Article

Cite This: ACS Appl. Electron. Mater. 2019, 1, 189−197 pubs.acs.org/acsaelm

Fabrication of an Advanced Asymmetric Supercapacitor Based on

Three-Dimensional Copper−Nickel−Cerium−Cobalt Quaternary
Oxide and GNP for Energy Storage Application
Lopamudra Halder, Anirban Maitra, Amit Kumar Das, Ranadip Bera, Sumanta Kumar Karan,
Sarbaranjan Paria, Aswini Bera, Suman Kumar Si, and Bhanu Bhusan Khatua*
Materials Science Centre, Indian Institute of Technology Kharagpur, Kharagpur 721302, West Bengal, India
*
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ABSTRACT: We demonstrate a cost-effective synthesis of 3D quaternary copper−nickel−cerium−cobalt oxide (Cu−Ni−Ce−

Co oxide) through a one-step hydrothermal protocol followed by a heat treatment process. The mesoporous Cu−Ni−Ce−Co
oxide (with pore diameter 4.34 nm) shows a higher specific surface area (86.9 m2 g−1). The as-synthesized quaternary oxide
provides an ultrahigh specific capacitance of 2696 F g−1 at 1 A g−1 along with a moderate cycle stability of 86.5% after 3000
charge−discharge cycles. Furthermore, an asymmetric supercapacitor (ASC) was established by assembling Cu−Ni−Ce−Co
oxide and graphene nanoplatelets (GNP) as positive and negative electrode materials, respectively, and the supercapacitor
performances were executed thoroughly. The ASC delivers a remarkable energy density of ≈51 Wh kg−1 at a power density of
581.9 W kg−1 together with long-term cyclic stability (92% specific capacitance retention after 3000 cycles). The compositional
and morphological features together with superior electrochemical properties can make it advantageous for practical use in
energy and power applications.
KEYWORDS: quaternary oxide, specific capacitance, energy density, mesoporous, cross-linked

1. INTRODUCTION oxides and hydroxides. From the device fabrication approach,

The ever-rising energy crisis and depletion of fossil fuel have
instigated researchers for the exploration of an efficient energy
storage system. Today, supercapacitors or ultracapacitors have
emerged as eminent energy storage devices to accomplish the
demand of energy scarcity. Owing to rapid inflation of portable
electronics and hybrid vehicles, fabrication of such a device has
drawn considerable attention by researchers.1,2 High output
performance (higher power density, good rate capability, and
prolonged cycle life), excellent cyclic stability, and environ-
mental friendliness are the salient features of a super-
capacitor.3−6 Based on the energy storage mechanism,
supercapacitors can be classified into two classes: electric
double-layer capacitors (EDLCs) and pseudocapacitors.7,8
Usually EDLCs involve porous, carbonaceous materials like
graphene,9 heteroatom (N2,10 B,11 Fe,12 S13) doped graphene,
carbon nanotubes, and carbon nanohorns, while pseudocapa-
citors solely employ binary, ternary, or even quaternary metal
supercapacitors are categorized into two parts: (a) symmetric
(with sandwiching two similar type supercapacitor electro-
des)14 and (b) asymmetric (sandwiching two dissimilar type
electrode materials).15 Asymmetric supercapacitors (ASCs)
based on a battery type positive electrode and capacitor type
negative electrode material have drawn considerable interest
due to their enlarged potential window, which eventually
improves the energy (E) and power density (P).16 Ternary or
higher order metal oxides are being widely employed as
positive electrode material in supercapacitor application
because of their high specific capacitance, composition
tunability, and low cost. The rationale behind working on
the quaternary metal oxide is as follows: these mixed oxides
Received: November 1, 2018
Accepted: January 14, 2019
Published: January 14, 2019

