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In situ microwave-assisted solvothermal synthesis

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via morphological transformation of ZnCo2O4 3D

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Cite this: RSC Adv., 2021, 11, 5928

nanoflowers and nanopetals to 1D nanowires for
hybrid supercapacitors†
Ganesh Koyyada,a Nadavala Siva Kumar, ‡b Ibrahim H. Al. Ghurabi,b
Mourad Boumaza,b Jae Hong Kima and Koduru Mallikarjuna *cd

Over recent decades, the conversion of energy and its storage have been in the lime light due to the
depletion of fossil resources. The electrochemical energy storage devices like supercapacitors and
batteries, and their materials and fabrication methods have been extensively evaluated, which is the best
solution for the energy crisis. Herein, zinc cobaltite (ZnCo2O4; ZCO) nanostructures grown on nickel (Ni)
foam by microwave-assisted solvothermal fabrication for hybrid supercapacitors are reported. Two
different structures/samples, ZCO-15/Ni (nanoflowers) and ZCO-30/Ni (nanowires), were obtained by
simply adjusting the reaction time. The electrochemical and physicochemical properties of the as-
prepared samples were systematically determined. Particularly, ZCO-15/Ni exhibits excellent structural
stability due to its dual morphologies: nanoflowers and nanopetals, and exhibits a large electroactive
surface area (25.61 m2 g
1), pore diameter (48.38 nm), and robust adhesion to Ni foam, enabling ion and
Received 9th November 2020
Accepted 6th January 2021
electron transport. ZCO-15/Ni foam electrode delivers an excellent specific capacity of 650.27 C g
1 at
0.5 A g
1 and admirable cyclic performance of 91% capacitance retention after 5000 cycles compared
DOI: 10.1039/d0ra09507a
to ZCO-30/Ni electrode. The excellent electrochemical performance of ZCO makes them promising
rsc.li/rsc-advances electrode materials for batteries, hybrid supercapacitors, and other alternative energy storage applications.

of providing a higher power density with an improved long-life

1. Introduction than batteries and storing more than the conventional energy
Environmental change and consumption of petroleum prod- storage devices.7–9 Generally energy storage of the SCs depend
ucts have unequivocally impacted the normal biological system on ionic adsorption (for electrical double-layer capacitors,
and human economies (bio-economics). In order to overcome EDLCs) or fast surface redox reactions (for pseudocapaci-
these difficulties to create and design low-cost renewable tors).10–12 The combined electrode of EDLCs and pseudocapa-
sources and ecologically friendly storage and conservation of citors form asymmetric supercapacitors, and they can extend
energy-related devices to encounter the increasing market the cell voltage.13 Besides, the combination of supercapacitors
demand for the improvement of convenient electronic and (EDLCs) and battery-type electrodes led to one more hybrid
electric devices and vehicles.1–3 Supercapacitors (SCs) and li-ion called supercapattery (supercapacitor + battery) or hybrid
batteries (energy storage) and fuel cells (conversion) are the supercapacitor, which performs as the power source and energy
most promising alternative technologies for energy and envi- source.14 In general, transition metal oxides (TMOs) display
ronmental applications.4–6 Particularly, SCs are also called high electrochemical performance characteristics by a faradaic
electrochemical capacitors or ultracapacitors, and are capable redox reaction.15 The zinc-, nickel-, cobalt-, iron-based oxides of
energy storage-type materials that exhibiting Faradaic redox
reaction. Cobalt-based oxides, with their advantages of great
a
School of Chemical Engineering, Yeungnam University, 280 Daehak-ro, Gyeongsan-si, theoretical specic capacity and signicant redox response, are
Gyeongsangbuk-do, South Korea
b
an excellent battery-type cathode material for hybrid super-
Department of Chemical Engineering, King Saud University, P. O. Box 800, Riyadh,
11421, Saudi Arabia
capacitor applications.16,17 Also, spinel metal cobaltites such as
c
Department for Management of Science and Technology Development, Ton DucThang NiCo2O4,18 MnCo2O4,19 CuCo2O4,20 MgCo2O4,21 and ZnCo2O4 22
University, Ho Chi Minh City, Vietnam. E-mail: koduru.mallikarjuna@tdtu.edu.vn are favorable electrode materials for hybrid supercapacitors
d
Faculty of Applied Sciences, Ton DucThang University, Ho Chi Minh City, Vietnam because of their low electrical resistivity and excellent redox
† Electronic supplementary information (ESI) available. See DOI: performance than the pristine metal oxides. The zinc cobaltite
10.1039/d0ra09507a (ZnCo2O4; ZCO) has been viewed as a capable electrode material
‡ The authors are equally contributed.

