391

Table 1
The specific capacitance values of PPy-Vanadium oxide composite synthesized on PG electrode at a mass loading of 0.19 mg cm
2 by potentiodynamic and galvanostatic
methods under optimum conditions.

Polymerization Solution Cm/F g
1 (Cs/mF cm
2)

Potentiodynamic method potential Galvanostatic method

range:
0.20 V and 1.2 V vs. Ag/AgCl, v ¼ 100 mV s
1 step I: 10 s at 500 mA, step II: 20 s at 300 mA,
step III: 20 s at 200 mA

Py þ TBABF4 349 (66.4) 341 (64.8)

Py þ TBAClO4 304 (57.9) 336 (63.9)
Py þ TBABF4 þ HBF4 364 (69.2) 425 (80.8)
Py þ TBAClO4 þ HClO4 353 (67.2) 402 (76.4)
Py þ TBABF4 þ HBF4 þ VO(BF4)2 499 (94.8) 522 (99.2)
Py þ TBAClO4 þ HClO4 þ VO(ClO4)2 394 (74.8) 411 (78.1)

cPy ¼ 25 mM, cTBABF4 or TBAClO4 ¼ 25 mM, cVO(BF4)2 or VO(ClO4)2 ¼ 10 mM, cH2O ¼ 100 mM, cHBF4 or HClO4 ¼ 25 mM

method yields 499 F g
1. As a consequence, the galvanostatic
method was preferred to produce the PPy-vanadium oxide com-
posite film.
The influence of surfactant and water on the specific capacitance
of the PPy-vanadium oxide composite coating were also elaborated.
Surfactants are known to provide higher porosity and therefore
higher surface area, which enables more accessible ions during the
electrochemical process [43]. Also adding a small amount of water
Fig. 1. (A) Chronopotentiometric curves recorded during the synthesis of coatings at a
mass loading of 0.19 mg cm
2 in the acetonitrile solutions containing (a) Py, TBABF4
and HBF4, (b) Py, TBABF4, HBF4 and VO(BF4)2, (c) Py, TBABF4, HBF4, VO(BF4)2 and CMC
on PG electrode (d) Py, TBABF4, HBF4, VO(BF4)2 and CMC on V-intercalated PG elec-
trode. (B) Cyclic voltammograms obtained in 100 mM H2SO4 solution for (a) uncoated
PG electrode, and for the coatings shown in Fig. 1A in the same order, v ¼ 100 mV s
1
(cPy ¼ 25 mM, cTBABF4 ¼ 25 mM, cHBF4 ¼ 25 mM, cVO(BF4)2 ¼ 10 mM, cCMC ¼ 0.5 mg/ml).
to the polymerization medium increases the conductivity since the
basicity of water is stronger than Py and water can easily attract the
protons released during the electropolymerization [44,45]. So
oligomers form longer chains and their solubility reduces. This
phenomenon leads to a faster deposition on the electrode surface
[44]. However, if water volume is increased in the solvent mixture,
the growth of the polymer slows down and the amount of the
polymer gained decreases. This may be due to the inhibition at the
stability of cation radicals of monomer and oligomers in the water
and eventually the overoxidation of polymer [44,46].
In order to determine optimum concentrations of TX100, H2O,
and other additives (VO(BF4)2 and HBF4), the composite coated
electrodes were prepared galvanostatically using optimum condi-
tions from a polymerization solution containing 25 mM Py, 25 mM
TBABF4 and various concentrations of the additives. The relation
between the concentrations of the additives and specific capaci-
tance values are demonstrated in Table 2. As expected, the capac-
itance value improved until a certain concentration was reached
and afterwards, it decreased except the case for VO(BF4)2. Herein,
the capacitance value increased until VO(BF4)2 concentration was
reached up to 10 mM and then remained constant. Thus, the opti-
mum concentrations of VO(BF4)2, H2O, HBF4, and TX100 were
determined as 10 mM, 100 mM, 25 mM and 25 mM, respectively
(Table 2). When all additives are taken into consideration, the
specific capacitance increases from 425 F g
1 to 555 F g
1. These
results emphasize the significance of both contents and their
concentrations.
Sodium carboxymethyl cellulose (CMC), a kind of cellulose
derivated from carboxymethylation of the hydroxyl group of cel-
lulose, is a water-soluble ionic cellulose ether that forms suspen-
sions or emulsions in aqueous systems [47]. In order to improve the
mechanical stability of the composite coatings, 0.50 mg/mL CMC
suspension solution is added to the polymerization solution
(Fig. 1Ac and Fig. 1Bd). Moreover, CMC is able to establish cross link
with metal ions as well as hydrogen bonding with the lone pairs of
nitrogen in PPy, thus enhancing the material properties [48,49]. As
seen in Table 2, there is a significant increase, from 555 F g
1 to
686 F g
1, in the specific capacitance value with the addition of
CMC.
The presence of ordered graphite layers on the bare PG electrode
surface can be observed in Fig. 2a. The interlayered structures have
been considered to be advantageous for ion intercalation/dein-
tercalation [26,33]. Carbons can be intercalated at more negative
potentials than any other Li-intercalation material [50]. In this
study, electrochemical intercalation of vanadium into PG was per-
formed by scanning the potential between 0.0 and
2.0 V with a
scan rate of 100 mV s
1 prior to the electrodeposition of the com-
posite film. Fig. S2 shows the potential cycling scans taken during
the intercalation in the polymerization solution, containing
 E. Karaca et al. / Electrochimica Acta 273 (2018) 379e391 383

Table 2
The specific capacitance values obtained in 100 mM H2SO4 solution for the coated PG electrodes prepared galvanostatically at a mass loading of 0.19 mg cm
2 under
optimum conditions using various concentrations of the variables.

Solution (cPy: 25 mM, cTBABF4: 25 mM) (Coating) Cm /F g
1

Py þ TBABF4 þ 25 mM HBF4 þ50 mM H2O þ VO(BF4)2 c VO(BF4)2/mM

(PPy-VOx) e 425
5.0 429
10 432
15 432
20 432
Py þ TBABF4 þ 25 mM HBF4 þ 10 mM VO(BF4)2 þ H2O c water/mM
(PPy-VOx) 50 432
100 522
125 468
175 459
275 456
Py þ TBABF4 þ 10 mM VO(BF4)2 þ100 mM H2O þ HBF4 c HBF4/mM
(PPy-VOx) e 485
25 522
50 488
100 449
Py þ TBABF4 þ 10 mM VO(BF4)2 þ 100 mM H2O þ 25 mM HBF4 þ TX100 c TX100/mM
(PPy-VOx) e 522
15 526
25 555
40 537
Py þ TBABF4 þ 10 mM VO(BF4)2 þ 100 mM H2O þ 25 mM HBF4 þ 25 mM TX100 þ CMC c CMC/mg/mL
(PPy-VOx-CMC) e 555
0.5 686
Py þ TBABF4 þ 10 mM VO(BF4)2 þ 100 mM H2O þ 25 mM HBF4 þ 25 mM TX100 þ 10 mM non-intercalation 686
CMC þ V intercalation between
2.0 and 0.0 V vs. Ag/AgCl 25 cycles (v ¼ 100 mV s
1) 726
(PPy-VOx-CMC (intercal.)) 50 cycles (v¼100 mV s
1) 763
75 cycles (v ¼ 100 mV s
1) 547
50 cycles (v ¼ 50 mV s
1) 637