© 2019 American Chemical Society 189 DOI: 10.1021/acsaelm.8b00038

ACS Appl. Electron. Mater. 2019, 1, 189−197
ACS Applied Electronic Materials
through their mixed and various valence states impart greater
electrochemical conductivity and enhance the specific
capacitance (Cs) compared to their corresponding mono-
metallic and bimetallic oxides.17,18 The prominent morpho-
logical features (nanostructure and three-dimensional (3D)
architecture) and large specific surface area promote the rate of
ion diffusion, resulting in greater electrochemical activity.19−21
However, many studies have been reported related to ternary
metal oxides, but very limited work has been found on
quaternary metal oxides. For instance, Tu et al. reported the
synthesis of Mn−Ni−Co ternary oxide nanowires, revealing a
specific capacitance (Cs) of 638 F g−1 at 1 A g−1.22 Zhang et al.
acquired a Cs value of 2481.8 F g−1 at 1 A g−1 for Zn−Ni−Co
nanowire arrays.23 Ryu et al. reported a specific capacity of 178
C g−1 at 1 A g−1 specific current for Cu−Zn−Co oxide
nanoflakes grown on Ni foam.24 Yao et al. reported an
ultrahigh specific capacitance of 490.7 F cm−3 at 1 mA cm−2
current density for hierarchical molybdenum−nickel−cobalt
ternary oxide.25 Wei et al. synthesized Ce−Ni−Mn−Co oxide
through the solvothermal method, which results in a Cs value
of 1840.6 F g−1 at 1 A g−1.26 Another quaternary Zn−Ni−Al−
Co oxide has been reported by Zhang et al., exhibiting a
specific capacity of 839.2 C g−1 at 1 A g−1.27 However, studies
related to the electrochemical activity of Cu−Ni−Ce−Co
oxide are rare. The electrochemical contribution of the
quaternary mixed oxide (with Cu, Ni, Ce, and Co ions) can
provide rich redox reactions compared to their mono- or
bimetallic oxides due to the synergistic effect and enhanced
oxidation states, which improves the capacitance property. Cu
possesses ultrahigh electrical and thermal conductivity.28,29 Ce
is a rare earth element of 4f series with high electrical
conductivity.30,31 Ni is the most abundant element on earth. It
increases capacitive behavior and active site density.32,11,21 Co
is beneficial in increasing electronic conductivity. The
electrochemical activity of the metal oxides still suffers from
low conductivity and structural degradation,6 resulting in lower
energy density. However, a decent energy density along with a
remarkable power density can be achieved by building up
hybrid asymmetric supercapacitors in an aqueous electrolyte.
These hybrid supercapacitors are comprised of a battery type
electrode (as source of energy) and a capacitor type electrode
(as source of power). Therefore, use of the two different
potential windows from the two electrodes can provide
maximum voltage window.33−36 Furthermore, synthesizing
the nanostructured, free-standing material of high electro-
chemical activity without any conductive substrate (nickel
foam,37 carbon cloth/fiber,38 and copper foam39) is a great
challenge.
In this work, a multicomponent electrode material based on
Cu−Ni−Ce−Co oxide has been developed through a facile
and substrate-free (Ni foam, Cu foam, and carbon fabric/
cloth) hydrothermal route followed by a postannealing
treatment. The precursor shows a 3D cross-linked, nanoflake
structure, which on annealing collapses, and numerous
nanoparticles (68−73 nm) were grown on the surface of
nanoflakes. The increased porosity (pore diameter 4.34 nm)
and ultrahigh surface area (86.9 m2 g−1) of the electrode
material further boost the ion transportation phenomenon and
expedite the electrode−electrolyte interaction. The electrode
material in two-electrode configuration exhibits Cs of 2696 F
g−1 at 1 A g−1 which shows 86.5% Cs retention after 3000
charge−discharge cycles. Furthermore, GNP gives Cs of 163 F
g−1 at 1 A g−1 current density. To meet the requirement of
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higher energy density together with wider potential window, an
ASC (asymmetric supercapacitor) has been fabricated using as-
synthesized quaternary oxide as positive and GNP as negative
electrode materials including 1 M aqueous KOH soaked
