Journal of Electroanalytical Chemistry 839 (2019) 96–107

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Journal of Electroanalytical Chemistry

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

Solution processed nanostructured cerium oxide electrode: Electrochemical T

engineering towards solid-state symmetric supercapacitor device
Bidhan Pandita, Nitish Kumara, Pankaj M. Koinkarb, Babasaheb R. Sankapala,
⁎

a
Nano Materials and Device Laboratory, Department of Physics, Visvesvaraya National Institute of Technology, South Ambazari Road, Nagpur 440010, Maharashtra,
India
b
Department of Optical Science, Tokushima University, 2-1 Minamijosanjima Cho, Tokushima 7708506, Japan

ARTICLE INFO ABSTRACT

Keywords: Present work portrays the surface morphology dependent electrochemical behaviors tuned by annealing the
Cerium oxide chemical bath deposited (CBD) cerium oxide electrodes. The altered nanostructure properties are well-supported
Energy storage by in-depth structural and morphological analysis. Cerium oxide electrode annealed at 200 °C exhibits good
Supercapacitor surface properties enabling maximum electro-active porous cavities to penetrate electrolyte ions towards en-
Symmetric device
hanced electron transfer. Consequently, the electrode exhibits maximum specific capacitance of 750 F/g with
remarkably stable charge-discharge cycles. Fabricated symmetric solid-state supercapacitor device impressively
expands potential window to 1.2 V with the aid of PVA-LiClO4 gel electrolyte with a peak specific capacitance of
321.3 F/g with top-up of 61.4 Wh/kg specific energy. The series combination of two devices confirms the strong
energy storage ability by glowing ‘VNIT’ acronym designed through 21 red LEDs from the practical point of view.

1. Introduction
Till date, CeO2 has been investigated extensively in unanimous
applications such as solid-state electrolytes for electrochemical devices
[1], automotive exhaust cleaning [2], sensors [3], fuel cells [4], me-
chanical polishing [5], electrochromic thin-film application [6], low
temperature water-gas shift [7], buffer layer [8], hybrid solar cells [9],
H2S removal [10], chemical–mechanical planarization [11], ultraviolet
absorbents [12], and more recently for medicine [13]. Several methods
such as hydrothermal, sol-gel, solvothermal, spray pyrolysis, micro-
emulsion, thermal decomposition, thermal hydrolysis, mechan-
ochemical processing, and co-precipitation have been adopted to syn-
thesize CeO2 [14].
In nanocrystalline oxides, the energetics may be substantially re-
duced due to defects and increases the nonstoichiometry levels and
electronic carrier generation [15]. Structural defects arisen due to
partial pressure of oxygen and high mobility of oxygen vacancies can
exhibit the potential application in energy-related devices [16]. Hence,
nanostructured CeO2 has attracted much attention due to improved
electronic transport and redox properties along with enhanced surface
to volume ratio compared to other bulk and nanostructured materials.
The fluorite-structured cerium oxide forms a close pack structured array
of atoms with four coordinate O2− and eight coordinate Ce4+. As en-
vironmentally abundant rare earth element, CeO2 has drawn great
attention with a ground state of 4f15d16s2. Hence, it can form not only
steady Ce3+ by losing one 5d and two 6s electrons but stable Ce4+ by
losing one extra 4f electron. The oxidation state can mutate expediently
and quickly between Ce3+ and Ce4+ declares CeO2 as an outstanding
redox material which is necessary requirement for supercapacitor ap-
plication. Maheswari et al. [17] prepared hexagonal CeO2 nanoparticles
which exhibit maximum specific capacitance of 523 F/g whereas Zhang
et al. [18] developed a hierarchical porous manganese dioxide/cerium
dioxide (MnO2/CeO2) nanocomposite by hydrothermal approach to
exhibit a maximum specific capacitance of 274.3 F/g. Silver decorated
CeO2/reduced graphene oxide (rGO) nanocomposite synthesized by
hydrothermal method have exhibited 710.42 F/g specific capacitance
as reported by Vanitha et al. [19]. To achieve maximum capacitance,
Arul et al. [20] have synthesized hybrid CeO2/Fe2O3 composite by
adopting co-precipitation method and abled to achieve 142.6 F/g. In
spite of using route through complex synthesis, high temperature or
surface capping agent, CeO2 and even the corresponding composites
have failed to attain a peak capacitive value. Hence, there is prime
requirement to adopt a simple and low-cost chemical approach to
produce large area with low temperature process for the controlled
growth of CeO2 nanostructures.
In this prospective, the synthesis of cerium oxide has been per-
formed towards high performance supercapacitive electrode on flexible
stainless steel (SS) substrate by using solution processed chemical bath

⁎
Corresponding author.
E-mail address: brsankapal@phy.vnit.ac.in (B.R. Sankapal).

https://doi.org/10.1016/j.jelechem.2019.02.047
Received 16 December 2018; Received in revised form 21 February 2019; Accepted 23 February 2019
Available online 08 March 2019
1572-6657/ © 2019 Published by Elsevier B.V.
B. Pandit, et al. Journal of Electroanalytical Chemistry 839 (2019) 96–107

Fig. 1. (a) XRD patterns of bare stainless steel (SS), CO, CO100, CO200, and CO300 thin films, (b) FTIR of corresponding samples.

Fig. 2. (a) XPS survey spectrum of CO200 sample, (b, c) core level XPS spectra of Ce 3d and O 1s, (d) EDX spectra of CO200 thin film.

deposition (CBD) method. To improve the electrochemical performance
through removal of the intrinsic hydroxide, as-synthesized films were
air annealed at various temperatures up to 300 °C and the effect was
correlated in terms of structural, morphological, and electrochemical
properties. This concludes that the CeO2 electrode annealed at 200 °C
exhibits excellent electrochemical performances among the others.
Finally, a solid-state approach was adapted to assemble flexible solid-
state symmetric supercapacitor (FS-SC) device using PVA-LiClO4 gel
electrolyte as mediator. Significantly, two flexible supercapacitor de-
vices connected in series provided an efficient self-powered nanosystem
for powering commercial light-emitting diodes (LEDs), demonstrating
their practical application. The excellent electrochemical performance
elegantly integrated with mechanical bending approach to exhibit its
potential ability towards advanced flexible and wearable energy sto-
rage devices.
2. Experimental parameters
2.1. Electrode and device fabrication
Chemical bath deposition (CBD) method was employed to synthe-
size cerium oxide film on stainless steel (SS) substrate. In Brief, cerium
(III) nitrate (Ce(NO3)3, 6H2O) was used as cationic solution, while
hydrogen peroxide (H2O2, 30%) was used as anionic precursor during

