Journal of Colloid and Interface Science 483 (2016) 261–267

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Journal of Colloid and Interface Science

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

Regular Article

Enhanced electrochemical performance of monoclinic WO3 thin film

with redox additive aqueous electrolyte
Pragati A. Shinde a, Vaibhav C. Lokhande b, Nilesh R. Chodankar a, Taeksoo Ji b, Jin Hyeok Kim c,⇑,
Chandrakant D. Lokhande a,⇑
a
Thin Film Physics Laboratory, Department of Physics, Shivaji University, Kolhapur 416 004, MS, India
b
Department of Electronics and Computer Engineering, Chonnam National University, 300 Yongbong-Dong, Puk-Gu, Gwangju 500-757, South Korea
c
Department of Materials Science and Engineering, Chonnam National University, 300 Yongbong-Dong, Puk-Gu, Gwangju 500-757, South Korea

g r a p h i c a l a b s t r a c t
Figure showing the FESEM image of CBD prepared WO3 thin film with maximum obtained specific capacitance at constant scan rate of 5 mV s
1 in the
electrolyte having different concentration of redox species HQ.

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

Article history: To achieve the highest electrochemical performance for supercapacitor, it is very essential to find out a
Received 19 June 2016 suitable pair of an active electrode material and an electrolyte. In the present work, a simple approach
Revised 2 August 2016 is employed to enhance the supercapacitor performance of WO3 thin film. The WO3 thin film is prepared
Accepted 3 August 2016
by a simple and cost effective chemical bath deposition method and its electrochemical performance is
Available online 12 August 2016
tested in conventional (H2SO4) and redox additive [H2SO4 + hydroquinone (HQ)] electrolytes. Two-fold
increment in electrochemical performance for WO3 thin film is observed in redox additive aqueous
Keywords:
electrolyte compared to conventional electrolyte. WO3 thin film showed maximum specific capacitance
Chemical bath deposition
Redox additive aqueous electrolyte
of 725 Fg
1, energy density of 25.18 Wh kg
1 at current density of 7 mA cm
2 with better cycling stability
Supercapacitor in redox electrolyte. This strategy provides the versatile way for designing the high performance energy
Thin film storage devices.
WO3 Ó 2016 Elsevier Inc. All rights reserved.

⇑ Corresponding authors.
E-mail addresses: jinhyeok@chonnam.ac.kr (J.H. Kim), l_chandrakant@yahoo.com (C.D. Lokhande).