25 mM Py, 25 mM TBABF4, 10 mM VO(BF4)2, 100 mM H2O, 25 mM
HBF4, 25 mM TX100 and 0.5 mg/mL CMC. The current density
gradually decreases due to the reduction of the vanadium species,
whereas the intercalation of vanadium increases. In other words,
the surface of PG electrode changes after each cycle, which in-
dicates the intercalation of vanadium in each cycle.
In order to understand the existence of V-intercalation, surface
analyses of the PG electrode were performed using SEM with
Backscattered Electron (BSE) detector (Fig. 2b) and EDX vanadium
mapping (Fig. 2c). BSE images of the flat samples have a good
material contrast that corresponds to an increase in the intensity
with the increasing atomic number [51]. The contrast of vanadium
on PG surface can easily be observed in Fig. 2b. In Fig. 2c, vanadium
element appears intensively and uniformly, indicating the inter-
calation of PG surface. In conclusion, the incorporation of vanadium
into the PG electrode is verified via surface analysis.
The PPy-VOx-CMC composite coating was formed galvanostati-
cally on V-intercalated PG surface in the polymerization solution
under the optimum conditions determined above. Table 2 shows
the parameters applied for the intercalation and the capacitance
values of the composite coating deposited on V-intercalated PG
surface. As seen in Table 2, there is a significant increase in the
specific capacitance of the samples produced under the optimum
condition of the intercalation (50 cycles, v ¼ 100 mV s
1). Thus, the
capacitance value of composite coating was enhanced (up to
763 F g
1) when compared to that of the PPy-VOx-CMC composite
coating on the non-intercalated-PG electrode (686 F g
1). (Table 2,
Fig. 1Ac and d, Fig. 1Bd and e).
3.1.3. X-ray diffraction analysis
The phase constitution of coatings was studied by XRD. Fig. 3
shows the typical X-ray pattern of PPy on graphite sheet (Fig. 3b)
and PPy-vanadium oxide composite coatings on both graphite
sheet and V-intercalated graphite sheet (Fig. 3c and d). In the XRD
spectrum of PPy, in addition to the peaks of graphite, a broad peak
with low intensity is observed at about 25 originating from the
amorphous nature of the polymer [52] (Fig. 3a and b). In the case of
the composite coatings with and without intercalation of vana-
dium, there are the peaks at (2Q) 16.2 , 23.4 , 30.9 , 48.9 , 54.5
which matched the standard XRD patterns of pure V2O5.H2O (ICDD
PDF 00-011-0673) and at (2Q) 24.9 , 34.3 and 42.6 which
matched the standard XRD patterns of pure VO2.H2O (ICDD PDF 00-
018-1445). The difference of these spectra is at their peak in-
tensities: the peaks due to V2O5.H2O and VO2.H2O for the com-
posite coating on V-intercalated graphite sheet surface (Fig. 3d) are
more intensive than those of the composite coating on graphite
sheet (Fig. 3c). This indicates the more insertion of vanadium oxides
into the composite coating in the case of V-intercalated graphite
sheet surface. Also, vanadium in lower valence states inserted into
the composite during the intercalation treatment is oxidized to the
higher valance states during the electrodeposition of the composite
coating. In addition, a small amount of water content of oxides can
greatly influence its electrochemical cycling and capacity in non-
aqueous batteries through the intercalation of the cation of elec-
trolyte [53].
3.1.4. Raman spectra of coatings
The Raman Scattering measurements were carried out to char-
acterize the PPy coating on graphite paper and PPy-VOx-CMC
coating on V-intercalated graphite paper within the range of
300e2000 cm
1 (Fig. 4). In the spectrum of PPy, the Raman bands
appeared at about 932 and 1238 cm
1 due to the ring deformation,
and 1056e1100 cm
1 due to the CeH in plane bending vibration
[54]. The peaks at 1380 and 1329 cm
1 are attributed to the anti-
symmetrical CeN stretching vibration mode [55]. Thi Le et al.
showed that the wavenumber is a representation of the redox state
384 E. Karaca et al. / Electrochimica Acta 273 (2018) 379e391

Fig. 2. (a) SEM image of bare PG surface (b) SEM-BSE images of V-intercalated PG surface, and (c) EDX vanadium mapping of V-intercalated PG surface.

Fig. 3. XRD Spectra of (a) bare graphite sheet, (b) PPy and (c) PPy-vanadium oxides
composite on graphite sheet and (d) PPy-vanadium oxides composite on V-interca-
lated graphite sheet.

of PPy, the peak at 1615 cm
1 corresponds to the oxidized state and
the peak at 1564 cm
1 refers to the reduced state of PPy [54,56]. As
seen in Fig. 4, this peak appears at 1580 cm
1 which is assigned Fig. 4. The Raman spectra of (a) PPy on graphite paper and (b) PPy-VOx eCMC on V-
mainly to the C]C stretching vibration mode. The shift of wave- intercalated graphite paper in the region of 300e2000 cm
1.

number and the appearance of intense peak at 932 cm
1 [54]

indicate that PPy in the coatings on electrode surface is partially
intercalated graphite paper, in addition to the characteristic bands
oxidized.
of PPy, the bands related to vanadium oxide and CMC appear at 426
As seen in the Raman spectrum of PPy-VOx-CMC coating on V-
and 683 cm
1 corresponding to VeOeV bond [57,58], and 1087 and
 E. Karaca et al. / Electrochimica Acta 273 (2018) 379e391
1110 cm
1 referring to CeC and CeO bonds, respectively [59,60].
The appearance of the additional bands confirms the existence of
PPy as well as vanadium oxides and CMC in the composite coating.
3.1.5. SEM analysis
SEM analysis has been conducted to investigate the surface
morphology of the PPy on PG, PPy-VOx composite on PG, and PPy-
VOx-CMC composite on V-intercalated PG electrodes (Fig. 5). If the
PG surface (Fig. 2a) is covered with PPy, the film growth yields a
typical cauliflower morphology as referred in the literature (Fig. 5a)
[61,62]. As vanadium oxides are inserted in the composite coating,
the film exhibits an increasingly porous structure (Fig. 5b and c),
leading to more access to the interior sites of the polymer for
dopant and/or electrolyte ions during the electrochemical process
[8]. As seen in Fig. 5c, small-sized nodules form on the cauliflower
structures due to the insertion of CMC together with intercalation
of vanadium, therefore the effective surface area of the coating in
contact with solution increases (Fig. 5d).This leads to the increase of
the capacitance, which is compatible with the results presented in
Table 2.
SEM-EDX analysis of the PPy-VOx-CMC composite on V-inter-
calated PG electrode was also performed (Fig. S3). EDX spectra
reveal that the product is mainly composed of C, N, O, F and V.
When point “a” marked in Fig. 5c was analyzed, an intense peak is
observed due to the presence of vanadium (Fig. S3a). Vanadium
particles are distributed homogeneously as seen in EDX vanadium
mapping of the coating (Fig. 5d). On the other hand, the peak cor-
responding to vanadium appears weaker when the EDX analysis is
performed from the whole surface (Fig. S3b). It is important to note
that a small amount of vanadium oxides (about atomic weight of
1.8% for vanadium from EDX (Fig. S3b)) in composite coating on V-
Fig. 5. SEM images of (a) PPy and (b) PPy-VOx composite on PG surfaces, and (c) PPy-VOx-CMC on V-intercalated PG surface, and (d) EDX vanadium mapping of the PPy-VOx-CMC on
V-intercalated PG electrode.
385
intercalated substrate significantly enhances the capacitance value
(Table 2).
3.2. Electrochemical behavior of VO(BF4)2 on pencil graphite
electrode in acetonitrile
Fig. 6 shows the cyclic voltammogram recorded at the potential
range between
1.5 V and 1.5 V vs. Ag/AgCl on PG surface in the
acetonitrile solution containing 25 mM TBABF4, 25 mM HBF4,
100 mM H2O, 10 mM VO(BF4)2 and also that of vanadium-free
(blank) solution for comparison. In the presence of VO(BF4)2, the
current densities at both negative and positive potentials are
greater than that of the blank solution as seen in Fig. 6. The increase
in current is an indication of fast charge transfer process [61,62].
The oxidation of VO2þ to VOþ 2 is recorded at peak potentials of 1.0 V
(vs Ag/AgCl) with its cathodic peak at about 0.80 V obtained during
the reverse cycle. A further reduction wave of VO2þ to V3þ appears
at about
0.50 V. The intensive cathodic peak at
1.3 V is attributed
to the formation of V2þ.
From the chronopotentiometric curves (Fig. 1A), the potentials
observed during the polymerization, about 2.0 V, 1.5 V, 1.0 V and
0.75 V vs Ag/AgCl, gradually decrease with the increase of specific
capacitance. As vanadium oxides are inserted into the composite
coating, the specific capacitance value increases and the potential
observed in the chronopotentiometric curve decreases from about
2.0 V to 1.5 V vs Ag/AgCl (Fig. 1Aab). When the graphite was inter-
calated with vanadium, the potential decreased down to about
0.75 V vs Ag/AgCl during galvanostatic deposition (Fig. 1Ad). This
result indicates the insertion of additional electroactive vanadium
species within the electroactive polymer and also the catalytic ef-
fect of vanadium species upon polymerization reaction. During the
386 E. Karaca et al. / Electrochimica Acta 273 (2018) 379e391
Fig. 6. Cyclic voltammograms of PG electrode in an acetonitrile solution containing (a)
TBABF4 and (b) VO(BF4)2 and TBABF4, v ¼ 100 mV s
1 (cTBABF4 ¼ 25 mM, cVO(BF4)
2 ¼ 10 mM).
electrooxidation of Py and PPy (R1, R2), vanadium ions in lower
valance (VO2þ) are concurrently oxidized to higher valance (VOþ 2)
(R3), and thus oxidized forms of Py and PPy are produced chemi-
cally (R4, R5) as well as electrochemically in the composite matrix:
Simultaneous electrogeneration of the VOþ 2 ions during the poly-
merization reaction causes the formation of a much greater amount
of pyrrole and polypyrrole cations.
Py /Pyþ þ e

