Journal of Power Sources 458 (2020) 228005

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Journal of Power Sources

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Oxygen vacancies enhance supercapacitive performance of CuCo2O4 in

high-energy-density asymmetric supercapacitors
Yamin Feng a, b, Weifeng Liu c, Yin Wang d, Wenning Gao a, Jitao Li a, Kuili Liu a, **,
Xiaoping Wang a, Jian Jiang b, *
a
College of Physics and Telecommunication Engineering, Zhoukou Normal University, 466001, Zhoukou, PR China
b
Chongqing Key Laboratory for Advanced Materials & Technologies of Clean Energies, Chongqing, 400715, PR China
c
School of Physics, Huazhong University of Science and Technology (HUST), Wuhan, 430074, PR China
d
Hubei Key Laboratory of Low Dimensional Optoelectronic Materials and Devices, Hubei University of Arts and Science, Xiangyang, 441053, PR China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

� Mesoporous CuCo2O4 nanoflowers with

enriched oxygen vacancies are
synthesised.
� The sample exhibits abundant active
sites and enhanced electronic
conductivity.
� The electrode delivers high specific
capacitance and excellent cyclic
performance.
� The device displays a high energy den­
sity of 58.7 Wh kg 1 (at 800 W kg 1).

A R T I C L E I N F O A B S T R A C T

Keywords: Although the emerging CuCo2O4 electrode material proves to be promising for use in energy-storage applica­
Oxygen vacancies tions, its slow reaction kinetics and poor conductivity limit its broad utilisation. To address this challenging
CuCo2O4 fundamental issue, herein, oxygen-vacancy-enriched CuCo2O4 nanoflowers is prepared using a facile hydro­
Electrochemical performances
thermal method followed by thermal treatment in a hypoxic atmosphere. Because of the presence of oxygen
Supercapacitor
defect sites and impurity bands, such flower-like CuCo2O4 nanomaterials with large specific surface areas
demonstrate much superior electrical conductivity and favourable hydrophilic properties, which are highly
encouraging for supercapacitor applications. Impressively, when evaluated as an active electrode material, it
exhibits a remarkable specific capacitance (1006 F g 1 at 1 A g 1, i.e., 1.2 F cm 2 at 1.2 mA cm 2), excellent rate
capability (69.4% capacitance retention at 20 A g 1) and ultra-long cycling lifespan (85.5% specific capacitance
retention after 10,000 cycles). Moreover, when being paired with activated carbon, the quasi-solid-state asym­
metric supercapacitors provide a maximum energy density of 58.7 Wh kg 1 at a power density of 800 W kg 1
and extraordinary cycling stability (71.2% retention after 10,000 cycles). These results firmly verify that the
proper incorporation of oxygen vacancies into metal oxides provides a new efficient pathway to advance elec­
trode behaviours.

* Corresponding author.,
** Corresponding author.
E-mail addresses: liukuili@163.com (K. Liu), jjiang@swu.edu.cn (J. Jiang).