http://dx.doi.org/10.1016/j.jcis.2016.08.011
0021-9797/Ó 2016 Elsevier Inc. All rights reserved.
262 P.A. Shinde et al. / Journal of Colloid and Interface Science 483 (2016) 261–267
1. Introduction
The growing human population, environmental pollution and
industrialization along with diminishing fossil fuel are the major
problems for future generations. To overcome increasing energy
demands, there is an emergent need to extract energy from the
pollution free renewable energy resources as well as store this
energy in effective and clean energy storage devices, to fulfil the
present energy demands of society. For storage of electrical energy,
supercapacitor (SC) is most efficient and eco-friendly medium. SCs
are considered as one of the most promising electrochemical
energy storage devices, attracting much attention due to their long
listed features compared to present batteries technology, including
high power density, good electrochemical stability and environ-
ment friendly nature [1]. On the basis of charge storage mecha-
nism, SCs can be divided into two group’s namely electric double
layer capacitors (EDLCs) and pseudocapacitors. The SCs which
store charge as a result of their electrostatic accumulation at the
surface are termed as EDLCs [2] while those utilizing fast and
reversible faradic reactions as pseudocapacitors [3]. To achieve
the high energy storing capacity for SCs, the active electrode must
contain some features like high electrical conductivity, high speci-
fic surface area with appropriate porosity, and excellent cycling
stability. Till today, variety of electrode materials have been inves-
tigated for SC including carbon based materials, conducting poly-
mers and transition metal oxides [1–3]. Among different active
electrode materials, transition metal oxides are the most promising
one because they create capacitance from very fast redox reactions
and more importantly they store more energy as compared to the
EDLCs. In general, the transition metal oxides such as MnO2 [4],
CuO [5], WO3 [6], and Ni(OH)2 [7] have been used as active elec-
trode material for SCs.
Among the long listed pseudocapacitive electrode materials,
WO3, an electrochemically stable transition metal oxide, has
attracted great research interest due to its excellent physio-
chemical properties and diverse potential applications [8].
Depending on the preparation conditions, WO3 exists in different
crystal structures viz., tetragonal, hexagonal, monoclinic,
orthorhombic and triclinic [9]. Recently, WO3 is used as active elec-
trode material for SC devices, because of its multiple oxidation
states, high chemical stability, low cost, high reversibility and
non-toxic nature. Gao et al. [10] prepared WO3 nanowires by
hydrothermal method and achieved a specific capacitance of
521 Fg
1 at the current density of 1 Ag
1 in H2SO4 electrolyte.
Wang et al. [11] synthesized hexagonal mesocrystals formed by
W18O49 nanowires, by template-free solvothermal method and
obtained specific capacitance 579 Fg
1 at scan rate of 20 mV s
1in
H2SO4 electrolyte. Ma et al. [12] prepared flower-like WO3H2O–
rGO composite by hydrothermal method which exhibits specific
capacitance of 244 Fg
1 at 1 Ag
1 in H2SO4 electrolyte. However,
the reported values of specific capacitance and energy densities
are not sufficient to use these electrodes for device fabrication.
Therefore, more research towards improving electrochemical per-
formance of WO3 is proceeded to meet the requirements of practi-
cal applications.
The improvement of electrochemical characteristics of SCs by
optimising the electrode material is difficult due to the intrinsic
limitations of electrode materials. Therefore, it is essential to focus
on other components of the SCs such as the electrolyte, separator,
and packing material [13]. The electrolyte plays a crucial role in
SCs, as it takes leading role in charge-discharge process. An elec-
trolytes with good electrochemical properties such as the higher
ionic conductivity and better compatibility with active electrode
material are desired for development of efficient SCs and still there
is a room for developing better electrolyte system for SCs [13].
Despite to this, some recent reports [14] have showed the higher
electrochemical performance for SCs comprising the redox
species doped electrolytes. Typically, the redox species such as
p-phenylenediamine [15], indigo carmine [16], hydroquinone
[17], KI [18] and VOSO4 [19] are added to conventional electrolyte
to develop the more capable SCs.
In this investigation, WO3 thin films are developed on low cost
stainless steel substrates by chemical bath deposition (CBD)
method without assistance of any surfactant or binder. These films
are characterised by different characterization techniques to
obtain more information regarding the structure, morphology
and the elements of WO3 thin films. Further, the effect of elec-
trolyte systems (conventional and redox additive aqueous elec-
trolyte) on electrochemical performance of WO3 thin films is
studied. Hydroquinone (HQ) is used as a redox additive into
conventional H2SO4 electrolyte to form redox additive aqueous
electrolyte. As far as authors are aware of, this is the first report
on WO3 thin film based SCs with redox additive aqueous
electrolyte.
2. Experimental
2.1. Chemicals
AR grade tungsten metal powder and 30% H2O2 were utilized as
received without further purification. The stainless steel (SS) sub-
strate was mirror polished with emery polish paper and washed
with double distilled water and then air dried. To prepare all
solutions, double distilled water (DDW) was used throughout the
experiment.
2.2. Preparation of WO3 thin films
WO3 thin film was deposited on SS substrate by CBD method. In
a typical synthesis, 2.75 g tungsten metal powder was dissolved in
30 ml of H2O2. The reaction being exothermic, was carried out in an
ice bath. The solution was diluted to 250 ml by addition of DDW to
form a transparent homogenous peroxotungstate solution. After
stirring for 30 min, 40 ml of above solution was transferred to
100 ml beaker and SS substrate was immersed in it and beaker
was placed in water bath at 353 K for 6 h. Yellowish coloured
WO3 film was deposited on SS substrate. The reaction bath was
cooled down to room temperature and SS substrate was taken
out from the bath, washed several times with DDW and dried at
room temperature. Finally, the film was annealed at 673 K temper-
ature to remove water content and improve crystalline structure.
The mass of WO3 deposited on unit area was 1.5 mg cm
2 calcu-
lated using gravimetric method. The film thickness of 2.1 lm was
determined using the following formula,
m
t¼ ð1Þ
Aq
where t is the thickness of the thin film, m is the mass of the
deposited material, A is the area of the film and q is the density
of deposited material.
2.3. Material characterization
The WO3 thin film was characterized by XRD technique using
Bruker AXS D8 advance model with copper radiation (Ka
k = 1.5418) for crystallographic study. The Raman spectrum
was measured using Brucker MultiRAM, Germany. The X-ray
 P.A. Shinde et al. / Journal of Colloid and Interface Science 483 (2016) 261–267 263