Whatman filter paper serving as a separator. The ASC can
reversibly perform in the potential window of 0−1.4 V. The
ASC reveals ultrahigh Cs of 183.3 F g−1 at 1 A g−1 with
remarkable energy density of ≈51 Wh kg−1 at power density of
581.9 W kg−1. It reveals significant cycle stability of 92% Cs
retention even after 3000 charge−discharge cycles.
2. EXPERIMENTAL SECTION
2.1. Materials Details. Cobalt chloride hexahydrate, nickel
chloride hexahydrate, copper chloride hexahydrate, cerium sulfate
hexahydrate, urea, and ammonium fluoride were obtained from Merck
Chemicals, India. Polyvinylpyrrolidone (PVP) and potassium
hydroxide (KOH) were purchased from Loba Chemie. Graphene
nanoplatelets (multilayered, carbon purity >99.5%, thickness 8−10
nm) were obtained from J. K. Impex, Mumbai. Deionized (DI) water
used throughout the work was collected from a JL-RO100 Millipore-
Q Plus water purifier. All the analytical grade reagents were used
without any further purification. Commercially available stainless steel
(SS) fabric was used as a conducting current collector. It was rubbed
with emery polish paper followed by cleaning with distilled water and
ethanol by ultrasonication. The flexibility of the SS fabric is an added
advantage, which includes flexibility in the as-prepared ASC device.
2.2. Synthesis of Quaternary Oxide. The hybrid material was
synthesized through a simple, cost-effective, one-step hydrothermal
procedure followed by a postannealing treatment. In a typical process,
2 mM CoCl2·6H2O, 0.2 mM NiCl2·6H2O, 0.5 mM CuCl2·6H2O, and
0.3 mM Ce2(SO4)3·6H2O were dissolved in 50 mL of DI water along
with addition of 1−2 g of PVP. The solution was stirred for half an
hour to form a clear solution. Afterward, 1 mM Co(NH2)2 and 0.3
mM NH4F were added into the above reaction mixture. It was then
transferred into a 50 mL Teflon-lined stainless autoclave and heated
in a muffle furnace at temperature of 150 °C for 8 h. After cooling to
room temperature, the resultant product was rinsed with DI water and
ethanol eventually. Finally, the product was dried in a hot oven at ∼50
°C for 12 h. The as-obtained product was calcined at 300° C for 4 h.
Finally, a black product was obtained and termed Cu−Ni−Ce−Co
oxide. Prior to comparison of the electrochemical properties, Co
oxide, Cu−Co oxide, and Cu−Ni−Co oxide were prepared following
the same procedure using respective materials.
2.3. Characterizations. The crystallographic information about
as-synthesized electrode material was identified through X-ray
diffraction (XRD) analysis using an X-Pert PRO diffractometer
(PANalytical, Netherlands) with monochromatic Cu Kα radiation (λ
= 0.15418 nm) at an accelerating voltage and current of 40 kV and 30
mA, respectively. The measurement was done over the range (2θ) of
10°−80° at a scan rate of 0.5 °C/min. Field emission scanning
electron microscopic (FESEM) analysis was performed to observe the
morphology of the prepared materials, conducted in a Carl Zeiss-
SUPRA 40 (Oberkochen, Germany) at an working voltage of 5 kV.
The microstructure of the electrode materials was identified through
high-resolution transmission electron microscopic (HRTEM) analysis
(HRTEM: JEM-2100, JEOL, Tokyo, Japan), operated at an
accelerating voltage of 200 kV. The TEM-EDX mapping was also
performed during TEM analysis. The nitrogen adsorption isotherm
was conducted using a Quantachrome ChemBET TPR/TPD analyzer
at 77 K. The active surface area was measured by introducing the
Brunauer−Emmett−Teller (BET) model while the pore size and
volume were calculated by the Barrett−Joyner−Halenda (BJH)
method. The electrochemical measurements, i.e., cyclic voltammetry
(CV), galvanostatic charge−discharge (GCD), and electrochemical
impedance spectroscopy (EIS), were performed on a Biologic (SP-
150) electrochemical workstation to evaluate the supercapacitive
performances of the synthesized materials. The preparation and
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Figure 1. Schematic illustration for the synthesis of electrode material and assembly of the ASC device.