https://doi.org/10.1016/j.jpowsour.2020.228005
Received 16 November 2019; Received in revised form 29 January 2020; Accepted 8 March 2020
Available online 20 March 2020
0378-7753/© 2020 Elsevier B.V. All rights reserved.
Y. Feng et al.
1. Introduction
With an increasing demand for electric vehicles and portable elec­
tronic devices, the need for high-performance electrical energy storage
systems has become urgent. Supercapacitors have been paid much at­
tentions as one of the most important energy-storage systems because of
their high power density, excellent reversibility, fast charge–discharge
rates and excellent cycling stability [1–5]. The electrochemical proper­
ties of supercapacitors mainly depend on their electrode materials.
Various ternary transition metal oxides, including NiCo2O4 [6–8],
CuCo2O4 [9–11], NiMn2O4 [12] and CoMoO4 [13], have been widely
investigated as pseudocapacitive electrode materials, owing to the
abundant oxidation states available for reversible redox reactions and
synergistic effects of multiple metal species compared with
single-component metal oxides. Among these electrode materials,
CuCo2O4 has attracted wide attentions as a considerate storage electrode
due to its greater electrochemical activity than single-component copper
oxides or cobalt oxides [9,10,14–20]. Particularly, Cu, as an eco-friendly
and cost-effective element, partial replacement of Co demonstrates to be
a better way of reduce the toxic characteristic and high-cost of cobalt
oxides. Nonetheless, CuCo2O4 still suffers from inferior conductivity and
insufficient concentrations of active sites, which adversely affects its
energy density and impedes its large-scale application.
To overcome these challenges, various strategies have been pro­
posed: (i) controlling the synthesis of CuCo2O4 electrodes to achieve
particular nanostructures (onion structures, nanosheets, double-shelled
hollow spheres, etc.) with enhanced surface area [9,10,14]; (ii)
enwrapping CuCo2O4 particles with highly conductive materials (carbon
nanotubes, carbon quantum dots, reduced graphenes, etc.) to improve
their conductivity and inhibit their volume expansion [15–17]; and (iii)
creating heteronanostructures by forming composites with other metal
electrode materials (MnCo2O4, CuCo2S4, MnO2, etc.) to enrich the
electrochemical performance through synergistic effects [18,20,21].
However, despite all these recent progresses, the complex fabrication
processes and poor conductivity of the aforementioned materials
severely restrict their practical application. Therefore, intrinsically
improving the conductivity of CuCo2O4 electrodes are vital for fully
utilising their pseudocapacitance.
Notably, introduction of oxygen vacancies has been demonstrated as
a convenient strategy to increase the electrical conductivity of metal
oxides and enlarge electroactive surface area exposed to the electrolyte.
This approach is expected to be a facile, effective and reliable strategy to
improve the capacitive properties of electrode materials [22–25].
Inhibiting crystallisation or using a reductant has recently been reported
to be an effective strategy to induce oxygen vacancies. For instance, Cao
and co-workers showed that introducing Pd2þ during a hydrothermal
process can lead to poorly crystalline and oxygen-vacancy-rich Co3O4,
resulting in enhanced conductivity and redox reaction [26]. Lu et al.
developed an oxygen-vacancy strategy involving a simple phosphating
process, which substantially improved the electrochemical performance
of NiCo2O4 [25]. Despite substantial achievements having been made, to
our knowledge, there is no report on the effects of oxygen vacancies on
the electrochemical performance of CuCo2O4. Furthermore, the devel­
opment of a low-cost and effective strategy to generate oxygen vacancies
remains a challenge.
Herein, we report the fabrication of a mesoporous, low-crystalline
CuCo2O4 (L-CCO) nanoflower electrode with enriched oxygen va­
cancies, which was synthesised by annealing precursor under a
controllable N2:O2 volume ratio. The L-CCO, which has a chaotic lattice
orientation and low crystallinity, functions as a shallow donor to
enhance the electrical conductivity as well as ensuring that sufficient