photoelectron spectroscopy (XPS) data was analysed for identify-

ing oxidation states of WO3 using ESCALAB 250Xi X-ray photoelec-
tron spectrometer microprobe. Surface morphology was investigated
using FESEM (FE-SEM; S-4700, Hitachi) with an attached energy
dispersive X-ray spectroscope (Varian, CARY, 300 Conc.). The ionic
conductivity of electrolyte was measured using conductivity meter
(model-1602). The contact angle measurement was carried out
using Rame-Hart NRL CA to study surface wettability of WO3 thin
film using 1 M H2SO4 and 1 M H2SO4 with addition of different con-
centrations of hydroquinone (HQ) as electrolytes. The supercapac-
itive properties of WO3 electrode were tested using automatic
battery cycler (WBCS3000) in a conventional three electrode cell
with WO3 thin film as a working electrode, platinum as a counter
electrode and saturated calomel electrode (SCE) as a reference
electrode. Electrochemical impedance spectroscopy (EIS) measure-
ment was performed using electrochemical workstation (ZIVE SP
5) to study the interface between electrode and electrolyte.

3. Results and discussion

3.1. Growth mechanism of WO3 thin film

In present study, WO3 thin film is prepared by CBD method

without addition of any surfactant. In CBD method, film formation
takes place in two steps such as nucleation and particle growth.
Heterogeneous nucleation occurs via adsorption of colloidal parti-
cles, in which clusters of molecules undergo rapid decomposition
with temperature and combine on the substrate to form nuclei.
Once the nucleation centres are created on the substrate, aggrega-
tion process begins. During aggregation, the large number of ions
aggregates around the nucleation centres to form clusters of ions.
These clusters collapse in each other to initiate the formation of
nanostructure on substrate leading to thin, uniform and well
adherent film.
In present case, after dissolution tungsten metal powder in
H2O2, peroxotungstate complex is formed as [20], Fig. 1. (a) The XRD pattern and (b) Raman spectrum of WO3 thin film.

þ
2W þ 10H2 O2 ! W2 O2

11 þ 2H þ 9H2 O
The peroxotungstate complex is usually unstable and when
bath is heated to 353 K, it decomposes slowly and precipitation
formation starts in the solution when, ionic product exceeds the
solubility product. The heterogeneous chemical reaction takes
place by recombination of ions on SS substrate to form WO3 thin
film as
þ information about different O-W-O stretching vibrations in the
W2 O2