successive fabrication of the corresponding ASC device are presented

in Figure 1.
2.4. Preparation of Working Electrodes. Electrochemical
measurements of the prepared electrode and GNP (active materials)
were performed in a three-electrode setup. The working electrodes
were prepared in the following method: the active materials were
mixed with acetylene black (AB) and poly(vinylidene fluoride)
(PVDF) in a ratio of 8:1:1 (w/w/w) and were dispersed in N-methyl-
2-pyrrolidone (NMP) solvent to make a uniform slurry. The slurry
was coated on a piece of stainless steel (SS) mesh fabric of dimensions
1 × 1 cm2 (SS fabric was used as current collector here) and dried for
8 h at 60−65 °C. The electroactive material coated SS fabric was used
as the working electrode, while platinum and saturated calomel
electrodes (SCE) were employed as a counter and reference
electrodes, respectively. An ASC device has been fabricated employing
Cu−Ni−Ce−Co oxide coated SS as positive and GNP coated SS as
negative electrodes material, using Whatman 40 filter paper soaked in
1 M KOH as a separator. The porosity of the filter paper accelerates
the diffusion phenomena of the electrolyte. The mass ratio (m+:m−) of
the positive to negative electrode (Cu−Ni−Ce−Co oxide:GNP) was Figure 2. XRD patterns of (a) Cu−Ni−Ce−Co oxide, (b) JCPDS
calculated to be 0.1818. card number 054-0844, and (c) JCPDS card number 071-0567.