PPy / PPyþ þ e

VO2þ þH2O / VOþ þ
2 þ 2H þ e


VOþ þ
2 þ Py þ 2H / VO
2þ
þ Pyþ þ H2O
VOþ þ
2 þ PPy þ2H / VO
2þ
þ PPyþ þ H2O
3.3. EIS measurements
To reveal the electrochemical properties of the coatings, EIS
measurements were carried out in 100 mM H2SO4 solution and
presented in the forms of Nyquist and Bode plots in Fig. 7. As seen in
Fig. 7, the slopes of the Nyquist plots and the phase angles in Bode
plots gradually increase with the insertion of VOx and CMC into the
composite coating, and sequentially, with the intercalation of va-
nadium on PG surface. The impedance data were processed using
ZSimpWin V3.50 fitting program. The inset of Fig. 7 shows an
equivalent circuit fitting the impedance data of the coatings. The
fitting values for the parameters corresponding to the circuit ele-
ments are listed in Table 3. The chi-squared fitting parameter is
always less than 2  10
3. Rs and Rct represent the uncompensated
resistance and chargeetransfer resistance, respectively. Q is con-
stant phase elements (CPE) used instead of doubleelayer capaci-
tance (Cdl) to define the inhomogeneities in system [63]. W is
Warburg arising from a diffusionecontrolled process at low fre-
quency. The total resistance (Rtotal) of a coated electrode is
considered to be equal to the sum of Rs and Rct values. The Rtotal
values of the coatings gradually decrease with the insertion of VOx
and CMC. Eventually, the lowest Rtotal value is observed for the PPy-
VOx-CMC composite coating synthesized on V-intercalated PG
electrode due to the synergetic effect between PPy and VOx (see
Table 4 and Section 3.4 for details), as discussed in the literature for
other composites [64e70]. The lowest Rtotal can also be associated
with the presence of CMC, which increases the effective surface
area of the coating (Fig. 5d), and the ideal combination of the four
components (PPy, VOx, TX100 and CMC), which leads to a lower
charge transfer resistance or a better capacitive performance.
3.4. Galvanostatic chargeedischarge measurements
Capacitive behaviors of the coatings obtained above were
investigated by chronopotentiometric chargeedischarge curves at
the current density of 1 mA/cm
2 in 100 mM H2SO4 electrolyte.
Fig. 8 shows the charge-discharge curves of the coated electrodes.
These nonlinear curves result from the pseudocapacitive behavior
of coatings [9,71e73]. The specific capacitances were calculated
from Eq (2) using the charge-discharge curves The specific capac-
itance values of PPy, PPy-VOx, and PPy-VOx-CMC on PG electrodes,
and PPy-VOx-CMC composite on V-intercalated PG electrode are
544 F g
1, 597 F g
1, 765 F g
1 and 870 F g
1, respectively.
In order to extract the specific capacitance of the composite
material, cyclic voltammetry and charge-discharge tests were
performed in 100 mM H2SO4 to determine the individual values for
bare PG and V-intercalated PG (Table 4). According to data pre-
sented in Table 4, the capacitive contribution of the substrate ap-
pears to be a small quantity. As a result, the capacitance values of
the composite using cyclic voltammetry and charge-discharge tests
are found as 698 F g
1 (763e65) and 774 F g
1 (870e96), respec-
tively. Consequently, a significant portion of the capacitance is
associated with the composite. In addition, the specific capacitance
R1 values of PPy on PG are found 403 (425e22) F g
1 and 508
(544e36) F g
1 by cyclic voltammetry and charge-discharge tests,
R2 respectively. The sum of these capacitances with V-intercalated PG
electrodes gives 468 (403 þ 65.0) F g
1 and 604 (508 þ 96.0) F g
1,
R3 respectively. These capacitance values still appear to be lower than
those of PPy-VOx-CMC on V-intercalated PG electrode (668 F g
1 by
R4 cyclic voltammetry and 774 F g
1 by charge-discharge). The differ-
ences between the capacitance values are up to 33% for cyclic
R5 voltammetry and 22% for charge-discharge. The increase of the
capacitance can be attributed to the synergetic effect of the com-
posite with homogenously encapsulated VOx in PPy, as discussed in
the literature for other composites [64,65,67e70].
In the case of composite, additional electroactive vanadium
species are encapsulated within the electroactive PPy, which
enhanced the capacitive properties. The improvement of the spe-
cific capacitance values can be correlated with the redox reactions
of PPy and VOx in the composite coating. During the electro-
oxidation of PPy (R2), vanadium oxide in lower valance (V2O4) is
also concurrently oxidized to higher valance V2O5 (R3). Addition-
ally, oxidized form PPyþ is also produced chemically (R8) in com-
posite matrix similar to the studies in the literature [74e77]. The
greater capacitance obtained from the composite indicates the
validity of the catalytic reaction among the species (R8).
PPy / PPyþ þ e
R2
V2O4 þ H2O /V2O5 þ 2Hþ þ 2 e
R3
PPyþ þ e
/ PPy R6
V2O5 þ 2Hþ þ 2 e
/ V2O4 þ H2O R7
V2O5 þ 2 PPy þ2Hþ / V2O4 þ 2 PPyþ þ H2O R8
While the reactions R2 and R3 occur during the charging pro-
cess, the reactions R6 and R7 take place during the discharging
 E. Karaca et al. / Electrochimica Acta 273 (2018) 379e391 387

Fig. 7. The Nyquist plots obtained in 100 mM H2SO4 solution for coatings of (a) PPy, (b) PPy-VOx, and (c) PPy-VOx-CMC on PG electrodes, and (d) PPy-VOx-CMC on V-intercalated PG
electrode. (Their Bode plots and equivalent circuit are also shown as inset).