11 þ 2H ! 2WO3 þ 2O2 þ H2 O
Yellow coloured WO3 film is deposited on SS substrate.
3.2. Structural, morphological and elemental analysis
The crystallographic analysis of WO3 thin film is performed
using X-ray diffraction (XRD) data as shown in Fig. 1(a). The XRD
pattern shows characteristic diffraction peaks corresponding to
monoclinic structure of WO3 (JCPDS card No. 00-005-0363). The
sharp and intense peaks indicate high degree of crystallinity of
WO3 film. The WO3 crystal structure is formed by shearing of
WO6 octahedra at edges and corners. Due to this ordered stacking
of WO6 octahedra, large numbers of interstitial sites are formed
inside the crystal lattice. These interstitial sites improve electro-
chemical performance by providing effective accommodation for
guest ions, rendering the absorption and desorption of ions at
the surface and also the intercalation/deintercalation into the inner
parts [9,21]. This helps to improve its electrochemical perfor-
mance. Absence of any other additional peaks in the XRD pattern,
ð2Þ
demonstrates that WO3 film possesses high purity. The peaks
marked with ‘D’ are attributed due to SS substrate. The previous
reports on phases of WO3 used in supercapacitor application are
shown in Table 1. Additionally, to get information about the molec-
ular and electronic structure of WO3 film, Raman spectroscopy
technique is employed. Raman spectrum of WO3 thin film within
frequency range of 100–1000 cm
1 shown in Fig. 1(b), gives the
ð3Þ
WO3 crystal lattice. It displays two main intense peaks at 807
and 710 cm
1, assigned to vibrational stretching modes of the t
(O-W-O). The peak at wavenumber 271 cm
1 is associated with
the bending mode d (O-W-O), which is in good agreement with
the earlier report [22].
Morever, to find out the oxidation states of W and O in WO3
film, XPS measurements were performed. Fig. 2(a) shows the full
scan spectrum of WO3, which exhibits peaks for W and O and trace
amount of C related to adventitious carbon. The narrow scan XPS
spectrum for W 4f core level is presented in Fig. 2(b). The spin orbit
doublet peaks observed at binding energies of 37.89 and 35.76 eV
are attributed to the W 4f5/2 and W 4f7/2 respectively, are charac-
teristic of W6+ oxidation state [23]. The spin orbit splitting, the dif-
ference between binding energies of W 4f5/2 and W 4f7/2 levels is
about 2.13 eV. In addition, the high resolution spectrum of O 1s
in Fig. 2(c) shows the intense peak at binding energy of
530.55 eV corresponding to lattice oxygen O2
forming strong
W=O bond [23]. Hence, the results obtained from the Raman and
XPS studies are in well analogues with XRD study.
264 P.A. Shinde et al. / Journal of Colloid and Interface Science 483 (2016) 261–267

Table 1
Comparison of supercapacitor performance of film electrode with different phases of WO3.

Sr. No. Material Crystal structure Synthesis method Electrolyte Specific capacitance Energy density Ref.

1
1
1 WO3 Hexagonal Hydrothermal H2SO4 521 Fg at 1 Ag – [10]
2 WO3 Monoclinic SILAR Na2SO4 266 Fg
1 at 10 mV s
1 – [28]
3 WO3 Hexagonal Hydrothermal H2SO4 421.8 Fg
1 at 0.5 Ag
1 10 Wh kg
1 [29]
4 WO3–WO30.5H2O Hexagonal Microwave assisted H2SO4 290 Fg
1 at 25 mV s
1 – [30]
hydrothermal method
5 h-WO3nH2O Hexagonal Hydrothermal H2SO4 498 Fg
1 at 5 mV s
1 – [32]
6 WO3 Monoclinic CBD (H2SO4 + Hydroquinone) 711 Fg
1 at 5 mV s
1 25.18 Wh kg
1 Present work

Fig. 2. The XPS spectra of WO3 (a) survey scan spectrum, (b) W 4f core level spectrum and (c) O 1s core level spectrum.

Fig. 3. (a and b) The FESEM images at two different magnifications 2000 and 25,000.