electroactive sites are exposed to the electrolyte that can greatly
improve the kinetics of the redox reaction, resulting in excellent pseu­
docapacitive performance [23,26–28]. Benefiting from the aforemen­
tioned advantages, the as-prepared L-CCO electrode exhibits a large
specific capacitance of 1006 F g 1 at 1 A g 1 (1.2 F cm 2 at 1.2 mA
2
Journal of Power Sources 458 (2020) 228005
cm 2), demonstrating high rate capability and cycling stability (greater
than 85% capacitance retention after 10,000 cycles even at 50 mV s 1).
Furthermore, an asymmetric supercapacitor device with L-CCO as the
positive electrode and active carbon (AC) as the negative electrode was
fabricated. The device provides a substantial energy density of 58.7 Wh
kg 1 (64.5 μWh cm 2) at a power density of 800 W kg 1 (880 μW cm 2)
and shows notable long-term stability (71.2% capacitance retention
after 10,000 cycles within a broad operating potential window of 1.6 V).
2. Experimental
2.1. Fabrication of L-CCO electrodes
All chemical reagents used in this work were analytical grade and not
subjected to further purification. Before a typical procedure, a piece of
Ni foam with dimensions of 1 � 4 cm2 was carefully cleaned in HCl
aqueous solution by sonication for 20 min and then sequentially rinsed
with acetone, ethanol and deionised (DI) water. Meanwhile, the growth
solution was prepared by dissolving 2 mmol Co(NO3)2⋅6H2O, 1 mmol Cu
(NO3)2⋅3H2O, 6 mmol NH4F and 20 mmol urea in 70 mL of DI water and
stirring for about 30 min at room temperature. Then, the resultant
reddish-brown solution was transferred to a 100 mL Teflon-lined
stainless steel autoclave, and the as-prepared cleaned Ni foam was
immersed in the solution against the autoclave wall. Afterward, the
autoclave was tightly sealed and maintained at 120 � C for 8 h. After
naturally cooling, the sample was removed, washed with DI water and
ethanol several times and then dried in a vacuum oven at 60 � C for 5 h.
Finally, three 1 � 1 cm2 Ni foam pieces cut from the same precursor were
annealed at 300 � C for 2 h under different mixed atmospheres of N2 and
O2, denoted as low-crystalline CuCo2O4 (L-CCO, VN2:VO2 ¼ 9.5:0.5),
general-crystalline CuCo2O4 (G-CCO, VN2:VO2 ¼ 8:2) and high-
crystalline CuCo2O4 (H–CCO, VN2:VO2 ¼ 0:10). Then, the fabricated
electrodes were pressed under a pressure of 10 MPa for 1 min (Fig. S1).
The mass loading of L-CCO, G-CCO and H–CCO was approximately 1.19,
1.27 and 1.48 mg cm 2, respectively.
2.2. Fabrication asymmetric supercapacitor of L-CCO//AC
The asymmetric supercapacitor was assembled using L-CCO and AC
as the positive and negative electrodes, respectively. The AC electrode
was prepared by scraping the homogeneous slurry of active carbon,
acetylene black and polyvinylidene fluoride (PVDF) in a weight ratio of
8:1:1 into a Ni foam current collector. In the approximated solid-state
supercapacitor system, PVA/KOH gel was used as the electrolyte. In a
typical gel electrolyte preparation, 6 g of PVA and 3.6 g of KOH were
dissolved in 30 mL of DI water with stirring at 90 � C for 2 h until the gel
became transparent. The as-obtained L-CCO and AC electrodes were
immersed in the PVA/KOH gel for approximately 3 min and then
assembled with a piece of cellulose paper between them in a sandwich
configuration; the resultant approximated solid-state asymmetric
supercapacitor was used in subsequent testing.
2.3. Materials characterisation
The morphologies and microstructures of samples were investigated
using a field-emission scanning electron microscopy (FE-SEM, JEOL,
JSM-6701F) and transmission electron microscopy (TEM, JEOL, JEM-
2100) equipped with an energy dispersive X-ray spectrometer (EDS).
The crystallinity and phase purity of the obtained materials were
examined by X-ray diffraction (XRD, M18XHF-SRA, Mac Science,
Yokohama, Japan). The oxidation states and surface chemical compo­
sition of the products were characterised by X-ray photoelectron spec­
troscopy (XPS, Thermo Electron, MultiLab2000). The specific surface
areas and pore structures of the electrode materials were calculated via
the Brunauer–Emmett–Teller (BET) method using measurement data
from an ASAP 2460 (Micromeritics Instrument Corp.). The wetting
Y. Feng et al. Journal of Power Sources 458 (2020) 228005