Table 3
Impedance parameters obtained by fitting the impedance spectra recorded in 100 mM H2SO4 solution for the coatings of (a) PPy on PG (b) PPy-VOx composite on PG (c) PPy-
VOx-CMC composite on PG and (d) PPy-VOx-CMC composite on V-intercalated PG electrodes.

Rs/U cm2 Q1/F cm
2 n Rct/U cm2 W/Us
1/2 cm
2 Q2/F cm
2 n Rtotal U cm2 % Error

3
a 2.08 1.7  10 0.90 0.29 0.885 0.045 0.92 2.37 0.0021
b 1.75 2.0  10
3 0.97 0.31 0.496 0.049 0.92 2.06 0.0020
c 1.07 2.3  10
3 0.60 0.26 2.135 0.049 0.92 1.32 0.0015
d 0.71 4.0  10
3 0.60 0.24 0.487 0.057 0.95 0.94 0.0010

Table 4
The specific capacitances with the rate capabilities in parenthesis from cyclic voltammetry, and the specific capacitance with the cycle lives in parenthesis from
charge-discharge tests. The measurements are conducted in 100 mM H2SO4 solution for the bare PG, V-intercalated PG, PPy on PG and composite coating on V-
intercalated PG electrodes (for the coatings at a mass loading of 0.19 mg cm
2).

Cm/F g
1

Cyclic Voltammmetry (Rate capability) Galvanostatic Charge-Discharge at 1 mA cm
2

(remain after 1000 cycles)

Bare PG 22.0 (32%) 36.0 (20%)

V-intercalated PG 65.0 (63%) 96.0 (75%)
PPy on PG 425 (46%) 544 (37%)
PPy-VOx-CMC on V-intercalated PG 763 (80%) 870 (44%)

process.
The capacitive property (and cyclic stability) of PPy-VOx-CMC
composite on V-intercalated PG electrode was investigated in
aqueous solutions of H2SO4 and Li2SO4, and in an acetonitrile so-
lution of HBF4/TBABF4 (Fig. S4). The specific capacitance values (and
percentage of retained capacitance after 1000 cycles) were found as
774 F g
1 (44%), 690 F g
1 (35%) and 800 F g
1 (87%) at 1 mA cm
2
(15 mA cm
2), respectively, after the capacitances of V-intercalated
PG were subtracted. The highest specific capacitance and the cyclic
stability are recorded in the acetonitrile solution of 100 mM HBF4/
TBABF4. Moreover, the voltage window increased up to 1.3 V in
nonaqueous (HBF4) solution when compared to the voltage win-
dow for aqueous solutions (0.95 V). This can be expressed as an
advantage of organic electrolytes over aqueous electrolytes
[26,78,79].
When the effect of additives on cycle life of coatings in an
acetonitrile solution of HBF4/TBABF4 are investigated, it is observed
that the specific capacitance of the PPy, PPy-VOx and PPy-VOx-CMC
on PG electrodes, and PPy-VOx-CMC on V-intercalated PG electrode
still remains 32%, 63%, 81% and 87% after 1000 cycles, respectively.
Vanadium oxides encapsulated in PPy doubles the cycle life of the
coating. CMC in the coating increases the cyclic performance since
it possibly improves the mechanical stability of the composite. In
the case of vanadium intercalation, the composite coating exhibits
the highest cycling stability as the electrode material. For com-
parison, the stabilities of the bare PG and V-intercalated PG sub-
strates are also presented in Table 4. Accordingly, V-intercalation
provides the most significant contribution to the stability of PG
electrode. In addition, VOx inside the composite improves the sta-
bility of the composite coating.
Compared to the bare PG, the V-intercalated graphite PG elec-
trode does not only exhibit a higher specific capacitance at high
scan rates between 20 and 100 mV s
1, but also presents a better
rate capability (63%) than that of bare graphite (32%). These results
388 E. Karaca et al. / Electrochimica Acta 273 (2018) 379e391
Fig. 8. Galvanostatic chargeedischarge curves recorded in 100 mM H2SO4 solution at
1 mA cm
2 for coatings of (a) PPy, (b) PPy-VOx, and (c) PPy-VOx-CMC on PG electrodes,
(d) PPy-VOx-CMC on V-intercalated PG electrode at a mass loading of 0.19 mg cm
2,
and (e) bare PG electrode.
imply that V-intercalation is responsible for the improvement of
the rate capability. The greatest rate capability is obtained for PPy-
VOx-CMC on V-intercalated PG electrode (80%).
In the galvanostatic charge-discharge measurements,
2.0 mg cm
2 is consistently used as the mass loading to conduct
accurate comparative studies of the specific capacitances. The
specific capacitance of PPy-VOx-CMC on V-intercalated PG elec-
trode was found as 428 F g
1 at 2.0 A g
1 via charge-discharge
measurements in an acetonitrile solution of HBF4/TBABF4
(Fig. 9A). For the most representative result, the specific capaci-
tance of the composite is found as 236 F g
1 for a mass loading of
10 mg cm
2 at 2 A g
1 (Fig. 9B). The specific capacitances were also
determined in the same electrolytes for bare PG (11.0 F g
1) and V-
intercalated PG (32.0 F g-1) at the current density of 2.0 A g
1.
Accordingly, the substrate contribution to the capacitance value
stays minor. After subtracting the capacitance of V-intercalated PG
substrate, 2 mg cm
2 and 10 mg cm
2 loaded composites, respec-
tively, provide capacitance values of 396 Fg-1 and 204 Fg-1.
The asymmetric supercapacitor was prepared in a Teflon Swa-
gelok for the electrochemical measurements at room temperature
in an acetonitrile/adiponitrile solution of 100 mM HBF4/TBABF4.
The cathode was prepared by mixing carbon black and
Fig. 9. Galvanostatic chargeedischarge curves of PPy-VOx-CMC on V-intercalated PG
electrode at a mass loading of (a) 2 mg cm
2 and (b)10 mg cm
2recorded in an
acetonitrile solution of 100 mM HBF4/TBABF4 at 2 A g
1.
polyvinylidene fluoride (PVDF) binder (85:15 wt%) in N-methyl-2-
pyrrolidone (NMP) solvent to form a homogeneous slurry. After-
wards, the slurry was coated uniformly on graphite paper (SGL
Carbon GDL 39 AA). The coated electrodes were dried at 100  C for
12 h in vacuum. A filtered paper was used as the separator and PPy-
VOx-CMC composite (20 mg cm
2) on V-intercalated graphite pa-
per was used as the anode in Teflon Swagelok. In the symmetric
supercapacitor, PPy-VOx-CMC composites on V-intercalated
graphite paper were used as both anode and cathode. For pre-
conditioning, the electrodes and separator were immersed in the
electrolyte solution for 12 h before the electrochemical measure-
ments. The charge-discharge tests were performed at 1.5 A g
1
(Fig. 10). The results showed that the specific capacitance of
asymmetric supercapacitor (92.0 F g
1) was higher than that of the
symmetric supercapacitor (84.0 F g
1). The symmetric cell and
asymmetric cell cycled retained 82% and 74% of their initial ca-
pacities after 5000 cycles at 2.5 A g
1, respectively (Fig. S5). The
energy density (E, Wh kg
1) and power density (P, W kg
1) values
[52] were also determined at various current densities by using the
charge-discharge curves (Fig.S6), and presented as Ragone plot in
Fig. 11.
The energy density of PPy-VOx-CMC composite on V-interca-
lated graphite paper gradually decreases with the increase of the
current density. These findings can open up the possibility of using
this coating in supercapacitors with high performance. Some ex-
amples of the conducting polymerebased supercapacitor electrode
materials and their electrochemical properties are given in Table 5
for comparison. The electrode material prepared in this study ex-
hibits higher capacitance which supports the possibility of utilizing
the electrodes in electrochemical supercapacitors.
4. Conclusion
In summary, PPy-VOx composite films were galvanostatically
prepared in one step on V-intercalated PG substrates in the pres-
ence of carboxymethyl cellulose (CMC). The intercalation of vana-
dium on PG surface provides higher specific capacitances, which
are 800 F g
1 (5.3 A g
1 or 1 mA cm
2) at a mass loading of
0.19 mg cm
2, 396 F g
1 (2 A g
1) at a mass loading of 2.0 mg cm
2
and 204 F g
1 (2 A g
1) at a mass loading of 10.0 mg cm
2 for the
PPy-VOx-CMC composite coatings, when the capacitance of the
bare graphite is subtracted. Respectively, 87%, 72% and 64% of their
original capacities were retained after 1000 cycles. This can be
Fig. 10. Galvanostatic chargeedischarge curves recorded at 1.5 A g
1 for symmetric
and asymmetric supercapacitor at a mass loading of 20 mg cm
2 in an acetonitrile/
adiponitrile solution of 100 mM HBF4/TBABF4.
 E. Karaca et al. / Electrochimica Acta 273 (2018) 379e391 389