It is well known that in supercapacitive phenomenon, electro-
chemical interaction in between the electrolyte ions and active
electrode material occurs through the surface of electrode mate-
rial. Therefore, it is must to visualize the surface morphology of
WO3 thin film. Fig. 3(a and b) demonstrates the field emission
scanning electron microscope (FESEM) images for WO3 thin film
at two different magnifications, which exhibit the formation of
disc-like structures. These disc-like structures are randomly dis-
tributed through the substrate surface creating large number of
voids between them. Such voids provide large volume for easy dif-
fusion of electrolyte ions into interior of the active material. The
average diameter of the disc is about 1 lm, as seen at higher
magnification (25 k) (Fig. 3(b)). Additionally, the nanoparticles
in the range of 100–200 nm are observable on the surface of the
disc-like structure. Effectively, these nanoparticles improve the
resultant electroactive sites for electrochemical reactions. Such
nanoparticles decorated disc-like structures increase the active
surface area to improve the resultant electrochemical performance
of WO3 thin film. Further, elemental analysis of the WO3
microstructures carried out using EDAX spectrum reveals that W
and O are in stoichiometric atomic percentage.
3.3. Electrochemical performance of WO3 in H2SO4 and redox
electrolyte
It is known that, the electrolyte plays a crucial role in electro-
chemical performance of electrode material and recently to
improve the electrolyte activity different strategies are used. Pre-
sent strategy is the addition of redox species in conventional elec-
trolyte to improve the ionic conductivity of the electrolyte and also
to make redox capable electrolyte. In present study, electrochemi-
cal properties of WO3 are measured in 1 M H2SO4 and [H2SO4 + -
hydroquinone (HQ)] redox electrolytes, respectively. The different
amounts of hydroquinone (HQ) (from 0.1 to 0.4 M) are added in
the conventional 1 M H2SO4 electrolyte to form redox electrolyte.
The ionic conductivity of electrolytes is measured as a function
of concentration of HQ in 1 M H2SO4 and plotted in Fig. 4. The ionic
conductivity of an electrolyte depends on number of ions present
 P.A. Shinde et al. / Journal of Colloid and Interface Science 483 (2016) 261–267
Fig. 4. Ionic conductivity of H2SO4 + HQ redox additive aqueous electrolyte at
different concentrations of HQ and inset shows corresponding contact angle
images.
Fig. 5. Schematic representation of the redox process in hydroquinone.
in the solution and varies with the concentration of electrolyte. The
ionic conductivity of 1 M H2SO4 is increased to 129.4 mS cm
1 with
an increasing concentration of HQ from 0.1 to 0.2 M and decreases
for further increasing HQ concentration, indicating that HQ acts as
a good redox additive in H2SO4 with 0.2 M concentration. The
excess addition of HQ (>0.2 M) increases interaction of HQ mole-
cules, resulting in aggregation of free ions and crystallization of
HQ in H2SO4 causes slow diffusion of ions which decreases the
ionic conductivity.
The WO3 surface wettability measurement is carried out to
investigate the interaction between electrolyte and WO3 film sur-
face. Fig. 4 shows the contact angle images of WO3 film surface
in 1 M H2SO4 and 1 M H2SO4 electrolyte with different concentra-
tions of HQ. The contact angles of 49.7°, 40.3°, 32.6°, 18.6° and
15.7° for 1 M H2SO4 and 1 M H2SO4 with different concentrations
of HQ show the hydrophilic nature of WO3 film surface. By the
addition of HQ into H2SO4 electrolyte, contact angle decreases
which indicates that the WO3 film surface is more hydrophilic.
Such hydrophilic surface is useful for the electrolyte to have inti-
mate contact as required in electrochemical applications.
The schematic of HQ redox reaction process is shown in Fig. 5.
HQ, an electrochemically active organic compound gives two elec-
trons in faradic reactions. During the charge intercalation process,
HQ is oxidized into quinone with 2H+ and 2e
and during deinter-
calation quinone is reduced to HQ with gain of 2e
and 2H+ [27].
Additional ions provided by HQ in H2SO4 electrolyte further react
with active electrode material and increase pseudocapacitance.
The CV curves for WO3 electrode in operating potential window
of
0.5 to 0 V/SCE at the scan rate of 100 mV s
1 with increasing
265
HQ concentration are illustrated in Fig. 6(a). The CV curve shows
higher area under the curve up to 0.2 M HQ and decreases for fur-
ther HQ concentration. This observation is in consistent with GCD
curves presented in Fig. 6(b). It is observed that at the same current
density 10 mA cm
2, for 0.2 M HQ, GCD curve takes longer charge-
discharge time. The increase in both the current density and
discharge time are observed with concentration of HQ. The
(H2SO4 + 0.2 M HQ) redox electrolyte system provides additional
electrons and protons for fast and reversible intercalation and
deintercalation process. Fig. 6(c) illustrates CV curves at different
scan rates in H2SO4 + 0.2 M HQ electrolyte. The non-rectangular
shape of the CV curve gives indication of pseudocapacitive beha-
viour of WO3 electrode [24]. Even at a high scan rate of 100 mV s
1,
the symmetric nature of CV curve indicates good capacitive beha-
viour and high reversibility of WO3 electrode. Further, specific
capacitance of WO3 electrode for different scan rates is calculated
using following formula;
Z Vc
1
Cs ¼ Iv dv ð4Þ
mv ðV c
V a Þ Va
where Cs is the specific capacitance, v is the potential scan rate, Vc–Va
is the potential range, I is the average current density per unit area,
and m is the mass deposited (1.5 mg cm
2). Fig. 6(d) demonstrates
Cs as a function of scan rate for WO3 electrode in H2SO4 and in redox
electrolyte with different concentrations of HQ. It is observed that
Cs value enormously increased with HQ addition than that of con-
ventional H2SO4 electrolyte as redox additives are directly involved
in the charge transfer redox reactions between surface of electrode
and electrolyte. It is clear that H2SO4 + 0.2 M HQ electrolyte demon-
strates highest Cs of 711 Fg
1, which is much larger as compared to
376 Fg
1 in conventional H2SO4 electrolyte at the scan rate of
5 mV s
1. The Cs obtained in present work in redox electrolyte is
higher when compared with literature [28–32] (Table 1). The
decrease in capacitance with scan rate is ascribed to the presence
of inaccessible inner active sites that cannot maintain the redox
transitions due to the diffusion effect of ions in WO3 electrode
[25]. The higher Cs is also contributed to the microstructure com-
posed of very fine discs, which in turns offers the large number of
electrochemical active sites for easy transport and diffusion of elec-
trolyte ions.
The GCD curves for WO3 electrode in H2SO4 + 0.2 M HQ redox
electrolyte at different current densities in the potential range of