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for supercapacitors,23 Li-ion batteries,24 and electrocatalysts25 of 180  C, which was monitored by an infrared temperature
because of cost-benet and scalable alternative; moreover, it sensor. Aer the reaction, it was cooled to room temperature
has several benets such as low price, abundant resources and and the Ni foam was taken out, washed several times with DI
environmental friendliness. The report says that spinel ZCO has water and ethanol, and then dried at 70  C for 12 h. Lastly, the
improved electrical properties and the electrochemical activity dried sample was annealed at 400  C for 4 h (@5  C min
1) to
is greater than that of ZnO or Co3O4.26 Therefore, it is antici- obtain ZnCo2O4 nanostructures on Ni foam (discussed in the
pated to furnish a better redox response, including more FE-SEM section) and labeled as ZCO-15/Ni. For comparison, the
contribution from Zn and Co ions, than those of single metal authors also prepared another sample with similar synthesis
zinc oxide and cobalt oxide.27 These striking characteristics are conditions except for the microwave reaction time of 30 min
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a big advantage for using supercapacitors with high efficiency. and labeled it as ZCO-30/Ni.
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In order to improve the electrochemical performance of hybrid

supercapacitors, one has to design electrodes with abundant
electroactive sites and high transfer rates and for ions of the 3. Results and discussion
electrolyte and electrons participating in the faradaic reactions 3.1 XRD
simultaneously.1,28 Recently, various morphologies of ZCO The XRD patterns of ZCO-15/Ni and ZCO-30/Ni nanostructures
nano/microstructures on the surface of various conductive (see the FE-SEM section) scratched from the Ni foam are
substrates like carbon cloth, FTO, ITO, and Ni foam were depicted in Fig. 1. For both the samples, the diffraction peaks
prepared29,30 and used directly as integrated electrodes for are centered at 2q values around 18.80, 31.19, 36.78, 38.80,
hybrid supercapacitors. The advantages of preparing electrodes 44.58, 55.58, 59.27, and 65.09 , which match with the planes of
through this novel method are as follows: the use of polymer (111), (220), (311), (222), (400), (422), (511), and (440) standard
binders and conductive additives can be avoided; the tedious ZCO crystal (JCPDS no: 23-1390),27,31 respectively. No impurities
procedure of ordinary electrode preparation can be simplied; were observed in both the samples, indicating that pure ZCO
and ordered nanoarrays on a conductive substrate can provide samples were produced. The crystallite size (D) of the samples
a more effective surface area for materials.28,31 were evaluated from the (311) plane diffraction peak with
In this work, we strategically prepared mesoporous ZCO Scherrer equation: D ¼ 0.9l/(b cos q), where l is the mono-
nanostructures on the surface of a conducting substrate (Ni chromatic wavelength of the X-ray (1.54056  A), q is the Bragg
foam) through the microwave-assisted solvothermal synthesis diffraction angle, and b is the half-peak width of the corre-
method. By altering the microwave reaction time, we obtained sponding diffracted peak. The average crystallite sizes of ZCO-
two different ZCO morphologies: nanoowers and nanowires. 15/Ni and ZCO-30/Ni were about 18.8 and 16.9 nm, respectively.
The two electrodes were subjected to CV, GCD, and EIS analyses
to assess the electrochemical performance. The ZCO nano-
owers on Ni foam exhibited a large integral area indicated by 3.2 FE-SEM
the CV curve, higher time response from the GCD curves, and The morphology, like the shape and size, of the prepared elec-
lower internal and charge-transfer resistance, which leads to trode material would signicantly affect the electrochemical
high electrochemical performance compared to others. The properties. In this case, the authors prepared two different
outcomes suggest that ZCO nanostructures grown directly on Ni morphologies by changing the microwave reaction time (see the
foam are promising electrode candidates for hybrid Experimental section) and are shown in Fig. 2. Remarkably,
supercapacitors.

2. Experimental procedure
2.1 Fabrication of ZCO nanoowers and nanowires on Ni
foam
The procured chemical reagents were of analytical grade and
used without further purication. Before deposition, the
surface oxide layer on the Ni foam (1.5  4 cm2) was cleaned
with 1 M HCl solution, absolute ethanol, and DI water by
ultrasonication. The synthesis of ZCO supported on Ni foam
was conducted using a microwave-assisted synthesis method
using a hydrothermal reactor. Calculated amount of Zn(NO3)2-
$4H2O (2 mM), Co(NO3)2$4H2O (4 mM), NH4F (10 mM), and
urea (20 mM) were dissolved in 20 mL of DI water and 20 mL of
absolute ethanol (1 : 1) and stirred for 30 min to get a pink
colored solution. Then, the treated Ni foam was submerged in
the pink-colored precursor solution, and the solution was Fig. 1 XRD patterns of ZCO-15/Ni (a) and ZCO-30/Ni (b) samples
placed in an autoclave, properly sealed, and placed in a micro- scratched out from the Ni foam and compared with standard JCPDS
wave synthesis chamber for 15 min at a maximum temperature data.

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Fig. 2 FE-SEM morphologies of (a and b) ZCO-15/Ni and (c and d) ZCO-30/Ni.