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B. Pandit, et al.
Fig. 3. (a–c) FESEM images of CO200 thin film, (d, e) HRTEM images, and (f) SAED pattern of CO200 sample.
the process. The precursor solution was prepared by dissolving 0.04 M
Ce(NO3)3 in 50 mL double-distilled water (DDW) with constant stirring
to get uniform distribution of Ce(NO3)3 in the solution. Furthermore,
2.5 mL of H2O2 was added in the prepared solution under vigorous
stirring where mirror-polished SS substrate was immersed vertically at
a constant temperature of 60 °C. After 1 h, the yellowish cerium oxide
film deposited on SS substrate was taken out from bath and rinsed
several times in double distilled water (DDW). Subsequently, the as-
prepared film was annealed at different temperatures for reviewing the
complete effect in electrochemical behaviors. The thin films annealed at
100, 200 and 300 °C are denoted as CO100, CO200, and CO300,
whereas the as-synthesized film prepared at room temperature is de-
noted by CO, respectively. The evolution of thin film from a solution
phase in chemical bath deposition (CBD) involves two steps in de-
position: nucleation and growth. The addition of hydrogen peroxide to
Ce(III) nitrate solution at 60 °C slowly oxidizes the cations to a higher
valence state. Temperature provided by CBD reaction gradually makes
the Ce3+ solution supersaturated, and thereby initiate precipitation
with the formation of dense spherical agglomerates. Subsequently,
nucleation process begins and CeO2 nanoparticles are gradually nu-
cleated and then grow on stainless steel (SS) substrate as thin film form
under the favorable deposition condition.
Initially, Ce3+ ions in association with H2O2 form cerium oxide and
hydroxide as:
3Ce3 + + H2 O2 + 5H2 O = 2CeO2 + Ce(OH)3 + 9H+ (1)
Pure oxide film with improved crystallinity is obtained by removing
further Ce(OH)3 phase through air annealing.
For the formation of solid-state device, the PVA-LiClO4 gel elec-
trolyte was synthesized by adding 6 g of LiClO4 and 6 g of polyvinyl
alcohol (PVA) powder into 60 mL of deionized DDW [21]. The mixture
was heated at 90 °C with constant stirring until the solution became
clear and viscous. The PVA-LiClO4 gel was painted on the prepared
films pre-coated on flexible SS substrates. Then, films were kept into the
fume hood at room temperature to vaporize the excess water. When the
gel electrolyte got solidified, the two electrodes were sandwiched and
packaged to assemble FS-SC device [22,23].
2.2. Characterizations
The thin films were characterized by Bruker AXS D8 Advance X-ray
diffractometer (XRD) with copper (Kα) radiation (λ = 1.5406 Å). Also,
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Journal of Electroanalytical Chemistry 839 (2019) 96–107
Raman (LabRAM HR, 532 nm laser excitation) technique and Fourier
transform infrared spectroscopy (FTIR, Thermo Nicolet, Avatar 370)
were used for structural property determination. Chemical-state ana-
lysis was carried out by X-ray photoelectron spectroscopy (XPS) using
PHI 5000 VersaProbe II (ULVAC INC, Japan). Surface morphological
analysis was executed by field emission scanning electron microscopy
(FESEM) technique using JEOL-JSM 6360 unit and high-resolution
transmission electron microscopy (HRTEM) using JEOL 2100 with LaB6
source. The Brunauer–Emmett–Teller (BET) technique was engaged to
analyze surface area using Belsorp II, BEL Japan INC. The electro-
chemical investigations such as cyclic voltammetry (CV), galvanostatic
charge-discharge (GCD), and electrochemical impedance spectroscopy
(EIS) were analyzed by using a PARSTAT-4000 potentiostat/galvano-
stat (Princeton Applied Research, USA).
3. Results and discussion
3.1. Structural analysis
Effects of annealing temperatures on the structural properties of the
as-deposited samples were analyzed by XRD and results are depicted in
Fig. 1a. Sample CO shows three intense peaks at 2θ values of 28.54,
33.07 and 47.47° that corresponds to (111), (200) and (220) planes of
cubic CeO2 (JCPDS card no. 81-0792) along with clearly visualized
diffraction peak of Ce(OH)3 at 55.65° (JCPDS card no. 19-0284). The
CO100 sample shows the co-existence of Ce(OH)3 and CeO2, conse-
quently named as cerium oxy-hydroxide. Interestingly, all the hydro-
xide peaks completely disappear in CO200 sample, indicating the for-
mation of pure CeO2 phase at 200 °C with complete transformation of
hydroxide to oxide. With further increase in annealing temperature
(300 °C), the diffraction peaks are found to narrow down, indicating
enhancement of crystallinity with the further growth of crystallites.
FTIR spectra of the corresponding samples are shown in Fig. 1b. The
band at around 3445 cm−1 indicates the existence of stretching vibra-
tion of surface OH groups [24,25]. It can be observed that there is a
great decrease in the band after annealing which indicates the removal
of hydroxide. The CO200 and CO300 samples exhibit almost identical
shapes of band, confirming the synthesis of CeO2 with removal of hy-
droxide content.
Fig. S1 shows the visible Raman spectra of CO200 sample carried
out at room temperature. The strongest peak appeared at 457 cm−1
represents the optical Raman F2g mode originated from stretching
B. Pandit, et al.
Fig. 4. Electrochemical performances in 0.5 M NaOH electrolyte. (a) CV curves for CO, CO100, CO200 and CO300 electrodes at scan rate of 100 mV/s, (b–e) CV
curves of corresponding electrodes at different scan rates ranging from 2 to 100 mV/s, (f) specific capacitance at a function of scan rate.
vibrations of oxygen [26]. The small hump around 600 cm−1 is related
to the oxygen defective CeO2 layers [27]. Moreover, the typical internal
vibration of nitrates are associated with the peaks arise at 740 and
1049 cm−1, respectively [28]. The results are in good agreement with
structural outcomes from XRD analysis.
The valence states of elements in CO200 sample are studied by the
detail analysis of XPS and results are depicted in Fig. 2a. The wide
survey spectrum is similar with previous literatures [29,30]. KLL and
MNN are the Auger groups for O and Ce, respectively [31]. The Ce 3d
core level peak can be confirmed by XPS analysis for CO200 sample, as
depicted in Fig. 2b. The main peaks of Ce4+ 3d3/2 and Ce4+ 3d5/2 are
shown at binding energies of 916.89 and 898.47 eV, respectively. The
minute existence of Ce3+ 3d3/2 and Ce3+ 3d5/2 are located at 901.13
and 882.66 eV, individually. Two additional ‘shake-up’ satellite lines
SU1 and SU2 are shown at 906.27 and 887.02 eV, separately. This Ce
3d spectrum is well consistent with previously reported literatures [32].
The presence of trivalent Ce3+ can either be due to the formation
oxygen vacancies or surface defects [33]. The presence of oxygen va-
cancies is superior in nanostructures as larger number of the atoms
present on the surface; resulting reduced coordination of surface atoms
with the reduction of the particle size [26]. Moreover, minute Ce3+
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Journal of Electroanalytical Chemistry 839 (2019) 96–107
sites were formed because of surface defects present in the form of
amorphous Ce2O3 and hence cannot be detected by XRD, as per pre-
vious report [34]. The oxygen vacancies lead to the transformation
between Ce4+ and Ce3+, may be a key issue in reactions on the elec-
trode. It is obvious that CeO2 has a strong oxygen storage and release
capacity via the redox shift between Ce4+ and Ce3+ under oxidizing
and reducing states, respectively.
XPS studies concentrating on oxygen species were also conducted
(Fig. 2c). The O 1s spectrum clearly exhibits two different surface
oxygen species where the main peak at 529.55 eV is ascribed to lattice
oxygen whereas the additional peak at 532.23 eV is assigned to oxygen