attributed to the CMC which enhances the mechanical stability of

Fig. 11. Ragone Plot of the symmetric and asymmetric supercapacitors examined in
this study.
the composite. Asymmetric supercapacitor delivers an energy
density of 18 Wh kg
1 and at a power density of 0.43 kW kg-1 at
0.5 A g
1 in the potential range of 1.2 V for mass loading of
20 mg cm
2.
The improved electrochemical properties of PPy-VOx-CMC
composite on V-intercalated graphite can be attributed to the ef-
fects of the VOx particles within the PPy coating. Vanadium in-
tercalates on the graphite paper prior to the deposition reaction
and converts into VOx during the electrodeposition of the com-
posite. Therefore, VOx layer exists between the graphite paper and
the coating. Throughout the formation of PPy, VOx is simulta-
neously encapsulated inside the polymer. Hence, VOx homoge-
nously deposits inside the coating as well as the interface between
the coating and the electrode without the assist of a binder. The
results indicate that both the vanadium intercalation and the
composite formation in acetonitrile medium in the presence of
VO(BF4)2 and CMC have significant impacts on morphology, which
also greatly influences the capacitive performance. Eventually, ac-
cording to the charge-discharge measurements, VOx and PPy do not
only exist on the electrode surface with CMC for a long cycle-life,

Table 5
Comparison of electrochemical performance of PPy-Metal oxide based supercapacitors.

Electrode Voltage V Electrolyte Specific Capacitance Energy Density Power Density Cycles (Retained Ref.
F g
1 (mA cm
2) Wh kg-1 kW kg 1 Capacitance)
(mass loading)

PPy-Graphene 0.7 H2SO4 e 50.1 0.4 1000 (86%) [80]