3. RESULTS AND DISCUSSION (2 and 1 μm) revealed the formation of interconnected 3D

The structure and chemical composition of the calcined
electrode material were investigated by XRD analysis (Figure
2). The as-obtained peaks of the calcined electrode material
confirm the development of Cu−Ni−Ce−Co oxide, since the
peaks match well with cubic phase of Cu0.48Ni0.16Co2.36O4 of
JCPDS card number 054-0844 of space group Fd3m and
Ce7O12 phase of JCPDS card number 071-0567. The major
diffraction peaks appearing at 2θ values 18.8°, 31.1°, 36.6°,
38.3°, 44.1°, 55.4°, 59.03°, and 64.9° were indexed to the
(111), (220), (311), (222), (400), (422), (511), and (440)
crystal planes of Cu0.48Ni0.16Co2.36O4, respectively. Addition-
ally, the sharp and intense peak at 27.8° along with a tiny peak
at 32.4° reveals (211) and (113) crystal planes of Ce7O12
(JCPDS card number 071-0567). The diffraction peaks of the
quaternary oxide show a slight change in its peak position due
to the differences in ionic radius of Co, Cu, Ni, and Ce.30
The surface morphology of the precursor and the hybrid
material was evaluated through FESEM analysis. The FESEM
images (Figure 3a−c) of the precursor at lower magnification
191
nanoflake-based nanoflower morphology. The high-magnifica-
tion FESEM images exhibit highly ordered nanoflakes with
smoother surfaces. The interconnected nanoflakes with an
average width of 42−52 nm were found to cross-link with each
other to form a three-dimensional interconnected network
structure. A minute amount of nanoparticles (size of 48−60
nm) was scattered on the smooth surface of the nanoflakes.
After annealing, the cross-linked network structure of the
precursor composite was well retained, but the Cu−Ni−Ce−
Co precursor got dehydrated to form the oxide with collapsing
the smooth nanoflake architecture.40 Each nanoflake was found
to split into a few layers, finally transforming into thinner and
looser nanostructure that probably provided more open space
and large numbers of active sites for redox reaction to take
place. The surface became rough as numerous nanoparticles
(size of ≈68−73 nm) were anchored on the surface of the
nanoflake layers (Figure 3d−f). This surface roughness can
increase the active surface area through which electrolyte can
penetrate into the deeper pores of the electrode, facilitating
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Figure 3. (a−c) FESEM images of Cu−Ni−Ce−Co precursor, (d−f) FESEM images of Cu−Ni−Ce−Co oxide, (g, h) HRTEM images, and (i)
SAED pattern of Cu−Ni−Ce−Co oxide.
easy electrolyte access to boost the capacitive performance.41
The microstructure of the Cu−Ni−Ce−Co oxide material
after annealing was further confirmed by HRTEM analysis.
Figure 3g displays dense nanoflake morphology with trans-
parent outer regions, which eventually signifies the porous
nature of the material. The appearance of numerous nano-
particles is observed on the surface of the nanoflakes in the
HRTEM image, consistent with the FESEM analysis. These
large numbers of nanoparticles produce many redox-active
sites, which promotes the electrochemical reaction. The
nanoparticles show a uniform distribution with size ranging
from 33 to 41 nm. These mesopores help in electrolyte
penetration into electrodes and fast charge transfer reaction.
The HRTEM image (Figure 3h) reveals the presence of
different lattice fringes of the quaternary oxide. The interplanar
spacings of 0.24, 0.23, 0.20, and 0.15 nm were measured
corresponding to the (311), (222), (400), and (511) lattice
planes of Cu−Ni−Ce−Co oxide. The selected area diffraction
pattern (SAED) as represented in Figure 3i shows well-defined
diffraction rings indicating the polycrystalline nature of Cu−
Ni−Ce−Co oxide. The diffraction rings can be indexed to
(111), (311), (400), and (511) planes, which agrees well with
the XRD results.
Figure 4 represents electrochemical measurements of all
prepared electrode materials in the three-electrode config-
uration utilizing 1 M aqueous KOH solution. Before
performing the electrochemical characterizations, the electro-
des were charged/discharged for ∼100 recurring cycles at
constant current density (1 A g−1)to obtain a stable Cs value26
that enables adequate wetting of the surface of the electrodes
by the aqueous KOH electrolyte. CV analysis was performed
to examine the redox reaction occurring between the metal
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ions and the alkaline electrolyte. For comparison of electro-
chemical properties, CV analyses of Co oxide, Cu−Co oxide,
Cu−Ni−Co oxide, and Cu−Ni−Ce−Co oxide (as presented
in Figure 4a) have been performed at 2 mV s−1 within the
potential window of 0−0.4 V. Figure 4b reveals the CV plot of
the hybrid electrode (Cu−Ni−Ce−Co oxide) material
between a voltage window of 0−0.4 V (vs Hg/Hg2Cl2) at
different scan rates of 2, 5, 10, 30, 50, and 80 mV s−1. A couple
of well-defined strong redox peaks (anodic peak at 0.338 V and
cathodic peak at 0.215 V) were observed in the CV curve of
hybrid electrode material, demonstrating the faradaic capaci-
tive behavior. The redox peaks are associated with the
following probable quasi-reversible redox reaction of Cu−
Ni−Ce−Co oxide mediated by the OH− ion from KOH
electrolyte.
(Cu Ce)NiCoO + H 2O + OH− ↔ CoOOH + NiOOH + e−
(I)
CoOOH + OH− ↔ CoO2 + H 2O + e− (II)
The shape of the CV curve remains analogous even at higher
scan rates, revealing excellent electrochemical reversibility and
rate capability of the electrode material.42 The peak current
density increases linearly with corresponding scan rates,
implying the rate of electron transport is rapid enough even
at much higher scan rates.43 The Cu−Ni−Ce−Co oxide
electrode shows a larger integrated area under the CV curve
than Cu−Ni−Co oxide, Cu−Co oxide, and Co oxide,
suggesting better electrochemical performance of the quater-
nary oxide system which is attributed to fast charge transport
and better electronic conductivity.44 Figure 4c represents
discharge curves of electrode materials Co oxide, Cu−Co
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Figure 4. (a) CV plots of four different electrode materials at 2 mV s−1 scan rate, (b) CV plots of Cu−Ni−Ce−Co oxide at various scan rates, (c)
GCD plots of all electrode materials at 1 A g−1 current density, (d) GCD plot of Cu−Ni−Ce−Co oxide.at various current densities, (e) variation of
Cs of electrode materials with applied current density, and (f) cyclic stability of Cu−Ni−Ce−Co oxide.