vacancies related to surface adsorbed oxygen and hydroxyl groups [35].
3.2. Morphological analysis
Surface morphology of active electrode material has an influential
importance over electrochemical actions. FESEM images displayed in
Fig. S2 demonstrate that the whole substrate is uniformly covered by
nanoparticle-like surface architecture. The surface properties have
changed to nanoparticles structure with enhancement in grain size as
the annealing temperature increases from 100 to 300 °C. At the anneal
B. Pandit, et al.
Fig. 5. (a) GCD curves of CO, CO100, CO200 and CO300 electrodes at current density of 1.5 mA/cm2, (b–e) GCD curves at different current densities ranging from
1.5 to 2.25 mA/cm2, (f) specific capacitance at a function of current density.
temperature of 300 °C, the size of particles is found to be enlarged,
resulting in the larger grains. The hydroxide content was completely
removed when the annealing temperature tuned at 200 °C. EDX of
CO200 sample was analyzed to determine the composition which ex-
hibits the existence of Ce and O elements quantitatively for the syn-
thesized material (Fig. 2d). Moreover, the other less intense peaks are
for stainless steel (SS) composed of various alloys. Fig. 3a–f shows the
FESEM and corresponding HRTEM images of the CO200 sample. The
nanoparticles of CO200 are highly uniform, and porous (Fig. 3a–c),
enabling enough space for electrolyte ions to allow an easy access
which is prime requirement for energy storage towards supercapacitor
application. The typical HRTEM image of the CO200 shown in Fig. 3e
discerns lattice fringes with interplanar spacing of 0.31, 0.27, and
0.19 nm; corresponding to (111), (200), and (220) planes of CeO2 re-
spectively. Moreover, the concentric rings appeared in recorded SAED
pattern also confirms the same (111), (200), and (220) planes of the
cubic structured CeO2 (Fig. 3f). The EDS elemental mapping was ana-
lyzed to locate the distribution profile of associate components in
CO200 as depicted in Fig. S3a–c. It confirms the formation of CeO2 by
showing the well-distribution of Ce and O elements on the SS surface.
3.3. Supercapacitive performance of CeO2 electrodes
Fig. 4a shows the comparative CV plots for CO, CO100, CO200 and
CO300 electrodes in 0.5 M NaOH electrolyte at scan rate of 100 mV/s
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Journal of Electroanalytical Chemistry 839 (2019) 96–107
within a constant potential window of −0.5 to −1.1 V. All the elec-
trodes reveal typical reversible redox behavior containing sharp oxi-
dation and reduction peaks, originating due to the pseudocapacitive
charge storage behavior [36]. The only difference is that the CO200
electrode shows maximum current response in the same potential
window as compared to the others as it allows an easier path for
electrochemical reactions due to its hierarchical nanostructure enabling
high surface area (Fig. S4) and superior electrical conductivity origi-
nating by the removal of hydroxide content. The scan rate dependent
CV curves for all the electrodes are shown in Fig. 4b–e. Obviously,
CO200 electrode shows highest specific capacitance of 750 F/g at a
scan rate of 2 mV/s (Supporting information S5). The redox peaks are
originated from the following reversible reactions [20].
Ce+4O2 + OH Ce+3O2 OH + e (2)
Actually, the formation of CeO2 with improved atomic order leads
to enhanced conductivity and amplified utilization rate of active elec-
trode material for electrolyte ions. The specific capacitance decreases
from 259 to 190 F/g as the annealing temperature increases from 200
to 300 °C (Fig. 4f), possibly attributing to the bulk crystallites which
reduces the electroactive surface for forming electrical double layer
with the electrolyte [37]. The aggregated nanostructure does not allow
access to the inner electroactive sites for the electrochemical reactions
as it blocks the path of electrolyte ions.
The comparative galvanostatic charge-discharge (GCD) plots at
B. Pandit, et al.
Fig. 6. (a) Cycling stability of CO, CO100, CO200 and CO300 electrodes for 4000 cycles, (b–e) corresponding CV curves for different cycle numbers at 100 mV/s scan
rate, (f) Nyquist plot of impedance from 100 mHz to 100 kHz.
constant current density of 1.5 mA/cm2 were performed within the
same potential window and are depicted in Fig. 5a. At the starting of
discharge curves, insignificant iR drops reveal the low internal re-
sistance involved during fast GCD cycles [38]. The GCD profiles of all
electrodes at different current densities depicted in Fig. 5b–e are not
linear in nature, demonstrating the involvement of faradaic reaction
mechanism between electrode and electrolyte [39]. The CO200 elec-
trode shows more energy storage capacity by exhibiting greater dis-
charging time compared to other electrodes. The CO200 shows a
maximum specific capacitance of 698 F/g at a current density of
1.5 mA/cm2 by offering supreme conductive pathways for the pene-
tration of electrolyte ions. The less contribution of electroactive mate-
rial during redox reactions arises at higher current density rate, as a
result the specific capacitance decreases with the increase of current
density as shown by Fig. 5f.
Long-term cyclic stability is a crucial parameter towards the prac-
tical ability of synthesized electrode material. The cyclic stabilities of
all the electrodes were executed at 100 mV/s scan rate within the same
potential window where the CO200 electrode exhibits a maximum re-
tention by maintaining 94.9% of its initial capacitance even after
4000 cycles while that for CO, CO100 and CO300 is found to be 90.8,
88.8, and 92.4% respectively (Fig. 6a). The unperturbed CV curves even
after 4000 cycles for all the electrodes are depicted in Fig. 6b–e which
not only demonstrates very low degradation with excellent chemical
stability of CeO2 in NaOH electrolyte but constant power delivery for a
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Journal of Electroanalytical Chemistry 839 (2019) 96–107
long duration with good reversibility as well.
The origin of the diverse behaviors of all the electrodes can be more
specifically investigated by the EIS point of view as it defines the inner
restive and capacitive characteristics of electrode. The EIS of electrodes
were investigated in the frequency range of 0.1 Hz to 100 kHz and is
shown in Fig. 6f. The straight line at low frequency region in Nyquist
plot shows the pure capacitive behavior of electrodes. The first X-axis
intercept represents the equivalent series resistance (RS) which is as-
sociated with the resistive factors of electrolyte, electrode and elec-
trode-electrolyte interfaces [40]. On the other hand, the charge transfer
resistance (RCT) referred by the small semicircular arc in high frequency
region closely depends on the structure and morphology of the elec-
trode [41]. In the present case, CO200 shows very low RS (1.05 Ω/cm2)
and RCT (0.27 Ω/cm2) values, establishing good electrochemical re-
sponse due to well-established interface between electrode and elec-
trolyte ions. Actually, the conductive contact area between SS substrate
and oxide layer significantly reduces the interfacial charge transfer
resistance, increasing the utilization rate of active materials and con-
sequently result in superb capacitive value. The simulation result in
association with equivalent circuit matches well with experimental
curve (Fig. 7a). The constant phase element (CPE) is associated with
semi-infinite diffusion of the electrolyte ions whereas the Warburg
component (W) specifies the shift from the high to low frequency region
[42]. The supercapacitive merit can be described as relaxation time
constant (τ0) which clearly defines the boundary between the resistive
B. Pandit, et al. Journal of Electroanalytical Chemistry 839 (2019) 96–107