(
)
Sym. PPy-V2O5 2 LiCl 295 (0.5 A g
1) 82 0.8 5000 (80%) [23]
(1.2 mg cm-2)
Asym. PPy-FeO//CoeV2O5 1.4 KOH 196 (1 A g
1) 38.2 0.70 5000 (95%) [9]
(
)
Asym. VS2//CeFe/PANI 1.7 KOH 118 (5 A g
1) 27.8 3.0 10000 (95%) [81]
(
)
Sym. Polyaniline-V2O5 fibers 2.0 KCl 96.1 (0.15 A g
1) 26.7 0.22 2000 (73%) [73]
(2 mg cm
2)
Sym. Polyaniline-V2O5 1.6 LiCl 311 (0.5 A g
1) 69.2 0.72 5000 (92%) [22]
(1.98 mg cm
2)
Sym. PPy-MnO2 1.0 Na2SO4 65 (1 A g
1) 17.0 2.8 1000 (93%) [82]
(2 mg cm
2)
Asym. MnO2//PPy-Graphene 1.7 PVA-LiCl 68 (0.25 A g
1) 16.0 3.0 2000 (75%) [16]
(
)
Sym. PPy-Ru 2.0 PVA-H2SO4 122 (2 A g
1) 33.8 1.12 500 (82%) [7]
(
)
PPy-NiO 0.8 NaCl e 39.5 0.239 300 (25%) [12]
(
)
PPy-CuO 0.8 NaCl e 39.5 0.044 300 (67%) [83]
(
)
Asym. PPy//CoO 1.8 NaOH 47.2 (1 A g
1) 11.8 5.5 2000 (99%) [84]
(4 mg cm
2)
PPy-MoO3-Graphite Oxide 1.0 K2SO4 175 (0.1 A g
1) e e 600 (88%) [85]
Hybrid Li3VO4//carbon nanofibers 3.8 Gel Polymer Electrolyte (
) 110 0.17 2400 (86%) [86]
(0.2 A g
1)
(
)
CoCO3eCoO nanostructure 0.5 KOH 510 (1 A g
1) e e 5000 (82) [87]
(1.5 mg cm-2)
KxMnO2.nH2O 1.0 K2SO4 140 (0.1 A g
1) e e 800 (99%) [88]
(
)
Asym. NaxMnO2//MoO2 1.0 Na2SO4 2.04 F cm
3 0.92 mWh cm
3
e 6000 (97%) [89]
(0.57 mA cm
2)
(
)
Asym. NaxMnO2 3.8 LiPF6 140 mAh g
1 58.6 e 1000 (98%) [90]
(
)
Na2Ti3O7.CNT//AC 3.0 NaClO4/Propylene Carbonate (0.4 A g
1) 58.5 3.0 3000 (75%) [90]
(3.2 mg cm
2)
Na-TNT//AC 3.0 Propylene Carbonate/Dimethyl carbonate (0.25 A g
1) 34.0 0.89 1000 (80%) [91]
Sym. PPy-VOx-CMCon V intc. PG 0.8 HBF4/ACN/Adiponitrile 122 (0.5 A g
1) 11 0.29 5000 (82%) This study
(20 mg cm
2)
Asym. PPy-VOx-CMCon V intc. PG 1.2 HBF4/ACN/Adiponitrile 91 (0.5 A g
1) 18 0.43 5000 (74%) This study
(20 mg cm
2)
390 E. Karaca et al. / Electrochimica Acta 273 (2018) 379e391
but they also improve the specific capacitance. Although the
amount of VOx is so small, it provides a significant contribution to
the capacitance of the composite due to the homogenous encap-
sulation as well as synergetic effect. The findings given in this study
are promising for the possible future applications and demonstrate
the viability of an asymmetric supercapacitor.
Acknowledgements
We are grateful to the Turkish Scientific and Technical Research
_
Council for the Grant (No. TÜBITAK/117Z340).
Appendix A. Supplementary data
Supplementary data related to this article can be found at 10.
1016/j.electacta.2018.04.059.
References
[1] Y. Yan, B. Li, W. Guo, H. Pang, H. Xue, Vanadium based materials as electrode
materials for high performance supercapacitors, J. Power Sources 329 (2016)
148e169.
[2] L.-Z. Fan, J. Maier, High-performance polypyrrole electrode materials for redox
supercapacitors, Electrochem. Commun. 8 (2006) 937e940.
[3] J. Zhang, L.-B. Kong, H. Li, Y.-C. Luo, L. Kang, Synthesis of polypyrrole film by
pulse galvanostatic method and its application as supercapacitor electrode
materials, J. Mater. Sci. 45 (2010) 1947e1954.
[4] J.S. Kwon, B.C. Kim, G.G. Wallace, J.H. Park, S.H. Kim, J.M. Ko, H. Ahn, Nafion-
Doped polypyrrole as a supercapacitor electrode in ionic liquid, Mol. Cryst. Liq.
Cryst. 520 (2010), 262/[538]-266/[542].
[5] R.K. Sharma, A.C. Rastogi, S.B. Desu, Pulse polymerized polypyrrole electrodes
for high energy density electrochemical supercapacitor, Electrochem. Com-
mun. 10 (2008) 268e272.
[6] B. Muthulakshmi, D. Kalpana, S. Pitchumani, N.G. Renganathan, Electro-
chemical deposition of polypyrrole for symmetric supercapacitors, J. Power
Sources 158 (2006) 1533e1537.
[7] Y. Zhou, Y. Xie, Capacitive performance of ruthenium-coordinated poly-
pyrrole, New J. Chem. 41 (2017) 10312e10323.
[8] B.L. He, Y.K. Zhou, W. Zhou, B. Dong, H.L. Li, Preparation and characterization
of ruthenium-doped polypyrrole composites for supercapacitor, Mater. Sci.
Eng. 374 (2004) 322e326.
[9] A. Maitra, A.K. Das, S.K. Karan, S. Paria, R. Bera, B.B. Khatua, A mesoporous
high-performance supercapacitor electrode based on polypyrrole wrapped
iron oxide decorated nanostructured cobalt vanadium oxide hydrate with
enhanced electrochemical capacitance, Ind. Eng. Chem. Res. 56 (2017)
2444e2457.
[10] S. Peng, Q. Xu, L. Fan, C. Wei, H. Bao, W. Xu, J. Xu, Flexible polypyrrole/cobalt
sulfide/bacterial cellulose composite membranes for supercapacitor applica-
tion, Synth. Met. 222 (2016) 285e292.
[11] H. Wei, C. He, J. Liu, H. Gu, Y. Wang, X. Yan, J. Guo, D. Ding, N.Z. Shen, X. Wang,
S. Wei, Z. Guo, Electropolymerized polypyrrole nanocomposites with cobalt
oxide coated on carbon paper for electrochemical energy storage, Polymer 67
(2015) 192e199.
[12] S. Peng, L. Fan, C. Wei, H. Bao, H. Zhang, W. Xu, J. Xu, Polypyrrole/nickel sul-
fide/bacterial cellulose nanofibrous composite membranes for flexible
supercapacitor electrodes, Cellulose 23 (2016) 2639e2651.
[13] J. Wei, G. Xing, L. Gao, H. Suo, X. He, C. Zhao, S. Li, S. Xing, Nickel foam based
polypyrroleeAg composite film: a new route toward stable electrodes for
supercapacitors, New J. Chem. 37 (2013) 337e341.
[14] C.H. Ng, H.N. Lim, Y.S. Lim, W.K. Chee, N.M. Huang, Fabrication of flexible
polypyrrole/graphene oxide/manganese oxide supercapacitor, Int. J. Energy
Res. 39 (2015) 344e355.
[15] Y.S. Lim, Y.P. Tan, H.N. Lim, N.M. Huang, W.T. Tan, M.A. Yarmo, C.-Y. Yin,
Potentiostatically deposited polypyrrole/graphene decorated nano-
manganese oxide ternary film for supercapacitors, Ceram. Int. 40 (2014)
3855e3864.
[16] W.-H. Khoh, J.-D. Hong, Solid-state asymmetric supercapacitor based on
manganese dioxide/reduced-graphene oxide and polypyrrole/reduced-
graphene oxide in a gel electrolyte, Colloids Surf. Physicochem. Eng. Aspects
456 (2014) 26e34.
[17] M. Jin, G. Han, Y. Chang, H. Zhao, H. Zhang, Flexible electrodes based on
polypyrrole/manganese dioxide/polypropylene fibrous membrane composite
for supercapacitor, Electrochim. Acta 56 (2011) 9838e9845.
[18] Z.H. Dong, Y.L. Wei, W. Shi, G.A. Zhang, Characterisation of doped polypyrrole/
manganese oxide nanocomposite for supercapacitor electrodes, Mater. Chem.
Phys. 131 (2011) 529e534.
[19] R.K. Sharma, A.C. Rastogi, S.B. Desu, Manganese oxide embedded polypyrrole
nanocomposites for electrochemical supercapacitor, Electrochim. Acta 53
(2008) 7690e7695.
[20] M. Yu, Y. Zeng, Y. Han, X. Cheng, W. Zhao, C. Liang, Y. Tong, H. Tang, X. Lu,
Valence-optimized vanadium oxide supercapacitor electrodes exhibit ultra-
high capacitance and super-long cyclic durability of 100 000 cycles, Adv.
Funct. Mater. 25 (2015) 3534e3540.
[21] C.-H. Lai, C.-K. Lin, S.-W. Lee, H.-Y. Li, J.-K. Chang, M.-J. Deng, Nanostructured
Na-doped vanadium oxide synthesized using an anodic deposition technique
for supercapacitor applications, J. Alloy. Comp. 536 (2012) S428eS431.
[22] M.-H. Bai, T.-Y. Liu, F. Luan, Y. Li, X.-X. Liu, Electrodeposition of vanadium