performances of the electrode materials were characterised using con­ electrochemical workstation (CHI 600E, Shanghai Chenhua) using a
tact angle measurements (Dataphysics OCT-20). three-electrode mode. Cyclic voltammetry (CV) and galvanostatic
charge–discharge (GCD) measurements as well as electrochemical
impedance spectroscopy (EIS) were carried out at ambient temperature
2.4. Electrochemical characterisation using a classical three-electrode configuration with 3 M KOH as the
electrolyte. The as-prepared electrodes were directly used as the
Electrochemical measurements were performed via an

Fig. 1. (a) Schematic illustration of the preparation of the L-CCO, G-CCO and H–CCO on Ni foam substrate. (b) XRD pattern of L-CCO, G-CCO and H–CCO. (c–e) SEM
images with different magnifications of the prepared L-CCO.

3
Y. Feng et al.
working electrode, a platinum plate acted as counter electrode and a
Hg/HgO electrode served as reference electrode in the three-electrode
system. EIS measurements were performed in a frequency range of
0.01 Hz–100 kHz at the open-circuit potential with 5 mV amplitude. The
formulas used to calculate the specific capacitance, energy density and
power density are given in the supporting information.
3. Results and discussion
A schematic of the synthesis process of L-CCO, G-CCO and H–CCO on
Ni foam is shown in Fig. 1(a). First, a thin layer of the precursors is
formed on the Ni foam surface via a hydrothermal method. Then, the as-
synthesised precursors are subsequent annealed in different calcination
conditions to form L-CCO, G-CCO or H–CCO, respectively (details in
Experimental Section). To elucidate the composition and crystalline
structure of the products, XRD patterns were collected; the results are
illustrated in Fig. 1(b). The patterns of all samples show diffraction
peaks at 2θ angles of 18.9� , 31.0� , 36.7� , 38.4� , 44.7� , 55.3� , 59.2� and
65.1� , which can be perfectly indexed to the (111), (220), (311), (222),
(400), (422), (511) and (440) facets of spinel-structured CuCo2O4
(JCPDS no. 76–1887). Notably, with increase in the volume ratio of N2
in the calcination condition, the intensity of the CuCo2O4 diffraction
peaks decreased, and simultaneously, the pattern showed wide diffrac­
tion peaks, suggesting L-CCO with weak crystallinity. Fig. 1(c–e) pre­
sents different magnification SEM images of the as-prepared L-CCO. As
Fig. 2. Low TEM images of (a, b) L-CCO, (c) G-CCO and (d) H–CCO.High-resolution TEM image of (e) L-CCO, (f) G-CCO and (g) H–CCO. (h) EDS images of L-CCO. (i)
Nitrogen adsorption-desorption isotherms and (j) pore-size distributions of L-CCO, G-CCO and H–CCO.
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Journal of Power Sources 458 (2020) 228005
shown in Fig. 1(c), L-CCO exhibits a flower-like structure uniformly
covering the Ni foam. High magnification SEM images (Fig. 1(d–e))
indicate that the sample consist of numerous 2D nanowires, and each
nanowire with a length of approximately 3 μm and an average diameter
of 25 nm. Furthermore, SEM images of as-prepared G-CCO and H–CCO
electrodes are displayed in Fig. S2, revealing no obvious morphological
changes for the samples during different atmosphere processing. The
structures and morphologies of L-CCO, G-CCO and H–CCO were further
investigated by TEM. Fig. 2(a) presents TEM images of L-CCO at low
magnification, showing slender bent nanowires gathered together into
nanoflowers, which is also consistent with the SEM results. Fig. 2(b–d)
show the corresponding TEM images of L-CCO, G-CCO and H–CCO,
respectively. It is found that the nanowires of L-CCO G-CCO and H–CCO
consist of a plentiful number of ultrasmall nanoparticles. Moreover,
there are numerous mesoporous structures in nanowires, which can be
ascribed to the gaseous species releases from the CuCo-precursors during
the thermal treatment process. Such the specific structure is favourable
for electrolyte penetration when the materials are used as super­
capacitor electrodes. High-resolution TEM (HRTEM) images of the three
samples (Fig. 2(e–g)) reveal that the H–CCO (Fig. 2(g)) is highly crys­
talline, with an interplanar spacing of 0.47 nm, which is consistent with
the CuCo2O4 (111) plane. Remarkably, the L-CCO sample with poor
polycrystallinity exhibits the smallest grain size, and no well-defined
lattice fringes are observed after the hypoxic atmosphere treatment
(Fig. 2(e)). The small grain sizes and abundant amorphous regions
Y. Feng et al.
enhance the immersion of the electrolyte ions and provide more sites for
the redox reaction, which is also consistent with the XRD analysis re­
sults. EDS was further used to verify the element composition, as shown