Fig. 7. (a) Nyquist plot of CO200 electrode from 100 mHz to 100 kHz, inset shows corresponding equivalent circuit, (b) real and imaginary capacitance vs. frequency
plot of CO, CO100, CO200 and CO300 electrodes, (c) corresponding Bode plots, (d) Bode plot of CO200 electrode.

Table 1
Comparative electrochemical performance of CO, CO100, CO200 and CO300 electrodes.
Electrode Specific capacitance (F/g) Stability Resistive factors derived from EIS Relaxation time constant (ms) Phase angle
(degree)
Cyclic voltammetry Charge-discharge Retention (%) Cycles Total internal Charge transfer Imaginary Bode plot
(scan rate 2 mV/s) (current density resistance (ohm/ resistance (ohm/ capacitance vs.
1.5 mA/cm2) cm2) cm2) frequency plot

CO 182.69 120.58 90.8 4000 1.64 0.21 19.64 8.19 69.76

CO100 311.83 348.47 88.8 1.42 0.35 52.71 13.82 74.22
CO200 750 698.37 94.9 1.05 0.27 17.47 8.66 74.85
CO300 505.43 543.91 92.4 1.29 3.39 537.63 37.65 68.94

and capacitive behavior. The low value of τ0 corresponds to high power
posture which is in favor of supercapacitive eccentricity. The τ0 can be
calculated from 0 = f using imaginary frequency component (C″) vs.
1
0
frequency (f) plot [43] where
Z
C =
2 fZ2
and f0 and Z′ reveal the characteristic frequency and real part of im-
pedance (Z), respectively.
In comparison with other electrodes, the CO200 exhibits minimum
τ0 value as 17.47 ms (Fig. 7b) which clearly indicates the fast charge
transport phenomena to the inner pores during redox-active electro-
chemical reactions.
The bode plot distinguishes the charge storage abilities of the
electrodes by exhibiting frequency dependent phase angle. The com-
parison plot as shown in Fig. 7c has proven that the high frequency
region has similar nature of impedance. An ideal electrochemical
double layer capacitor exhibits well-known phase angle of 90°, whereas
pseudocapacitor shows variation in phase angle [44]. Table 1 shows the
all comparative parameters of the electrochemically examined elec-
trodes. The CO100 and CO200 electrodes exhibit almost same phase
angle though the CO200 demonstrates a maximum phase angle of
74.85°, exhibiting the suitability for the fabrication of low leakage su-
percapacitors. Time constant is often a significant factor of merit for
supercapacitor as estimated by the same equivalence 0 = f with a
1
0
projected phase angle at −45°, as herein the capacitive and resistive
impedances are identical [45]. Moreover, the short relaxations time
constant (8.66 ms) of CO200 electrode revealed by bode plot facilitates
fast ion diffusion at the interface of the electrode and electrolyte too
(Fig. 7d).
(3)
3.4. Performance of flexible symmetric supercapacitor (FS-SC) device
Electrode selection is vital for fabricating high performance flexible
solid-state symmetric and asymmetric supercapacitor devices [46–50].
The FS-SC device (dimension 3.5 × 4 cm2) based on CO200 electrodes
has been assembled using PVA-LiClO4 gel as shown by the schematic
Fig. 8. The CV curves of fabricated FS-SC device with scan rates from
100 to 2 mV/s retain a non-rectangular shape with redox peaks, de-
monstrating the non-linear dependence of stored charge with applied
voltage (Fig. 9a). The device shows superb reversibility by revealing
uniform increase in current response with the upsurge in scan rate.
Moreover, the symmetric behavior of cathodic and anodic peak currents
shows strong rare capability of the assembled device. The electro-active
material facilitates the way for intercalation/deintercalation of elec-
trolyte Li+ ions. With the full utilization of nanostructured morphology,
the device shows a maximum specific capacitance of 321.3 F/g as de-
picted in Fig. 9b.
The charge-discharge studies are tested under different current
densities varying from 3 to 6 mA/cm2 (Fig. 9c) and maximum specific

102
B. Pandit, et al.
Fig. 8. Schematic representation of the fabricated FS-SC device based on CO200 electrode and PVA-LiClO4 gel electrolyte.
capacitance reaches to 306.7 F/g at a current density of 3 mA/cm2. The
specific capacitance decreases with the increase of charge-discharge
rates due to the slow kinetics of electrolyte ions in solid interface which
is in contact with electrode surface (Fig. 9d). The obtained capacitance
values are used to evaluate the energy and power densities which are
the important parameters for supercapacitor device. The device gained
a maximum specific energy of 61.4 Wh/kg with a specific power of
3.5 kW/kg as demonstrated by Ragone plot (Fig. 10a). The device is
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Journal of Electroanalytical Chemistry 839 (2019) 96–107
Fig. 9. Electrochemical performance of FS-SC device
with PVA-LiClO4 gel electrolyte. (a) CV curves at
different scan rates ranging from 100 to 2 mV/s with
voltage window of 1.2 V, (b) specific capacitance at a
function of scan rate, (c) GCD curves at different
current densities ranging from 3 to 6 mA/cm2, (d)
specific capacitance as a function of current density.
able to deliver maximum specific power of 6.9 kW/kg with balance of
specific energy of 19.6 Wh/kg. Moreover, the obtained values of spe-
cific energy for the device is acceptable and the result is much higher
compared to previous results of the symmetric supercapacitor devices
such as porous carbon (7.22 Wh/kg) [51], MoS2/carbon cloth
(5.42 Wh/kg) [52], GO/PPy (15.1 Wh/kg) [53], SWCNTs/RuO2
(18.8 Wh/kg) [54], rGO-PEDOT/PSS (2.83 Wh/kg) [55], Pt/n-CNT@
PANI (30.22 Wh/kg) [56], ZnS/CNTs (22.3 Wh/kg) [57], ZnCo2O4/
B. Pandit, et al. Journal of Electroanalytical Chemistry 839 (2019) 96–107

Fig. 10. (a) Ragone plot, (b) cycling stability over

5000 cycles at 100 mV/s scan rate, inset shows CV
curves for different cycle numbers at scan rate of
100 mV/s, (c) Nyquist plot of impedance from
100 mHz to 100 kHz, (d) leakage current curve of
the device over 1.5 h, inset shows self-discharge
curve of the device after charging at 1.2 V.

Table 2
Summarized performance of FS-SC device compared to recently reported solid-state supercapacitor devices.
Electrode materials Device remarks Electrolyte Voltage Specific Specific energy Specific power Cyclic stability Ref.
window (V) capacitance (F/g) (Wh/kg) (kW/kg)
Retention (%) Cycles