oxideepolyaniline composite nanowire electrodes for high energy density
supercapacitors, J. Mater. Chem. 2 (2014) 10882.
[23] M.H. Bai, L.J. Bian, Y. Song, X.X. Liu, Electrochemical codeposition of vanadium
oxide and polypyrrole for high-performance supercapacitor with high
working voltage, ACS Appl. Mater. Interfaces 6 (2014) 12656e12664.
[24] S. Wang, K.A. Owusu, L. Mai, Y. Ke, Y. Zhou, P. Hu, S. Magdassi, Y. Long, Va-
nadium dioxide for energy conservation and energy storage applications:
synthesis and performance improvement, Appl. Energy 211 (2018) 200e217.
[25] G. Huang, C. Li, X. Sun, J. Bai, Fabrication of vanadium oxide, with different
valences of vanadium, -embedded carbon fibers and their electrochemical
performance for supercapacitor, New J. Chem. 41 (2017) 8977e8984.
[26] Y. Wang, Y. Song, Y. Xia, Electrochemical capacitors: mechanism, materials,
systems, characterization and applications, Chem. Soc. Rev. 45 (2016)
5925e5950.
[27] J.-W. Lee, B.N. Popov, Electrochemical intercalation of lithium into poly-
pyrrole/silver vanadium oxide composite used for lithium primary batteries,
J. Power Sources 161 (2006) 565e572.
[28] X. Zhou, X. Chen, T. He, Q. Bi, L. Sun, Z. Liu, Fabrication of polypyrrole/vana-
dium oxide nanotube composite with enhanced electrochemical performance
as cathode in rechargeable batteries, Appl. Surf. Sci. 405 (2017) 146e151.
[29] C. Liang, D. Fang, Y. Cao, G. Li, Z. Luo, Q. Zhou, C. Xiong, W. Xu, Polypyrrole-
encapsulated vanadium pentoxide nanowires on a conductive substrate for
electrode in aqueous rechargeable lithium battery, J. Colloid Interface Sci. 439
(2015) 69e75.
[30] C.-J. Cui, G.-M. Wu, H.-Y. Yang, S.-F. She, J. Shen, B. Zhou, Z.-H. Zhang, A new
high-performance cathode material for rechargeable lithium-ion batteries:
polypyrrole/vanadium oxide nanotubes, Electrochim. Acta 55 (2010)
8870e8875.
[31] Y.K. Anguchamy, J.-W. Lee, B.N. Popov, Electrochemical performance of pol-
ypyrrole/silver vanadium oxide composite cathodes in lithium primary bat-
teries, J. Power Sources 184 (2008) 297e302.
[32] S. De, A. Dey, S.K. De, Characterization and transport properties of intercalated
polypyrroleevanadium pentoxide xerogel nanocomposite, Solid State Com-
mun. 137 (2006) 662e667.
[33] F. Yakuphanoglu, M.E. Aydin, Effects of polymerization medium on electrical
conductivity and optical properties of organic semiconductor-based poly-
pyrrole, Polym. Eng. Sci. 47 (2007) 1016e1020.
[34] M. Yamaura, T. Hagiwara, K. Iwata, Enhancement of electrical conductivity of
polypyrrole film by stretching: counter ion effect, Synth. Met. 26 (1988)
209e224.
[35] J. Yang, T. Lan, J. Liu, Y. Song, M. Wei, Supercapacitor electrode of hollow
spherical V2O5 with a high pseudocapacitance in aqueous solution, Electro-
chim. Acta 105 (2013) 489e495.
[36] R.B. Pujari, V.C. Lokhande, V.S. Kumbhar, N.R. Chodankar, C.D. Lokhande,
Hexagonal microrods architectured MoO3 thin film for supercapacitor
application, J. Mater. Sci. Mater. Electron. 27 (2015) 3312e3317.
[37] X. Xiao, Y. Wang, G. Chen, L. Wang, Y. Wang, Mn3O4/activated carbon com-
posites with enhanced electrochemical performances for electrochemical
capacitors, J. Alloy. Comp. 703 (2017) 163e173.
[38] D. Schopf, M. Es-Souni, Thin film nanocarbon composites for supercapacitor
applications, Carbon 115 (2017) 449e459.
[39] L. Groenendaal, G. Zotti, F. Jonas, Optical, conductive and magnetic properties
of electrochemically prepared alkylated poly(3,4-ethylenedioxythiophene)s,
Synth. Met. 118 (2001) 105e109.
[40] N. Pekmez, K. Pekmez, A. Yıldız, Electrochemical behavior of polyaniline films
in acetonitrile, J. Electroanal. Chem. 370 (1994) 223e229.
[41] H. Karami, Synthesis of aniline e pyrrole copolymer nanostructures by the
pulsed galvanostatic polymerization, Int. J. Electrochem. Sci (2016)
3056e3073.
[42] E. Karaca, N.O.€ Pekmez, K. Pekmez, Galvanostatic deposition of polypyrrole in
the presence of tartaric acid for electrochemical supercapacitor, Electrochim.
Acta 147 (2014) 545e556.
[43] D.P. Dubal, W.B. Kim, C.D. Lokhande, Surfactant assisted electrodeposition of
MnO2 thin films: improved supercapacitive properties, J. Alloy. Comp. 509
(2011) 10050e10054.
[44] Y. Şahin, K. Pekmez, A. Yıldız, Electropolymerization and in situ sulfonation of
aniline in watereacetonitrile mixture containing FSO3H, Synth. Met. 131
(2002) 7e14.
[45] M. Zhou, J. Heinze, Electropolymerization of pyrrole and electrochemical
study of polypyrrole. 3. Nature of “water effect” in acetonitrile, J. Phys. Chem.
B 103 (1999) 8451e8457.
[46] S. Ghosh, G.A. Bowmaker, R.P. Cooney, J.M. Seakins, Infrared and Raman
spectroscopic studies of the electrochemical oxidative degradation of poly-
pyrrole, Synth. Met. 95 (1998) 63e67.
[47] M. Yu, J. Li, L. Wang, KOH-activated carbon aerogels derived from sodium
carboxymethyl cellulose for high-performance supercapacitors and dye
adsorption, Chem. Eng. J. 310 (2017) 300e306.
 E. Karaca et al. / Electrochimica Acta 273 (2018) 379e391
[48] C. Wan, Y. Jiao, J. Li, Flexible, highly conductive, and free-standing reduced
graphene oxide/polypyrrole/cellulose hybrid papers for supercapacitor elec-
trodes, J. Mater. Chem. 5 (2017) 3819e3831.
[49] A.M. Ramos, S. Pereira, M.T. Cidade, G. Pereira, R. Branquinho, L. Pereira,
R. Martins, E. Fortunato, Preparation and characterization of cellulose nano-
composite hydrogels as functional electrolytes, Solid State Ionics 242 (2013)
26e32.
[50] F. Beguin, E. Frackowiak, Carbons for Electrochemical Energy Storage and
Conversion Systems, CRC Press, 2009.
[51] C. Commenda, J. Pühringer, Microstructural characterization and quantifica-
tion of ZneAleMg surface coatings, Mater. Char. 61 (2010) 943e951.
[52] A. De Adhikari, R. Oraon, S.K. Tiwari, J.H. Lee, N.H. Kim, G.C. Nayak, A V2O5
nanorod decorated graphene/polypyrrole hybrid electrode: a potential
candidate for supercapacitors, New J. Chem. 41 (2017) 1704e1713.
[53] J.R. Gonza lez, F. Nacimiento, M. Cabello, R. Alca ntara, P. Lavela, J.L. Tirado,
Reversible intercalation of aluminium into vanadium pentoxide xerogel for
aqueous rechargeable batteries, RSC Adv. 6 (2016) 62157e62164.
[54] H. Nguyen Thi Le, Raman spectroscopy analysis of polypyrrole films as pro-
tective coatings on iron, Synth. Met. 140 (2004) 287e293.
[55] M. Li, Z. Wei, L. Jiang, Polypyrrole nanofiber arrays synthesized by a biphasic
electrochemical strategy, J. Mater. Chem. 18 (2008).
[56] M. Karabacak, E. Kose, A. Atac, E.B. Sas, A.M. Asiri, M. Kurt, Experimental (FT-
IR, FT-Raman, UVeVis, 1H and 13CNMR) and computational (density func-
tional theory) studies on 3-bromophenylboronic acid, J. Mol. Struct. 1076
(2014) 358e372.
[57] J. Crane, M. Warwick, R. Smith, N. Furlan, R. Binions, The application of electric