in Fig. 2(h), demonstrating that elements Cu, Co and O are present. In
addition, Ni is also observed, originating from the Ni foam substrate. The
specific surface area (Fig. 2(i)) and pore size distribution (Fig. 2(j)) of
the samples were investigated via the BET and Barrett–Joyner–Halenda
(BJH) methods, respectively. The corresponding surface area of L-CCO
(62.9 m2 g 1) is distinctly larger than those of G-CCO (52.8 m2 g 1) and
H–CCO (51.4 m2 g 1). Meanwhile, the average pore diameter distribu­
tion for L-CCO (7.9 nm) is smaller than those for G-CCO (9.3 nm) and
H–CCO (10.7 nm), which is consistent with the TEM results. The changes
in the surface areas and pore diameters can be attributed to the decrease
in crystallinity, which is unfavourable for grain growth, resulting in a
smaller grain size and larger specific surface area. This observation is
also consistent with those in previous works for low crystallinity mate­
rials. Obviously, the introduction of oxygen vacancies positively affects
the surface structure of the samples, providing many electrochemically
active sites for redox reaction and facilitating electrolyte-ion penetration
into the surface of the active materials.
XPS analysis was carried out to further investigate the chemical
composition and oxidation state of the as-prepared L-CCO, G-CCO and
H–CCO. All Co 2p emission spectra (Fig. 3(a)) show two spin–orbit
doublets located at approximately 796 and 780 eV. With decreasing
crystallinity, the intensities of the peaks at 780.8 and 796.3 eV, assigned
to Co2þ, increase substantially, indicating that more Co3þ ions were
transformed into Co2þ in the sample of L-CCO and that oxygen vacancies
were introduced [25,26,29]. Similar changes are observed in the Cu 2p
XPS spectra (Fig. 3(b)). Two shake-up satellite peaks are easily observed
at 941.6 and 961.8 eV, confirming the presence of Cu2þ. In the spectra of
samples annealed under a hypoxic atmosphere (L-CCO), the peaks of Cu
2p3/2 and Cu 2p1/2 shift towards lower binding energies, as expected,
indicating that more Cuþ is formed in the L-CCO sample to compensate
for the oxygen vacancies [16,30]. Fig. 3(c) shows the O 1s spectra of
L-CCO, G-CCO and H–CCO. The spectra of all samples show three
characteristic peaks centred at 529.4, 531.2 and 532.5 eV, which are
Fig. 3. High-resolution XPS spectra of (a) Co 2p, (b) Cu 2p, (c) O 1s for L-CCO. (d) The concentration of Co2þ and oxygen defect calculated from XPS data.
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Journal of Power Sources 458 (2020) 228005
associated with lattice oxygen species (M O), oxygen defect sites and
hydroxyl groups (O–H), respectively [24–26]. The density of vacancy
defect sites in L-CCO (Fig. 3(d)) is clearly higher than those in G-CCO
and H–CCO [26,31]. The richness-enabled oxygen defects in the L-CCO
electrode may result in enhanced energy-storage performance.
To investigate the influence of oxygen vacancies on the electronic
structure of CuCo2O4, we conducted first-principles simulations to study
the electronic structures of perfect CuCo2O4 and CuCo2O4 with O-atom
vacancies (V–CCO); the results are displayed in Fig. 4. Fig. 4(a and b)
shows the atomic structure models of pristine CuCo2O4 and V–CCO. The
band gaps of CuCo2O4 and V–CCO are shown in Fig. 4(c and d). Two
impurity bands appear at the Fermi energy of V–CCO; these bands can
possibly enhance the electron conduction from the valence band to the
conduction band, confirming that the introduction of oxygen vacancies
effectively enhances the electrical conductivity of CuCo2O4. Fig. 4(e and
f) shows the calculated density of states of CuCo2O4 and V–CCO. Obvi­
ously, the Fermi level shifts towards the conduction band after the
introduction of oxygen vacancies, further confirming that our strategy
can effectively enhance the conductivity of the V–CCO.
The electrochemical behavior of the three samples were charac­
terised using a three-electrode electrochemical system with aqueous
KOH solution (3 M) as the electrolyte. Fig. 5(a) shows a comparison of
the CV curves of L-CCO, G-CCO and H–CCO at a scan rate of 10 mV s 1 in
the potential range from 0 to 0.6 V (vs. Hg/HgO). Notably, the enclosed
area in the cyclic voltammogram of L-CCO is larger than those in the
voltammograms of G-CCO and H–CCO, indicating that the L-CCO ex­
hibits the highest specific capacitance among the three samples. In
addition, with the conversion between different cobalt and copper
oxidation states, the CV curves of these three electrodes exhibit a pair of
well-defined redox peaks, signifying typical battery-type electro­
chemical behavior and mainly based on the following redox reactions
[9,16]:
CuCo2 O4 þ H2 O þ e ↔ 2CoOOH þ CuOH (1)