Porous carbon Symmetric PVA–KOH 0.8 81.3 7.22 0.1 ∼90.2 6000 [51]
MoS2/Carbon cloth Symmetric LiCl-PVA 1.6 368 5.42 0.128 96.5 5000 [52]
GO/PPy Symmetric LiCl/PVA 0.8 347.8 mF/cm2 15.1 4 86 2000 [53]
SWCNTs/RuO2 Symmetric H3PO4/PVA 1 138 18.8 96 – – [54]
rGO-PEDOT/PSS Symmetric PVA/H3PO4 1 448 mF/cm2 2.83 3.5895 95 10,000 [55]
Pt/n-CNT@PANI Symmetric PVA–H3PO4 1 217.7 30.22 9.072 96 5000 [56]
ZnS/CNTs Symmetric PVA–KOH 1 159.6 22.3 5 91.8 3000 [57]
ZnCo2O4/rGO Symmetric PVA/KOH 0.4 143 11.44 1.382 93.4 5000 [58]
PEDOT:PSS/MWCNT Symmetric PVA/KOH 1 380 13.2 4.99 90 1000 [59]
Waste paper fibers-RGO–MnO2 Symmetric PVA–Na2SO4 0.8 220 19.6 2.4 85.3 2000 [60]
CoS//AC Asymmetric PVA/KOH 1.8 47 5.3 1.8 92 5000 [61]
CuS/3D graphene//3D Asymmetric PVA/KOH 1.6 32 5 3.2 77 1000 [62]
graphene
NiCo2S4/polyaniline//AC Asymmetric PVA–KOH 1.6 152.1 54.06 27.1 85.5 5000 [63]
Carbon aerogel//Co3O4 Asymmetric KOH-PVA 1.5 57.4 17.9 7.5 85 1000 [64]
rGO/CoAl-LDH//rGO Asymmetric PVA-KOH 1.2 99.5 22.6 1.5 94 5000 [65]
NiCo-LDH//carbon nanorods Asymmetric KOH-PVA 1.7 147.6 59.2 34 82 5000 [66]
MnO2@PANI//3D graphene Asymmetric PVA/KOH 1.5 95.3 37 4.0185 89 5000 [67]
foam (GF)
NiCo2O4@PPy//activated Asymmetric KOH/PVA 1.6 165.4 58.8 10.2 89.2 5000 [68]
carbon (AC)
CoMoO4@NiMoO4.xH2O// Asymmetric PVA/KOH 1.6 153.6 41.8 12 89.3 5000 [69]
Fe2O3
TiN@GNSs//Fe2N@GNSs Asymmetric LiCl/PVA 1.6 60 15.4 6.4 98 20,000 [70]
Ni(OH)2/RGO/Ni//RGO Asymmetric PVA/KOH 1.6 69 24.5 10.3 83 6000 [71]
aerogel/Ni
CNT/polyaniline//CNT/MnO2/ Asymmetric Na2SO4/PVP 1.6 – 24.8 [72]
GR
Graphene(IL-CMG)//RuO2–IL- Asymmetric H2SO4/PVA 1.8 175 19.7 6.8 – – [73]
CMG
γ-MnS//eggplant derived AC Asymmetric KOH agar gel 1.6 110.4 37.6 181.2 89.87 5000 [74]
(EDAC)
NiCo2O4/CC//porous graphene Asymmetric LiOH/PVA 1.8 71.32 60.9 11.36 96.8 5000 [75]
papers (PGP)
CeO2 Symmetric PVA-LiClO4 1.2 321.3 61.4 6.9 90.1 5000 Present
work