0.5 to 0 V/SCE are presented in Fig. 6(e). The Cs is calculated from
the discharge curve using the formula;
I  Td
Cs ¼ ð5Þ
DV  m
where Td is the discharge time and DV is the potential. The perfor-
mance of an efficient electrochemical capacitor is determined from
the energy density (ED) and power density (PD). The ED and PD are
evaluated from discharge curves at different current densities using
the formulae;
0:5  C s  ðV 2c
V 2a Þ
ED ¼ ð6Þ
3:6
ED  3600
PD ¼ ð7Þ
Td
The calculated ED and PD values from the discharge curve at
different current densities are plotted as Ragone plots shown in
Fig. 6(f). The energy density of WO3 electrode with HQ addition
is higher due to the increase in energy storage capacity by fast
and reversible redox reactions incorporated by redox electrolyte.
The specific capacitance and energy density of WO3 electrode in
conventional H2SO4 electrolyte are 352 Fg
1 and 12.25 Wh kg
1,
266 P.A. Shinde et al. / Journal of Colloid and Interface Science 483 (2016) 261–267

Fig. 6. (a and b) The cyclic voltammogram at fixed scan rate of 100 mV s
1and the galvanostatic charge-discharge curves at fixed current density of 10 mA cm
1 in H2SO4 and
in redox additive aqueous electrolyte with different concentrations of HQ, (c) the cyclic voltammogram at different scan rates in H2SO4 + 0.2 M HQ, (d) variation of specific
capacitance with scan rate in H2SO4 and in redox additive aqueous electrolyte with different concentrations of HQ, (e) the galvanostatic charge discharge curves for different
current density in H2SO4 + 0.2 M HQ and (f) Ragone plots for WO3 electrode.