CoOOH þ OH ↔ CoO2 þ H2 O þ e (2)
Y. Feng et al.
Fig. 4. The atomic structure of (a) CuCo2O4 and (b) V–CCO. Density functional theory (DFT) calculation total band structures of (c) CuCo2O4 and (d) V–CCO, the
density of states (DOS) of (e) CuCo2O4 and (f) V–CCO.
CuOH þ OH ↔ CuðOHÞ2 þ e (3)
GCD tests of the three samples were further conducted at a current
density of 1 A g 1, as shown in Fig. 5(b). As expected, the charge and
discharge times of the L-CCO electrode were relatively longer than those
of the G-CCO and H–CCO electrodes, which is consistent with the CV
results. Collectively, the results indicate that the L-CCO electrode ex­
hibits superior electrochemical performance compared with the G-CCO
and H–CCO electrodes, implying that the L-CCO electrode yields the
highest specific capacitance. This superior performance is attributed to
the presence of richness-enabled oxygen defects on the surface, which
can provide more active sites and lead to fast transmission of electrons
and ions. The poor crystallinity and oxygen vacancies are also beneficial
to the wetting ability, increasing the active substance contact with the
electrolyte. The static contact angle between the three samples and 3 M
KOH electrolyte was recorded; the results (Fig. S3) show that the static
contact angle increases from 48.6� for L-CCO to 55.2� for H–CCO.
To further evaluate the influence of the oxygen defects on the elec­
trochemical properties of the CuCo2O4 electrode, the capacitances of L-
CCO, G-CCO and H–CCO electrodes as a function of current density
(ranging from 1 to 20 A g 1 or 1.2–24 mA cm 2) are compared in Fig. 5
(c) and Fig. S4. The L-CCO electrodes exhibit the highest specific ca­
pacity of 1006 F g 1 (or areal capacitance of 1.2 F cm 2 and volumetric
capacitance of 141 F cm 3) than the G-CCO and H–CCO electrodes,
revealing that the oxygen-vacancy functionalization profoundly affects
the charge–discharge properties of the L–CCO–based electrodes. More­
over, the L-CCO electrode shows good reversible capability, with 69.4%
retention of its initial specific capacitance when the current density is
increased 20-fold.
In order to investigate the influence of introduced oxygen vacancies
on the electrode kinetics, EIS measurements were carried out at room
temperature; the results are shown in Fig. 5(d). Each Nyquist plot
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Journal of Power Sources 458 (2020) 228005
exhibits two distinct parts including a small semicircle in the high fre­
quency region and a straight line in the low frequency region, corre­
sponding to the charge-transfer reaction and ions diffusion, respectively
[32–34]. The Z-view software has been used to clarify the impedance
according to an equivalent circuit (see the inset in Fig. 5(d)). The EIS
data can be fitted by a pseudocapacitance (CPE2) from redox operation
of composites, bulk solution resistance (Rs), a charge transfer resistance
(Rct), and a constant phase element (CPE1) [35–37]. After fitting the EIS
spectra, both Rs (1.57 Ω) and Rct (0.40 Ω) of the L-CCO system are the
smallest values as compared to those of the G-CCO (Rs: 1.72 Ω; Rct: 0.75
Ω) and H–CCO (Rs: 1.76 Ω; Rct: 0.80 Ω) systems. This result reveals that
the introduction of oxygen vacancies can indeed effectively improve the
conductivity of the electrodes and boost their redox reaction kinetics.
The capacitive performances of the L-CCO electrodes were compre­
hensively measured and evaluated. The CV curves of the L-CCO elec­
trode (Fig. 5(e)) exhibit unchanging shapes as the scan rate increases
from 5 to 100 mV s 1, demonstrating its excellent pseudocapacitive
behavior with fast and reversible charge storage capability in the po­
tential window from 0 to 0.6 V. Furthermore, the GCD measurements at
various current densities are displayed in Fig. 5(f). All the curves at
various current densities are nonlinear and almost symmetric, indicating
an enhanced pseudocapacitive properties and a high coulombic effi­
ciency. The CV and GCD curves of G-CCO and H–CCO are also shown in
Fig. S5.
For supercapacitor practical application, its cycling performance is a
significant factor. Therefore, the cyclic stability of the as-prepared
electrodes was investigated using CV measurements at 50 mV s 1 as
shown in Fig. 5(g). After 10,000 cycles, the specific capacitance of the
electrodes maintains 85.5% of initial capacitance. Moreover, the CV and
EIS curves show unobvious variations even after prolonged 10,000 scans
(Fig. 5(h) and Fig. S6), suggesting that the fabricated L-CCO electrodes
with great redox reversibility can undergo long-term cycling tests. In
Y. Feng et al. Journal of Power Sources 458 (2020) 228005