104
B. Pandit, et al.
Fig. 11. (a) Capacitance retention at different bending angles, (b) CV curves with different bending angles at scan rate of 100 mV/s, (c–e) actual demonstration of FS-
SC device discharging through ‘VNIT’ panel consisting 21 red LEDs for 0 s, 15 s, and 30 s respectively.
rGO (11.44 Wh/kg) [58], PEDOT:PSS/MWCNT (13.2 Wh/kg) [59], and
waste paper fibers-RGO–MnO2 (19.6 Wh/kg) [60]. The results are su-
perior than the recently reported asymmetric devices such as CoS//AC
(5.3 Wh/kg) [61], CuS/3D graphene//3D graphene (5 Wh/kg) [62],
NiCo2S4/polyaniline//AC (54.06 Wh/kg) [63], carbon aerogel//Co3O4
(17.9 Wh/kg) [64], rGO/CoAl-LDH//rGO (22.6 Wh/kg) [65], NiCo-
LDH//carbon nanorods (59.2 Wh/kg) [66], MnO2@PANI//3D gra-
phene foam (GF) (37 Wh/kg) [67], NiCo2O4@PPy//activated carbon
(AC) (58.8 Wh/kg) [68], CoMoO4@NiMoO4.xH2O//Fe2O3 (41.8 Wh/
kg) [69], TiN@GNSs//Fe2N@GNSs (15.4 Wh/kg) [70], Ni(OH)2/RGO/
Ni//RGO aerogel/Ni (24.5 Wh/kg) [71], CNT/polyaniline//CNT/
MnO2/GR (24.8 Wh/kg) [72], graphene (IL-CMG)//RuO2–IL-CMG
(19.7 Wh/kg) [73], γ-MnS//eggplant derived AC (EDAC) (37.6 Wh/kg)
[74], and NiCo2O4/CC//porous graphene papers (PGP) (60.9 Wh/kg)
[75].
For commercialization of the device, stability is the most important
aspect to determine the hands-on application. Hence, the CV cycles
were repeated for 5000 times keeping the other parameters constant.
Impressively, the device is able to retain 90.1% capacitance (Fig. 10b)
from its initial value, conceding the fact that the advanced morphology
is against the corrosion by gel electrolyte. The stable CV curves for
different cycle numbers as shown in the inset of Fig. 10b shows the
worthy fabrication of device. Moreover, the stability performance is
appreciable compared to the previously reported solid-state super-
capacitor devices as shown in Table 2. Fig. 10c shows the Nyquist plot
of assembled device. The evaluated values of RS and RCT are as low as
0.8 Ω/cm2 and 3.3 Ω/cm2, respectively in spite of addition extra re-
sistive factors such as cell packaging, current collector-electrode as-
sembly, and separator; mainly accredited to the satisfactory penetration
of electrolyte ions to establish exceptional electrochemical behavior.
Leakage current and self-discharge values are two essential para-
meters of supercapacitors in terms of the practical usage. Leakage
current of the device was measured by charging at 1.2 V through
105
Journal of Electroanalytical Chemistry 839 (2019) 96–107
monitoring the current required to maintain that potential. As shown in
Fig. 10d, the leakage current dropped quickly in the beginning and then
tended to become stable finally (89 μA). Such small value of leakage
current, which is ascribed to the self-discharge course in the device,
means less shuttle reactions caused by the impurities in the electrode
materials [76]. The leakage current is comparable to the previously
reported literatures [77,78]. As shown in inset of Fig. 10d, the device
after being charged at 1.2 V underwent a rapid self-discharge process in
the first few hours, which gradually slowed towards a stable nature.
Finally the output voltage of the device reached about 0.68 V even after
1 day. The advantage of low self-discharge course is very desirable for
the applications of the devices in areas of stand-by power, electronic
photo flash, and so on.
In addition, the FS-SC device shows high mechanical strength by
delivering capacitance with a slight deviation of 3.9% during me-
chanical bending at 175° as depicted in Fig. 11a. Furthermore, the CV
curves of devices at various bending angles reveal that the electro-
chemical performances does not change significantly with different
bending angles of device as shown in Fig. 11b. The voltage window of
one FS-SC device is 1.2 V, so the series combination altogether gives a
total voltage up to 2.4 V. So, the system is charged with a voltage 2.4 V
and discharged through the ‘VNIT’ panel consisted with 21 red light-
emitting diodes (LEDs). The panel can glow till 30 s with pronounced
intensity as shown in Fig. 11c–e (Supplementary video).
4. Conclusions
A simple, binder-less, and solution-processed approach was engaged
to optimize diverse CeO2 nanostructures and tuned through air an-
nealing from 100 to 300° towards better electrochemical performance.
Unique hierarchical CeO2 nanoparticles offer high surface area which
increases the electrode-electrolyte interaction by minimizing penetra-
tion paths of both electrolyte ions and electrons. The tuned surface
B. Pandit, et al.
architecture of electrode annealed at 200 °C leads to excellent electro-
chemical performance in terms of modest potential window (0.6 V vs.
Ag/AgCl), superb specific capacitance (750 F/g), and long-term stabi-
lity (94.9%) which enables the design of FS-SC device. The formed
solid-state device delivers a high specific capacitance of 321.3 F/g with
a wider voltage window of 1.2 V. Importantly, the device has proven its
potential use as it delivers a remarkable specific energy of 61.4 Wh/kg,
exceptional specific power of 6.9 kW/kg and excellent stability. The
outstanding electrochemical characteristics of the CeO2 symmetric su-
percapacitor device specify the expediency of the nanoparticles for the
great performance energy storage field especially for eco-friendly, small
and light-weight electronic devices for advanced industry scalable ap-
plications.
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.jelechem.2019.02.047.
Acknowledgements
B.P. gratefully acknowledges VNIT, Nagpur and B.R.S. acknowl-
edges DST/TMD/MES/2k16/09 project, Government of India. P.M.K.
sincerely acknowledges the cooperation and facilities provided by Prof.
Akihiro Furube, Department of Optical Science, Tokushima University,
Japan. All the authors are thankful to Mr. Tomoyuki Ueki, Tokushima
University for his support towards XPS measurements.
References
[1] M. Mogensen, N.M. Sammes, G.A. Tompsett, Physical, chemical and electro-
chemical properties of pure and doped ceria, Solid State Ionics 129 (2000) 63–94.
[2] T. Masui, T. Ozaki, K.-i. Machida, G.-y. Adachi, Preparation of ceria–zirconia sub-
catalysts for automotive exhaust cleaning, J. Alloys Compd. 303-304 (2000) 49–55.
[3] P. Jasinski, T. Suzuki, H.U. Anderson, Nanocrystalline undoped ceria oxygen sensor,
Sensors Actuators B Chem. 95 (2003) 73–77.
[4] V. Esposito, E. Traversa, Design of electroceramics for solid oxides fuel cell appli-
cations: playing with ceria, J. Am. Ceram. Soc. 91 (2008) 1037–1051.
[5] S. Armini, J. De Messemaeker, C.M. Whelan, M. Moinpour, K. Maex, Composite
polymer core–ceria shell abrasive particles during oxide cmp: a defectivity study, J.
Electrochem. Soc. 155 (2008) H653–H660.
[6] N. Özer, Optical properties and electrochromic characterization of sol–gel deposited
ceria films, Sol. Energy Mater. Sol. Cells 68 (2001) 391–400.
[7] Q. Fu, H. Saltsburg, M. Flytzani-Stephanopoulos, Active nonmetallic Au and Pt
species on ceria-based water-gas shift catalysts, Sci. 301 (2003) 935–938.
[8] S. Logothetidis, P. Patsalas, C. Charitidis, Enhanced catalytic activity of nanos-
tructured cerium oxide films, Mater. Sci. Eng., C 23 (2003) 803–806.
[9] M. Lira-Cantu, F.C. Krebs, Hybrid solar cells based on MEH-PPV and thin film
semiconductor oxides (TiO2, Nb2O5, ZnO, CeO2 and CeO2–TiO2): performance im-
provement during long-time irradiation, Sol. Energy Mater. Sol. Cells 90 (2006)