respectively which increase to 725 Fg
1 and 25.18 Wh kg
1 in
H2SO4 + 0.2 M HQ redox electrolyte at the same power density of
1166 W kg
1. This is quite impressive when compared to superca-
pacitor based on hexagonal WO3 [29]. This result showed that, HQ
is an efficient redox additive in order to improve specific capaci-
tance and energy storage capacity of WO3 electrode.
A better electrochemical cycling stability of the electrode is a
prime requirement for SC application along with superior Cs, ED
and PD values. The cyclic stability of WO3 electrode was investi-
gated in H2SO4 and H2SO4 + 0.2 M HQ electrolytes at fixed scan rate
of 100 mV s
1 for 1000 CV cycles. Fig. 7(a) exhibits the Cs retention
of WO3 electrode as a function of cycle number and inset figure
shows 1st and 1000th CV cycles. It is seen that, for H2SO4 + 0.2 M
HQ electrolyte system, the specific capacitance increases from 0
to 20% with cycling up to 100 cycles, which may be due to the
voltammetric charges integrated from the positive and negative
sweeps of the CV cycles, which closes to each other in magnitude
with increasing cycle number [26]. From fig., the WO3 electrode
shows slightly low capacity retention (81%) in redox electrolyte
as compared to H2SO4 electrolyte (89%). The slight loss in capaci-
tance is attributed to more degradation of electrode material in
redox electrolyte [33], which may be a consequence of extensive
amount of redox reactions incorporated by redox electrolyte.
To illustrate the electrochemical performance of WO3 electrode
for SC application, the electrochemical impedance spectroscopy
study is applied in the frequency range of 100 kHz to 10 mHz by
applying a. c. amplitude of 10 mV. The Nyquist plots for WO3
electrode in conventional H2SO4 and redox additive aqueous elec-
trolytes are shown in Fig. 7(b) and inset figure shows the magnified
plots. At higher frequency region, both the Nyquist plots consist of
small semicircle as faradic charge transfer occurred at the
electrode-electrolyte interface. A straight line inclined at an angle
of 45° to the real axis in the lower frequency region specifies the
diffusion of electrolyte ions from surface of electrode to the
electrolyte [10]. The intercept of semi-circle to real Z0 - axis at high
frequencies provides the equivalent series resistance (ESR), which
is related to the intrinsic resistance of WO3 electrode, ionic resis-
tance of the electrolyte and the contact resistance at the interface
between electrode and electrolyte. The intercept of Nyquist plots
on real axis are at 0.54 and 2.2 X cm
2 in redox additive aqueous
electrolyte and in conventional H2SO4 electrolyte, respectively.
The decrease in overall resistance of WO3 electrode in redox

Fig. 7. (a) The plots of capacitive retention with number of cycles and inset figures show 1st and 1000th CV cycles and (b) the Nyquist plots in H2SO4 and H2SO4 + 0.2 M HQ
for WO3 electrode.
 P.A. Shinde et al. / Journal of Colloid and Interface Science 483 (2016) 261–267
additive aqueous electrolyte indicates increase in ionic conductiv-
ity of electrolyte. Furthermore, the decrease in semicircle arc of the
EIS curve for redox additive aqueous electrolyte reduces the charge
transfer resistance of the WO3 electrode. These results demon-
strate that redox additive aqueous electrolyte provides good con-
ductivity and less internal resistance of WO3 electrode as
compared to the conventional H2SO4 electrolyte.
4. Conclusions
In summary, for the first time, a general and cost effective
approach is employed to enhance supercapacitive performance of
monoclinic WO3 electrode by incorporation of the hydroquinone
(HQ) as a redox additive in H2SO4 electrolyte. The nanoparticles
composed disc-like WO3 structures are directly grown on stainless
steel substrate with a binder-less and surfactant-free CBD method.
The two-fold increment in electrochemical performance for WO3
electrode is observed in HQ incorporated aqueous H2SO4 elec-
trolyte. Consequently, monoclinic WO3 electrode exhibits high
specific capacitance of 725 Fg
1 with energy density of
25.18 Wh kg
1. The proposed strategy gives one more way to
improve the energy storing capacity of pseudocapacitive
electrodes.
Acknowledgement
This work was supported by the Human Resources Develop-
ment program (No. 20124010203180) of the Korea Institute of
Energy Technology Evaluation and Planning (KETEP) Grant funded
by the Korea government Ministry of Trade, Industry and Energy
and supported by Basic Science Research Program through the
National Research Foundation of Korea (NRF) funded by the Min-
istry of Science, ICT and Future Planning (NRF-2015R1A2A2A
01006856).
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