oxide, Cu−Ni−Co oxide, and Cu−Ni−Ce−Co oxide at 1 A
g−1 current density within a potential window of 0−0.4 V. The
longer discharge curve of Cu−Ni−Ce−Co oxide demonstrates
a higher specific capacitance and higher electrochemical
performance. Figure 4d depicts the GCD profile of Cu−Ni−
Ce−Co oxide at different current densities of 1, 2, 4, 8, 10, and
20 A g−1. The typical nonlinear discharge curve with a voltage
plateau between ∼0.4 and 0.15 V validates the pseudocapa-
citive nature of the electrode material signifying the quasi-
reversible redox reaction occurring at the electrode−electrolyte
interface. The Cs value was calculated using the following
relation based on the discharge current densities of the
electrode material:
i × Δt
Cs =
m × ΔV
where Cs is the specific capacitance in F g−1, i/m represents
current density in A g−1, and ΔV and Δt denote the potential
window in volts and discharge time in seconds, respectively.
The Cs value (2696 F g−1) obtained for Cu−Ni−Ce−Co oxide
(active mass of 0.008 g) at 1 A g−1 is higher than other as-
synthesized electrode materials, i.e., for Cu−Ni−Co oxide
2180 F g−1 (active mass: 0.008 g), Cu−Co oxide 800 F g−1
(active mass: 0.009 g), and Co oxide 570 F g−1 (active mass:
0.006 g). The Cs values for Cu−Ni−Ce−Co oxide were found
to be 2696, 2685, 2649, 2587, 2525, and 2412 F g−1 at 1, 2, 4,
8, 10, and 20 A g−1 current densities, respectively. The
calculated Cs of individual oxide materials as a function of
discharge current density has been shown in Figure 4e. The Cs
value decreased with enhanced current density because of the
unavailability of redox-active sites for further participation in
redox reaction and increased voltage drop.45 The hybrid
(1) quaternary oxide electrode reveals a good rate capability with
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retention of Cs of 89.4% even at a higher current density of 20
A g−1. Apart from CV, GCD test cycling stability is a significant
parameter to evaluate the stability of the electrode material.
Cycling performance was evaluated at a constant current
density of 1 A g−1 for 3000 GCD cycles. It reveals a retention
of 86.5% of initial Cs after 3000 consecutive GCD cycles (as in
Figure 4f).
The resistive behavior of Cu−Ni−Ce−Co oxide, Cu−Ni−
Co oxide, Cu−Co oxide, and Co oxide was investigated
through EIS analysis (as presented in Figure 5), performed in a
Figure 5. Nyquist plot of Cu−Ni−Ce−Co oxide, Cu−Ni−Co oxide,
and Cu−Co oxide (in the inset Co oxide). The equivalent fitted
circuit diagram is presented in the upper portion of the graph.
frequency range of 1 MHz−100 mHz. The corresponding
equivalent circuit diagram has been provided in the inset of
Figure 5. As perceived from the Nyquist plot, it is observed
that each of the impedance spectra has two major parts: a small
arc in the high-frequency region followed by a linear part in the
low-frequency region. The semicircular part denotes the charge
transfer resistance (Rct), while the steeper portion at the lower
frequency region signified presence of Warburg impedance
(W) which demonstrates the diffusion of electrolyte within the
electrode material. The initial intersection point of the
semicircular region with the real impedance axis at high
frequency region denotes the solution resistance (Rs). The
Nyquist plot of the hybrid electrode material does not indicate
an ideal capacitive behavior so a best-fitted curve, i.e., constant
phase element (CPE), has been incorporated along with the
equivalent circuit diagram. The fitted circuit is comprised of
several resistances (Rs, Rct, W, CPE) together with double-layer
capacitance (Cdl) arranged in a parallel series. Therefore, the
circuit resistance has been expressed as Rs + Q/(Rct + W) +
Cdl/Rct. The charge transfer resistance and solution resistance
for Cu−Ni−Ce−Co oxide were found to be 1.171 Ω and
0.287 Ω, respectively, which are lower than Cu−Ni−Co oxide
(Rct = 1.251 Ω, Rs = 0.4197 Ω), Cu−Co oxide (Rct = 1.38 Ω,
Rs = 0.825 Ω), and Co oxide (Rct = 1.63 Ω, Rs = 1.098 Ω).
To explore practical application of the prepared electrode