2076–2086.
[10] M. Flytzani-Stephanopoulos, M. Sakbodin, Z. Wang, Regenerative adsorption and
removal of H2S from hot fuel gas streams by rare earth oxides, Sci. 312 (2006)
1508–1510.
[11] X. Feng, D.C. Sayle, Z.L. Wang, M.S. Paras, B. Santora, A.C. Sutorik, T.X.T. Sayle,
Y. Yang, Y. Ding, X. Wang, Y.-S. Her, Converting ceria polyhedral nanoparticles into
single-crystal nanospheres, Sci. 312 (2006) 1504–1508.
[12] N. Imanaka, T. Masui, H. Hirai, G.-y. Adachi, Amorphous cerium−titanium solid
solution phosphate as a novel family of band gap tunable sunscreen materials,
Chem. Mater. 15 (2003) 2289–2291.
[13] C. Mandoli, F. Pagliari, S. Pagliari, G. Forte, P. Di Nardo, S. Licoccia, E. Traversa,
Stem cell aligned growth induced by CeO2 nanoparticles in PLGA scaffolds with
improved bioactivity for regenerative medicine, Adv. Funct. Mater. 20 (2010)
1617–1624.
[14] H. Chenguo, Z. Zuwei, L. Hong, G. Puxian, W. Zhong Lin, Direct synthesis and
structure characterization of ultrafine CeO2 nanoparticles, Nanotechnology 17
(2006) 5983.
[15] C. Sun, H. Li, L. Chen, Nanostructured ceria-based materials: synthesis, properties,
and applications, Energy Environ. Sci. 5 (2012) 8475–8505.
[16] Y. Li, W. Shen, Morphology-dependent nanocatalysts: rod-shaped oxides, Chem.
Soc. Rev. 43 (2014) 1543–1574.
[17] N. Maheswari, G. Muralidharan, Supercapacitor behavior of cerium oxide nano-
particles in neutral aqueous electrolytes, Energy Fuel 29 (2015) 8246–8253.
[18] H. Zhang, J. Gu, J. Tong, Y. Hu, B. Guan, B. Hu, J. Zhao, C. Wang, Hierarchical
porous MnO2/CeO2 with high performance for supercapacitor electrodes, Chem.
Eng. J. 286 (2016) 139–149.
[19] M. Vanitha, Keerthi, P. Cao, N. Balasubramanian, Ag nanocrystals anchored CeO2/
graphene nanocomposite for enhanced supercapacitor applications, J. Alloys
Compd. 644 (2015) 534–544.
[20] N.S. Arul, D. Mangalaraj, R. Ramachandran, A.N. Grace, J.I. Han, Fabrication of
106
Journal of Electroanalytical Chemistry 839 (2019) 96–107
CeO2/Fe2O3 composite nanospindles for enhanced visible light driven photo-
catalysts and supercapacitor electrodes, J. Mater. Chem. A 3 (2015) 15248–15258.
[21] B. Pandit, L.K. Bommineedi, B.R. Sankapal, Electrochemical engineering approach
of high performance solid-state flexible supercapacitor device based on chemically
synthesized VS2 nanoregime structure, J. Energy Chem. 31 (2019) 79–88.
[22] B. Pandit, D.P. Dubal, B.R. Sankapal, Large scale flexible solid state symmetric
supercapacitor through inexpensive solution processed V2O5 complex surface ar-
chitecture, Electrochim. Acta 242 (2017) 382–389.
[23] B. Pandit, D.P. Dubal, P. Gómez-Romero, B.B. Kale, B.R. Sankapal, V2O5 en-
capsulated MWCNTs in 2D surface architecture: complete solid-state bendable
highly stabilized energy efficient supercapacitor device, Sci. Rep. 7 (2017) 43430.
[24] B. Pandit, V.S. Devika, B.R. Sankapal, Electroless-deposited Ag nanoparticles for
highly stable energy-efficient electrochemical supercapacitor, J. Alloys Compd. 726
(2017) 1295–1303.
[25] C.D. Jadhav, B. Pandit, S.S. Karade, B.R. Sankapal, P.G. Chavan, Enhanced field
emission properties of V2O5/MWCNTs nanocomposite, Appl. Phys. A Mater. Sci.
Process. 124 (2018) 794.
[26] D. Deng, N. Chen, Y. Li, X. Xing, X. Liu, X. Xiao, Y. Wang, Cerium oxide nano-
particles/multi-wall carbon nanotubes composites: facile synthesis and electro-
chemical performances as supercapacitor electrode materials, Phys. E. 86 (2017)
284–291.
[27] Y. Hamlaoui, L. Tifouti, C. Remazeilles, F. Pedraza, Cathodic electrodeposition of
cerium based oxides on carbon steel from concentrated cerium nitrate. Part II: in-
fluence of electrodeposition parameters and of the addition of PEG, Mater. Chem.
Phys. 120 (2010) 172–180.
[28] Y. Hamlaoui, F. Pedraza, C. Remazeilles, S. Cohendoz, C. Rébéré, L. Tifouti,
J. Creus, Cathodic electrodeposition of cerium-based oxides on carbon steel from
concentrated cerium nitrate solutions: part I. Electrochemical and analytical char-
acterisation, Mater. Chem. Phys. 113 (2009) 650–657.
[29] Y. Zhang, F. Hou, Y. Tan, CeO2 nanoplates with a hexagonal structure and their
catalytic applications in highly selective hydrogenation of substituted nitroaro-
matics, Chem. Commun. 48 (2012) 2391–2393.
[30] X. Li, F. Chen, X. Lu, C. Ni, X. Zhao, Z. Chen, Layer-by-layer synthesis of hollow
spherical CeO2 templated by carbon spheres, J. Porous. Mater. 17 (2010) 297–303.
[31] S. Li, Q. Wang, T. Chen, Z. Zhou, Y. Wang, J. Fu, Study on cerium-doped nano-TiO2
coatings for corrosion protection of 316 L stainless steel, Nanoscale Res. Lett. 7
(2012) 227.
[32] H. Li, G. Wang, F. Zhang, Y. Cai, Y. Wang, I. Djerdj, Surfactant-assisted synthesis of
CeO2 nanoparticles and their application in wastewater treatment, RSC Adv. 2
(2012) 12413–12423.
[33] M.M. Khan, S.A. Ansari, D. Pradhan, D.H. Han, J. Lee, M.H. Cho, Defect-induced
band gap narrowed CeO2 nanostructures for visible light activities, Indus. Eng.
Chem. Res. 53 (2014) 9754–9763.
[34] S. Rajendran, M.M. Khan, F. Gracia, J. Qin, V.K. Gupta, S. Arumainathan, Ce3+-ion-
induced visible-light photocatalytic degradation and electrochemical activity of
ZnO/CeO2 nanocomposite, Sci. Rep. 6 (2016) 31641.
[35] L. Torrente-Murciano, A. Gilbank, B. Puertolas, T. Garcia, B. Solsona, D. Chadwick,
Shape-dependency activity of nanostructured CeO2 in the total oxidation of poly-
cyclic aromatic hydrocarbons, Appl. Catal. B 132-133 (2013) 116–122.
[36] Y. Kim, E.-s. Cho, S.-J. Park, S. Kim, One-pot microwave-assisted synthesis of re-
duced graphene oxide/nickel cobalt double hydroxide composites and their elec-
trochemical behavior, J. Ind. Eng. Chem. 33 (2016) 108–114.
[37] G. Wee, H.Z. Soh, Y.L. Cheah, S.G. Mhaisalkar, M. Srinivasan, Synthesis and elec-
trochemical properties of electrospun V2O5 nanofibers as supercapacitor electrodes,
J. Mater. Chem. 20 (2010) 6720–6725.
[38] B. Pandit, S.R. Dhakate, B.P. Singh, B.R. Sankapal, Free-standing flexible MWCNTs
bucky paper: Extremely stable and energy efficient supercapacitive electrode,
Electrochim. Acta 249 (2017) 395–403.
[39] B. Pandit, G.K. Sharma, B.R. Sankapal, Chemically deposited Bi2S3:PbS solid so-
lution thin film as supercapacitive electrode, J. Colloid Interface Sci. 505 (2017)
1011–1017.
[40] A.A. Yadav, A.C. Lokhande, J.H. Kim, C.D. Lokhande, High electrochemical per-
formance asymmetric supercapacitor based on La2O3//Co3O4 electrodes, J. Ind.
Eng. Chem. 56 (2017) 90–98.
[41] S.A. Pande, B. Pandit, B.R. Sankapal, Facile chemical route for multiwalled carbon
nanotube/mercury sulfide nanocomposite: high performance supercapacitive elec-
trode, J. Colloid Interface Sci. 514 (2018) 740–749.
[42] B. Pandit, S.S. Karade, B.R. Sankapal, Hexagonal VS2 anchored MWCNTs: first ap-
proach to design flexible solid-state symmetric supercapacitor device, ACS Appl.
Mater. Interfaces 9 (2017) 44880–44891.
[43] T. Li, M. Beidaghi, X. Xiao, L. Huang, Z. Hu, W. Sun, X. Chen, Y. Gogotsi, J. Zhou,
Ethanol reduced molybdenum trioxide for Li-ion capacitors, Nano Energy 26 (2016)
100–107.
[44] S.A. Pande, B. Pandit, B.R. Sankapal, Electrochemical approach of chemically
synthesized HgS nanoparticles as supercapacitor electrode, Mater. Lett. 209 (2017)
97–101.
[45] B. Pandit, B.R. Sankapal, Highly conductive energy efficient electroless anchored
silver nanoparticles on MWCNTs as a supercapacitive electrode, New J. Chem. 41
(2017) 10808–10814.