Fig. 5. Electrochemical performance of the H–CCO, G-CCO and L-CCO electrode: (a) CV curves at a scan rate of 10 mV s 1, (b) GCD tests at a current densities of 1 A
g 1, (c) specific capacitance at different current densities, (d) EIS spectra. Electrochemical performance of L-CCO electrode: (e) CV curves at different scan rates, (f)
GCD tests at various current densities, (g) cycling stability at a current densities of 50 mV s 1, and (h) the first and last 10,000 cycle plot. (i) Typical SEM image of L-
CCO after 10,000 cycles. (j) Schematic illustration displaying the merits of the L-CCO electrode for energy storage.

addition, the SEM morphology of L-CCO electrode cycled after 10,000
times is also shown in Fig. 5 (i). Clearly, after the long-term cycling, the
overall L-CCO architecture is evidently preserved with little structural
deformation, suggesting its robust mechanical stability. Compared with
other reported CuCo2O4, copper or cobalt oxide/hydroxide based com­
posites and other bimetallic oxide, the as-synthesised L-CCO electrode
shows superior capacitance and outstanding cycling performance
(Table S1).
The superior electrochemical performance of L-CCO is attributable to
the introduction of oxygen vacancies and its unique nanostructure, as
shown in Fig. 5(j). Most importantly, oxygen vacancies substantially
boost the reactive active sites towards the electrolyte and improve
electrical conductivity, resulting in intensive reaction kinetics and
reversible redox reactions. Second, the abundant mesopores between
the grains in the nanowires of L-CCO facilitate electrolyte penetration
into the inner part of the nanowires, making full use of the active elec­
trode. Third, the direct growth of L-CCO on a highly conductive Ni foam,
without polymer binders and conductive agents, reduces the contact
resistance and shortens the charge transmission route. Finally, the
unique structure with countless nanowires is firmly anchored onto the
central nanospheres, making them completely accessible to the elec­
trolyte and providing a fast ion-transport channel. Additionally, the
open space of nanowires and central nanospheres can accommodate a
volume change, thereby suppressing expansion or contraction during
repeated charging and discharging processes.
To evaluate the practical applications of the L-CCO electrode, addi­
tional electrochemical tests were conducted. An approximated solid-
state asymmetric supercapacitor device with a sandwich-like structure