material in a supercapacitor energy storage device, an ASC
device was fabricated utilizing Cu−Ni−Ce−Co oxide coated
stainless-steel as positive (Cu−Ni−Ce−Co oxide@SS) and
GNP coated stainless steel (GNP@SS) as negative electrodes
including 1 M KOH soaked laboratory Whatman filter paper.
To evaluate a stable voltage−window of the ASC, CV analysis
was conducted for both the positive and negative electrodes at
2 mV s−1 scan rate. The CV curve of Cu−Ni−Ce−Co oxide@
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SS reveals pseudocapacitive characteristic with a pair of
prominent redox peaks ranging from 0 to 0.4 V. On the
other hand, the CV curve of GNP@SS is nearly rectangular-
shaped, indicating EDLC behavior in a potential window of −1
to 0 V (as shown in Figure 6a), and the overall capacitance is a
joint contribution from EDLC and pseudocapacitor property.
Therefore, the total operating potential window was estimated
as the sum of potential windows of the positive and negative
electrodes. Thus, a potential window of 0−1.4 V has been fixed
for the electrochemical characterization of ASC. The charge-
balance equation (q+ ≈ q−) was employed to achieve the mass
ratio of Cu−Ni−Ce−Co oxide@SS to GNP@SS. The total
charge stored in electrode material has been calculated from
the equation
q = C × ΔV × m (2)
−1
where C, ΔV, and m denote the specific capacitance (F g ),
working potential (V), and mass of the active material coated
on SS, respectively. The mass ratio of the positive and negative
electrode materials was calculated by the following equation:
m+ C × ΔV −
= −
m− C+ × ΔV+ (3)
where m+ and m− are the effective masses, C+ and C− are
specific capacitance, and ΔV+ and ΔV− are working potentials
of positive and negative electrodes, respectively. Using the
charge balance equation, the obtained mass ratio for positive to
negative electrode was ≈0.1818. Figure 6b exhibits the typical
CV curves of as-fabricated Cu−Ni−Ce−Co oxide@SS//
GNP@SS ASC in a potential window of 0−1.4 V. The
appearance of well-defined redox peaks in between 0.55 and
1.4 V depicts pseudocapacitive characteristics, and the almost
rectangular shape from 0 to 0.55 indicates the existence of
EDLC features in the ASC. The corresponding GCD curves
are presented in Figure 6c at the varying current densities of 1,
2, 4, 8, 10, and 20 A g−1. The discharge curve shows slight
nonlinearity, which is in accordance with CV results. The Cs
values were obtained to be 183.3, 171.7, 155.8, 138.4, 129.6,
and 117.2 F g−1 at 1, 2, 4, 8, 10, and 20 A g−1 current density
(based on active mass of ASC). The cycle stability test
(represented in Figure 6f) of ASC was performed over 3000
charge−discharge cycles at 1 A g −1 current density.
Interestingly, the device exhibited 92% retention of initial Cs
even after 3000 charge−discharge cycles, depicting a long-term
cyclic stability. The energy and power density calculation is a
key parameter in evaluating electrochemical performance of
ASC. The energy and power density were calculated according
to following equations:
1
EASC = × CASC × (ΔV )2
2 (4)
PASC = EASC /T (5)
Here, EASC indicates the energy density (Wh kg−1), ΔV
symbolizes the voltage drop during the discharge process, CASC
is the total specific capacitance (F g−1), PASC implies power
density in W kg−1, and T represents the discharge time. In the
Ragone plot (represented in Figure 6e) the maximum obtained
energy density was ≈51 Wh kg−1 at a power density of 581.9
W kg−1. Even at a high power density of 9849.5 W kg−1 the
energy density was attained at 31.9 Wh kg−1, which is
competitive with those reported earlier. The electrochemical
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Figure 6. (a) CV profiles of Cu−Ni−Ce−Co oxide and GNP at a scan rate of 2 mV s−1, (b) CV plots of the ASC device at various scan rates, (c)
GCD plots of ASC at different current densities, (d) variation of Cs with various current densities, (e) Ragone plot of the ASC device, and (f) Cs
retention after 3000 consecutive charge−discharge cycles.