fields to aerosol assisted chemical vapor deposition reactions, J. Electrochem.
Soc. 158 (2011) D62eD67.
[58] I.E. Wachs, Catalysis science of supported vanadium oxide catalysts, Dalton
Trans. 42 (2013) 11762e11769.
[59] S.-N. Yuen, S.-M. Choi, D.L. Phillips, C.-Y. Ma, Raman and FTIR spectroscopic
study of carboxymethylated non-starch polysaccharides, Food Chem. 114
(2009) 1091e1098.
[60] F. Adar, Molecular spectroscopy workbench characterizing modified celluloses
using Raman spectroscopy, Spectroscopy 31 (2016) 22e27.
[61] F. Altaf, R. Qureshi, S. Ahmed, Surface protection of copper by azoles in borate
buffers-voltammetric and impedance analysis, J. Electroanal. Chem. 659
(2011) 134e142.
[62] H.-S. Kim, Electrochemical properties of graphite-based electrodes for redox
flow batteries, Bull. Kor. Chem. Soc. 32 (2011) 571e575.
€
[63] B. Zeybek, N. Ozçiçek Pekmez, E. Kılıç, Electrochemical synthesis of bilayer
coatings of poly(N-methylaniline) and polypyrrole on mild steel and their
corrosion protection performances, Electrochim. Acta 56 (2011) 9277e9286.
[64] J. Wang, Z. Wu, K. Hu, X. Chen, H. Yin, High conductivity graphene-like MoS2/
polyaniline nanocomposites and its application in supercapacitor, J. Alloy.
Comp. 619 (2015) 38e43.
[65] L. Wang, L. Chen, B. Yan, C. Wang, F. Zhu, X. Jiang, Y. Chao, G. Yang, In situ
preparation of SnO2@polyaniline nanocomposites and their synergetic
structure for high-performance supercapacitors, J. Mater. Chem. 2 (2014).
[66] Y. Liu, H. Wang, J. Zhou, L. Bian, E. Zhu, J. Hai, J. Tang, W. Tang, Graphene/
polypyrrole intercalating nanocomposites as supercapacitors electrode, Elec-
trochim. Acta 112 (2013) 44e52.
[67] W. Wang, Q. Hao, W. Lei, X. Xia, X. Wang, Graphene/SnO2/polypyrrole ternary
nanocomposites as supercapacitor electrode materials, RSC Adv. 2 (2012).
[68] J.-G. Wang, Y. Yang, Z.-H. Huang, F. Kang, Rational synthesis of MnO2/con-
ducting polypyrrole@carbon nanofiber triaxial nano-cables for high-
performance supercapacitors, J. Mater. Chem. 22 (2012).
[69] P. Lv, Y.Y. Feng, Y. Li, W. Feng, Carbon fabric-aligned carbon nanotube/MnO2/
conducting polymers ternary composite electrodes with high utilization and
mass loading of MnO2 for super-capacitors, J. Power Sources 220 (2012)
160e168.
[70] W. Zhou, J. Liu, T. Chen, K.S. Tan, X. Jia, Z. Luo, C. Cong, H. Yang, C.M. Li, T. Yu,
Fabrication of Co3O4-reduced graphene oxide scrolls for high-performance
supercapacitor electrodes, Phys. Chem. Chem. Phys. 13 (2011) 14462e14465.
[71] A.G. Tabrizi, N. Arsalani, H. Namazi, I. Ahadzadeh, Vanadium oxide assisted
391
synthesis of polyaniline nanoarrays on graphene oxide sheets and its appli-
cation in supercapacitors, J. Electroanal. Chem. 798 (2017) 34e41.
[72] E. Umeshbabu, G. Ranga Rao, Vanadium pentoxide nanochains for high-
performance electrochemical supercapacitors, J. Colloid Interface Sci. 472
(2016) 210e219.
[73] W.F. Mak, G. Wee, V. Aravindan, N. Gupta, S.G. Mhaisalkar, S. Madhavi, High-
energy density asymmetric supercapacitor based on electrospun vanadium
pentoxide and polyaniline nanofibers in aqueous electrolyte, J. Electrochem.
Soc. 159 (2012) A1481eA1488.
[74] H.P. Wong, B.C. Dave, F. Leroux, J. Harreld, B. Dunn, L.F. Nazar, Synthesis and
characterization of polypyrrole vanadium pentoxide nanocomposite aerogels,
J. Mater. Chem. 8 (1998) 1019e1027.
[75] F. Meng, X. Yan, Y. Zhu, P. Si, Controllable synthesis of MnO2/polyaniline
nanocomposite and its electrochemical capacitive property, Nanoscale Res
Lett. 8 (2013) 179.
[76] L. Shao, J.-W. Jeon, J.L. Lutkenhaus, Porous polyaniline nanofiber/vanadium
pentoxide layer-by-layer electrodes for energy storage, J. Mater. Chem. 1
(2013).
[77] Y. He, S. Du, H. Li, Q. Cheng, V. Pavlinek, P. Saha, MnO2/polyaniline hybrid
nanostructures on carbon cloth for supercapacitor electrodes, J. Solid State
Electrochem. 20 (2016) 1459e1467.
[78] M. Jayalakshmi, K. Balasubramanian, Simple capacitors to supercapacitors - an
overview, Int. J. Electrochem. Sci. 3 (2008) 1196e1217.
[79] C. Zhong, Y. Deng, W. Hu, J. Qiao, L. Zhang, J. Zhang, A review of electrolyte
materials and compositions for electrochemical supercapacitors, Chem. Soc.
Rev. 44 (2015) 7484e7539.
[80] A. Wang, X. Zhou, T. Qian, C. Yu, S. Wu, J. Shen, Supercapacitors based on
highly dispersed polypyrrole-reduced graphene oxide composite with a fol-
ded surface, Appl. Phys. A 120 (2015) 693e698.
[81] M.N. Rantho, M.J. Madito, F.O. Ochai-Ejeh, N. Manyala, Asymmetric super-
capacitor based on vanadium disulfide nanosheets as a cathode and carbon-
ized iron cations adsorbed onto polyaniline as an anode, Electrochim. Acta
260 (2018) 11e23.
[82] J.K. Gan, Y.S. Lim, N.M. Huang, H.N. Lim, Effect of pH on morphology and
supercapacitive properties of manganese oxide/polypyrrole nanocomposite,
Appl. Surf. Sci. 357 (2015) 479e486.
[83] S. Peng, L. Fan, W. Rao, Z. Bai, W. Xu, J. Xu, Bacterial cellulose membranes
coated by polypyrrole/copper oxide as flexible supercapacitor electrodes,
J. Mater. Sci. 52 (2016) 1930e1942.
[84] C. Zhou, Y. Zhang, Y. Li, J. Liu, Construction of high-capacitance 3D CoO@
polypyrrole nanowire array electrode for aqueous asymmetric supercapacitor,
Nano Lett. 13 (2013) 2078e2085.
[85] F. Yu, Y. Liu, Y. Zhu, F. Dai, L. Zhang, Z. Wen, Polypyrrole@MoO3/reductive
graphite oxide nanocomposites as anode material for aqueous super-
capacitors with high performance, Mater. Lett. 171 (2016) 104e107.
[86] F. Wang, Z. Liu, X. Yuan, J. Mo, C. Li, L. Fu, Y. Zhu, X. Wu, Y. Wu, A quasi-solid-
state Li-ion capacitor with high energy density based on Li3VO4/carbon
nanofibers and electrochemically-exfoliated graphene sheets, J. Mater. Chem.
5 (2017) 14922e14929.
[87] X. Ji, S. Cheng, L. Yang, Y. Jiang, Z.-j. Jiang, C. Yang, H. Zhang, M. Liu, Phase
transitioneinduced electrochemical performance enhancement of hierarchi-
cal CoCO3/CoO nanostructure for pseudocapacitor electrode, Nanomater.
Energy 11 (2015) 736e745.
[88] J. Shao, X. Li, Q. Qu, Y. Wu, Study on different power and cycling performance
of crystalline KxMnO2$nH2O as cathode material for supercapacitors in
Li2SO4, Na2SO4, and K2SO4 aqueous electrolytes, J. Power Sources 223 (2013)
56e61.
[89] X.F. Lu, Z.X. Huang, Y.X. Tong, G.R. Li, Asymmetric supercapacitors with high
energy density based on helical hierarchical porous Na x MnO2 and MoO2,
Chem. Sci. 7 (2016) 510e517.
[90] F. Wang, X. Wu, X. Yuan, Z. Liu, Y. Zhang, L. Fu, Y. Zhu, Q. Zhou, Y. Wu,
W. Huang, Latest advances in supercapacitors: from new electrode materials
to novel device designs, Chem. Soc. Rev. 46 (2017) 6816e6854.
[91] H. Wang, C. Zhu, D. Chao, Q. Yan, H.J. Fan, Nonaqueous hybrid lithium-ion and
sodium-ion capacitors, Adv. Mater. 29 (2017).