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Y. Feng et al. Journal of Power Sources 458 (2020) 228005

was fabricated, where AC was used as the anode (potential windows
from 1 to 0 V, Fig. 6(a) and Fig. S7). To achieve high charge storage
performance, the charge between the positive and negative electrodes
should be balanced; the calculated optimal mass ratio between the L-
CCO cathode and AC anode was 2.8 (details in Supporting Information).
After assembling the device, we evaluated the stable electrochemical
window of the L-CCO electrode to avoid damaging the device. According
to the CV tests, the operating cell voltage of the as-fabricated L-CCO
device can be extended to as high as 1.6 V without obvious polarisation,
as shown in Fig. 6(b). The CV curves of the as-fabricated L-CCO device
were recorded at different scan rates from 5 to 200 mV s 1, as illustrated
in Fig. 6(c). The shape of the CV curves of the device was well main­
tained even at higher scan rates, demonstrating good reversibility for
power devices. To further evaluate the electrochemical performance of
the device, GCD measurements were conducted at different current
densities (Fig. 6(d)). As shown in Fig. 6(e) and Fig. S8(a), the as-
fabricated L-CCO device delivers a specific capacitance ranging from
165 to 71.3 F g 1 (181.5–78.4 mF cm 2) with an increase in current
density from 1 to 20 A g 1 (1.5–31 mA cm 2). As revealed in Fig. 6(f)
and (g), the cycle performance of the device was further measured by
GCD measurements at a current density of 10 A g 1 for 10,000 cycles.
Notably, the total capacitance displayed good cycling stability, with a
capacitance retention of 71.2%, indicating excellent electrochemical
stability of the asymmetric supercapacitor device. Gravimetric power
density and energy density are two key parameters that should be
considered when assessing the practical applicability of electrochemical
supercapacitors (Fig. 6(h)). Remarkably, the device synthesised in our
work reaches a maximum energy density of 58.7 Wh kg 1 at a power
density of 800 W kg 1 (or 64.5 μWh cm 2 at 880 μW cm 2, Fig. S8(b)),
which is much higher than the energy densities of recently reported
supercapacitor devices such as NiCo2O4//AC (23.6 Wh kg 1 at 585.5 W
kg 1) [38], ZnCo2O4//AC (39.4 Wh kg 1 at 650 W kg 1) [39], NiC­
oMn–OH//RGO (42.8 Wh kg 1 at 749 W kg 1) [40],
Ni0⋅67Co0⋅33MoO4//RGO (25.7 Wh kg 1 at 775 W kg 1) [41],
FeCo2O4//FeCo2O4 (30.9 Wh kg 1 at 1551 W kg 1) [42],
CuCo2O4//rGO (45.2 Wh kg 1 at 1500 W kg 1) [43] and NiCo2S4@­
graphene//porous carbon (43.4 Wh kg 1 at 254.3 W kg 1) [44].
Notably, the energy density remained 25.3 Wh kg 1 as the power den­
sity increased to 16,000 W kg 1. To demonstrate the practical applica­
tion of the fabricated electrode in energy storage, a commercial
light-emitting diode is lighted by two L-CCO devices connected in se­
ries (Fig. 6(i)), demonstrating its potential suitability for energy-storage

Fig. 6. (a) CV curves of AC and L-CCO from 1.0 to 0 V and 0–0.6 V, respectively, in a three-electrode system. (b) CV curves of as-assembled L-CCO//AC device in
different operation voltages at a scan rate of 20 mV s 1. (c) CV curves, (d) GCD curves, (e) capacitance behaviors versus current density of L-CCO//AC device. (f)
Cycling stability of the L-CCO//AC device at a current density of 10 A g 1 during 10,000 cycles. (g) GCD curves of the 1st, 10000th cycle for the L-CCO//AC device.
(h) Ragone plot of the ASC device. (i) Image of the red LED powered by L-CCO//AC device. (For interpretation of the references to colour in this figure legend, the
reader is referred to the Web version of this article).

8
Y. Feng et al.
applications.
4. Conclusions
In summary, a mesoporous low-crystalline CuCo2O4 with enriched
oxygen vacancies was successfully synthesised via a facile in situ hy­
drothermal method followed by thermal treatment in a hypoxic atmo­
sphere. L-CCO shows a specific capacitance of 1006 F g 1 at 1 A g 1,
which is much higher than those of G-CCO and H–CCO. This superior
pseudocapacitive performance is attributed to the low crystallinity of
the L-CCO electrode with a mostly amorphous nanostructure and
abundant oxygen vacancies, which can provide more reaction sites and
fast ion intercalation, resulting in fast faradaic redox reactions and
outstanding rate capability. More importantly, an asymmetric super­
capacitor device assembled with L-CCO and AC as the positive and
negative electrodes delivered a maximum energy density of 58.7 Wh
kg 1 at a power density of 800 W kg 1. The device demonstrates
outstanding cycling stability in a wide potential window of 1.6 V with
71.2% capacitance retention even after 10,000 cycles. Our work reveals
that the oxygen vacancies can play an important role in enhancing
electrochemical performance, which is also expected to be effective
when applied to other transition metal oxides. Additionally, our prep­
aration of asymmetric supercapacitors with high power density and
energy density will enrich the next generation of energy-storage devices.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (11604395), the Key Technologies R&D Program of
Henan Province (192102210195), the Program for Science and Tech­
nology Innovation Talents in Universities of Henan Province (18HAS­
TIT032) and Chongqing Key Laboratory for Advanced Materials &
Technologies of Clean Energies (Grant No. JJNY201901).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jpowsour.2020.228005.
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