Table 1. Comparison of Electrochemical Performances of Our as Prepared ASC Device with Other Reported Asymmetric
Supercapacitors
operating voltage range energy density power density
ASC-based materials (V) Cs (F g−1) (Wh kg−1) (Wh kg−1) ref
CuCo2O4@ CuCo2O4//AC 1.5 57.6 F g−1 at 2 mA/cm2 18 125 43
ZNCO nanowires arrays//AC 1.5 113.9 F g−1 at 1 A g−1 35.6 187.6 44
Ni−Co−Fe−S@NCAs-NP 1.5 114 F g−1 at 0.2 A g−1 35.9 375 45
flowerlike Ni−Zn−Co oxide//AC 1.6 44.5 880 46
CuCo2S4@Ni−Mn LDH//AC 1.5 146.7 F g−1 at 2 A g−1 45.8 1499 47
ZICO//NG 1.5 129.74 F g−1 at 1 A g−1 40.5 750 30
Cu−Ni−Ce−Co oxide@SS//GNP@ 1.4 183.3 F g−1 at 1 A g−1 51 581.9 this work
SS

performance of our as-fabricated ASC device with previously
reported other ASC devices is displayed in Table 1.
Moreover, a practical application of the ASC has been
demonstrated by illuminating one red-light-emitting diode
(LED). Two ASC devices were connected serially and charged
for 30 s. Afterward, during discharging; the discharge current
from the ASCs flows through the red LED and lightens the red
LED bulb. The variation of intensity of the single red LED
light just after connection and after 5, 7, and 10 min intervals
are respectively presented graphically in Figure 7a−d.
195
The superior electrochemical performance of the ASC can
be attributed to various reasons. First, the complex
configuration with variable mixed valence states and the strong
synergy property of different metal ions (Cu, Co, Ni, and Ce)
enhance the electrochemical performances. Second, the three-
dimensional (3D) network architecture with distinct meso-
porous feature and large open spaces allowed the complete
utilization of the electrode material by electrolyte resulting in a
large number of electroactive sites for the redox reaction to
take place and hence improved the specific capacitance and
DOI: 10.1021/acsaelm.8b00038
ACS Appl. Electron. Mater. 2019, 1, 189−197
ACS Applied Electronic Materials
Figure 7. Photographs of the ASC device lightening the red LED light
(a) after connection and at different time intervals: (b) after 5 min,
(c) after 7 min, and (d) after 10 min.
cyclic stability. The rough surface feature increases the active
charge density; therefore, easy penetration of the electrolyte
into the inner pores of the electrode material improves the
charge transfer process and rate capability. Moreover, the
electronic conductivity of metal ions, ultrahigh surface area,
and porous structure are the added pluses for achievement of
better electrochemical outcome.
4. CONCLUSION
Based on above discussion, it can be demonstrated that 3D
quaternary mesoporous Cu−Ni−Ce−Co oxide nanoflakes has
been synthesized through a facile and cost-effective hydro-
thermal protocol followed by subsequent heat treatment
process. The self-supported 3D nanoflakes endowed with
mesoporous feature and rough surface escalate the electro-
chemical properties. An outstanding specific capacitance value
of 2696 F g−1 was obtained from the quaternary oxide material.
The high-performance ASC device based on Cu−Ni−Ce−Co
oxide@SS and GNP@SS (as positive and negative electrode
materials, respectively) exhibits a specific capacitance value of
183.3 F g−1 at 1 A g−1 current density. Moreover it delivered a
remarkable energy density of ≈51 Wh kg−1 at a power density
of 581.9 W kg−1 maintaining superior cyclic stability (≈92%
after 3000 charge−discharge cycles). Furthermore, two serially
connected ASC devices Cu−Ni−Ce−Co oxide//GNP can
successfully power up one red LED bulb. From the resultant
features, it can be envisioned that the Cu−Ni−Ce−Co oxide
can serve as self-supported electrode material contributing an
ultrahigh specific capacitance value, and the as-fabricated ASC
device can perform as an eminent candidate for energy storage
applications.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsaelm.8b00038.
TEM-EDS mapping analysis, surface area and pore size
distribution analysis, electrochemical performance of
GNP as negative electrode, electrochemical perform-
ances of prepared electrode materials, comparison of
ASC device performance employing other different
mixed oxides as positive electrodes (PDF)
196
Article
■ AUTHOR INFORMATION
Corresponding Author
*(B.B.K.) E-mail khatuabb@matsc.iitkgp.ernet.in; Tel +91-
3222-283982.
ORCID
Bhanu Bhusan Khatua: 0000-0002-1277-0091
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We are extremely thankful to the Indian Institute of
Technology Kharagpur for financial support.
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