[46] Z. Zhang, F. Xiao, L. Qian, J. Xiao, S. Wang, Y. Liu, Facile synthesis of 3D
MnO2–graphene and carbon nanotube–graphene composite networks for high-
performance, flexible, all-solid-state asymmetric supercapacitors, Adv. Energy
Mater. 4 (2014) 1400064.
[47] Z. Zhang, F. Xiao, S. Wang, Hierarchically structured MnO2/graphene/carbon fiber
and porous graphene hydrogel wrapped copper wire for fiber-based flexible all-
solid-state asymmetric supercapacitors, J. Mater. Chem. A 3 (2015) 11215–11223.
B. Pandit, et al.
[48] Z. Zhang, F. Xiao, J. Xiao, S. Wang, Functionalized carbonaceous fibers for high
performance flexible all-solid-state asymmetric supercapacitors, J. Mater. Chem. A
3 (2015) 11817–11823.
[49] Z. Zhang, K. Chi, F. Xiao, S. Wang, Advanced solid-state asymmetric supercapacitors
based on 3D graphene/MnO2 and graphene/polypyrrole hybrid architectures, J.
Mater. Chem. A 3 (2015) 12828–12835.
[50] Z. Zhang, S. Liu, J. Xiao, S. Wang, Fiber-based multifunctional nickel phosphide
electrodes for flexible energy conversion and storage, J. Mater. Chem. A 4 (2016)
9691–9699.
[51] X. Li, K. Liu, Z. Liu, Z. Wang, B. Li, D. Zhang, Hierarchical porous carbon from
hazardous waste oily sludge for all-solid-state flexible supercapacitor, Electrochim.
Acta 240 (2017) 43–52.
[52] M.S. Javed, S. Dai, M. Wang, D. Guo, L. Chen, X. Wang, C. Hu, Y. Xi, High per-
formance solid state flexible supercapacitor based on molybdenum sulfide hier-
archical nanospheres, J. Power Sources 285 (2015) 63–69.
[53] J. Cao, Y. Wang, J. Chen, X. Li, F.C. Walsh, J.-H. Ouyang, D. Jia, Y. Zhou, Three-
dimensional graphene oxide/polypyrrole composite electrodes fabricated by one-
step electrodeposition for high performance supercapacitors, J. Mater. Chem. A 3
(2015) 14445–14457.
[54] P. Chen, H. Chen, J. Qiu, C. Zhou, Inkjet printing of single-walled carbon nanotube/
RuO2 nanowire supercapacitors on cloth fabrics and flexible substrates, Nano Res. 3
(2010) 594–603.
[55] Y. Liu, B. Weng, J.M. Razal, Q. Xu, C. Zhao, Y. Hou, S. Seyedin, R. Jalili,
G.G. Wallace, J. Chen, High-performance flexible all-solid-state supercapacitor from
large free-standing graphene-PEDOT/PSS films, Sci. Rep. 5 (2015) 17045.
[56] Y. Wu, Q. Wang, T. Li, D. Zhang, M. Miao, Fiber-shaped supercapacitor and elec-
trocatalyst containing of multiple carbon nanotube yarns and one platinum wire,
Electrochim. Acta 245 (2017) 69–78.
[57] X. Hou, T. Peng, J. Cheng, Q. Yu, R. Luo, Y. Lu, X. Liu, J.-K. Kim, J. He, Y. Luo,
Ultrathin ZnS nanosheet/carbon nanotube hybrid electrode for high-performance
flexible all-solid-state supercapacitor, Nano Res. 10 (2017) 2570–2583.
[58] M.I. Kyu, Y. Seonno, O. Jungwoo, Three-dimensional hierarchically mesoporous
ZnCo2O4 nanowires grown on graphene/sponge foam for high-performance, flex-
ible, all-solid-state supercapacitors, Chem. Eur. J. 23 (2017) 597–604.
[59] D. Zhao, Q. Zhang, W. Chen, X. Yi, S. Liu, Q. Wang, Y. Liu, J. Li, X. Li, H. Yu, Highly
flexible and conductive cellulose-mediated PEDOT:PSS/MWCNT composite films
for supercapacitor electrodes, ACS Appl. Mater. Interfaces 9 (2017) 13213–13222.
[60] H. Su, P. Zhu, L. Zhang, F. Zhou, G. Li, T. Li, Q. Wang, R. Sun, C. Wong, Waste to
wealth: a sustainable and flexible supercapacitor based on office waste paper
electrodes, J. Electroanal. Chem. 786 (2017) 28–34.
[61] K. Subramani, N. Sudhan, R. Divya, M. Sathish, All-solid-state asymmetric super-
capacitors based on cobalt hexacyanoferrate-derived CoS and activated carbon, RSC
Adv. 7 (2017) 6648–6659.
[62] Z. Tian, H. Dou, B. Zhang, W. Fan, X. Wang, Three-dimensional graphene combined
with hierarchical CuS for the design of flexible solid-state supercapacitors,
Electrochim. Acta 237 (2017) 109–118.
[63] X. He, Q. Liu, J. Liu, R. Li, H. Zhang, R. Chen, J. Wang, High-performance all-solid-
state asymmetrical supercapacitors based on petal-like NiCo2S4/polyaniline na-
nosheets, Chem. Eng. J. 325 (2017) 134–143.
107
Journal of Electroanalytical Chemistry 839 (2019) 96–107
[64] W. Liu, X. Li, M. Zhu, X. He, High-performance all-solid state asymmetric super-
capacitor based on Co3O4 nanowires and carbon aerogel, J. Power Sources 282
(2015) 179–186.
[65] R. Zhang, H. An, Z. Li, M. Shao, J. Han, M. Wei, Mesoporous graphene-layered
double hydroxides free-standing films for enhanced flexible supercapacitors, Chem.
Eng. J. 289 (2016) 85–92.
[66] T. Wang, S. Zhang, X. Yan, M. Lyu, L. Wang, J. Bell, H. Wang, 2-Methylimidazole-
derived Ni–Co layered double hydroxide nanosheets as high rate capability and
high energy density storage material in hybrid supercapacitors, ACS Appl. Mater.
Interfaces 9 (2017) 15510–15524.
[67] K. Ghosh, C.Y. Yue, M.M. Sk, R.K. Jena, Development of 3D urchin-shaped coaxial
manganese dioxide@polyaniline (MnO2@PANI) composite and self-assembled 3D
pillared graphene foam for asymmetric all-solid-state flexible supercapacitor ap-
plication, ACS Appl. Mater. Interfaces 9 (2017) 15350–15363.
[68] D. Kong, W. Ren, C. Cheng, Y. Wang, Z. Huang, H.Y. Yang, Three-dimensional
NiCo2O4@polypyrrole coaxial nanowire arrays on carbon textiles for high-perfor-
mance flexible asymmetric solid-state supercapacitor, ACS Appl. Mater. Interfaces 7
(2015) 21334–21346.
[69] J. Wang, L. Zhang, X. Liu, X. Zhang, Y. Tian, X. Liu, J. Zhao, Y. Li, Assembly of
flexible CoMoO4@NiMoO4·xH2O and Fe2O3 electrodes for solid-state asymmetric
supercapacitors, Sci. Rep. 7 (2017) 41088.
[70] Z. Changrong, Y. Peihua, C. Dongliang, W. Xingli, Z. Xiao, C. Shi, T.B. Kang, H. Hui,
Z. Hua, M. Wenjie, F.H. Jin, All metal nitrides solid-state asymmetric super-
capacitors, Adv. Mater. 27 (2015) 4566–4571.
[71] K. Lu, J. Zhang, Y. Wang, J. Ma, B. Song, H. Ma, Interfacial deposition of three-
dimensional nickel hydroxide nanosheet-graphene aerogel on Ni wire for flexible
fiber asymmetric supercapacitors, ACS Sustain. Chem. Eng. 5 (2017) 821–827.
[72] Y. Jin, H. Chen, M. Chen, N. Liu, Q. Li, Graphene-patched CNT/MnO2 nano-
composite papers for the electrode of high-performance flexible asymmetric su-
percapacitors, ACS Appl. Mater. Interfaces 5 (2013) 3408–3416.
[73] B.G. Choi, S.-J. Chang, H.-W. Kang, C.P. Park, H.J. Kim, W.H. Hong, S. Lee,
Y.S. Huh, High performance of a solid-state flexible asymmetric supercapacitor
based on graphene films, Nanoscale 4 (2012) 4983–4988.
[74] T. Chen, Y. Tang, Y. Qiao, Z. Liu, W. Guo, J. Song, S. Mu, S. Yu, Y. Zhao, F. Gao, All-
solid-state high performance asymmetric supercapacitors based on novel MnS na-
nocrystal and activated carbon materials, Sci. Rep. 6 (2016) 23289.
[75] Z. Gao, W. Yang, J. Wang, N. Song, X. Li, Flexible all-solid-state hierarchical
NiCo2O4/porous graphene paper asymmetric supercapacitors with an exceptional
combination of electrochemical properties, Nano Energy 13 (2015) 306–317.
[76] C. Meng, C. Liu, L. Chen, C. Hu, S. Fan, Highly flexible and all-solid-state paperlike
polymer supercapacitors, Nano Lett. 10 (2010) 4025–4031.
[77] Q. Wang, X. Wang, B. Liu, G. Yu, X. Hou, D. Chen, G. Shen, NiCo2O4 nanowire
arrays supported on Ni foam for high-performance flexible all-solid-state super-
capacitors, J. Mater. Chem. A 1 (2013) 2468–2473.
[78] B. Anothumakkool, A. Torris, A. T, S.N. Bhange, S.M. Unni, M.V. Badiger,
S. Kurungot, Design of a high performance thin all-solid-state supercapacitor mi-
micking the active interface of its liquid-state counterpart, ACS Appl. Mater.
Interfaces 5 (2013) 13397–13404.