ZCO-15/Ni displays dual-morphology as shown in Fig. 2(a). Besides, ZCO nanoowers can be used as bridges to reinforce
Firstly, interconnected ZCO one-dimensional (1D) nanoplates the underlying ZCO nanoplates and reduce the effects of
were homogeneously grown on the surface of the Ni foam material volume expansion and fracture.33 Overall, this dual
(Fig. 2a and b). The obtained morphology will bear the cost of morphology of ZCO-15/Ni offers a higher BET surface area
a huge contact region for the redox response.32 Secondly, hier- (25.61 m2 g
1; discussed in the BET section) and also prevents
archical 3D ZCO nanoowers were randomly developed on the structural damage during the charging/discharging process.
nanoplates supported by Ni foam. These ZCO nanoowers Fig. 2(c and d) shows the FE-SEM images for ZCO-30/Ni sample
contain several petal-like nanoplates that are basic building and exhibits 1D nanowires with different diameters that are
blocks for the formation of nanoowers via the self-assembly uniformly distributed on the skeleton of Ni foam.
process shown at higher magnication FE-SEM (Fig. 2(b)).

Fig. 3 TEM (a and d), HR-TEM (b and e), and SAED patterns (c and f) for ZCO-15/Ni and ZCO-30/Ni, respectively.

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3.3 TEM From the structural and morphological studies, the possible
synthesis mechanism of ZCO-15/Ni and ZCO-30/Ni was
The morphology and structural parameters of ZCO-15/Ni and
proposed. Prior to the samples grown on Ni foam, the surface of
ZCO-30/Ni samples were analyzed using HRTEM and SAED
the Ni foam substrate was smooth, and aer the microwave-
patterns. Fig. 3(a and d) and (b and e) represent low- and high-
assisted solvothermal process for 15 min, numerous nano
magnication images of ZCO-15/Ni and ZCO-30/Ni aer ultra-
seeds were anchored on the surface of the substrate, which is
sonic treatment in ethanol. The prepared samples showing
derived from the combination of Zn2+, Co2+, and OH
ions. The
a number of nanoparticles are the basic building blocks that are
self-assembled to form aggregates.23 The SAED pattern (Fig. 3(c nucleation process and formation of nanoparticles, which acts
as anisotropic growth in the successive formation of petals on
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and f)) shows a clear lattice and its crystalline properties.

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Fig. 4 XPS spectra of ZCO-15/Ni and ZCO-30/Ni samples (a) survey scan, (b) O 1s, (c) Zn 2p, and (d) Co 2p.

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the Ni substrate. The ower-like structure is composed of

18.97
19.02
nanopetals, and these nanopetals comprise numerous nano-

Co
particles. Subsequently, these ower-like ZnCo-precursor

Elemental at%

19.06
nanosheets can be naturally turned into crystalline ower-like

Zn

20
ZnCo2O4 based on the Kirkendall effect.30 Aer 30 min of

61.03
61.92
microwave-assisted solvothermal reaction, nanowires were
grown on the surface of the Ni foam via the self-assembly

O
process.

795.90
796.10
Co4
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3.4 XPS
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780.60/(11.79)/[2.84]
780.70/(14.48)/[2.72]
The surface elemental composition and oxidation conditions of
ZCO-15/Ni and ZCO-30/Ni composites were investigated via XPS
(Fig. 4). The survey spectra for ZCO-15/Ni and ZCO-30/Ni were
recorded in the 1350–0 eV range and are depicted in Fig. 4(a). For

Co2+
both the samples, the survey scan spectra present comparable

Co2
XPS signals, indicating that they have similar composition (i.e.

794.50
794.75
Zn, Co, and O).34 Fig. 4(b) shows the O 1s core-level spectra of

Co3
ZCO-15/Ni and ZCO-30/Ni samples exhibiting three oxygen
components such as O1, O2, and O3. The binding energy posi-

779.90/(6.56)/[1.49]
779.80/(4.51)/[1.21]
tions for (ZCO-15/Ni)/(ZCO-30/Ni) were detected at 529.98/
529.22 eV (O1), 531.31/531.77 eV (O2), and 532.10/533.45 eV (O3).
For both the samples, the O1 peak represents metal–oxygen
bonds, the O2 component corresponds to the lattice oxygen, and

Co 2p

Co3+

Co1
the O3 peak can be attributed to the surface hydroxyl groups
(–OH) of the adsorbed water molecules on the surface of the

1044.78
1044.25
materials.35,36 The core-level spectra (Fig. 4(c)) of Zn 2p for ZCO-

Zn2
15/Ni and ZCO-30/Ni exhibit two major spin–orbit peaks attrib-
uted to Zn 2p3/2 and Zn 2p1/2. The peak binding energy values of

1021.36/(19.84)/[2.38]
(ZCO-15/Ni)/(ZCO-30/Ni) at 1021.25/1021.36 eV (Z1) and 1044.78/

1021.25/(20)/[2.42]
1044.25 eV (Z2) were observed, indicating that Zn mainly exhibits
Peak binding energy (eV  0.1)/(relative atomic concentration (%))/[[FWHM] (eV)]

the +2-oxidation state. Differences in the spin–orbit coupling and

binding energies between the two states were assessed to be
23 eV, consistent with previous reports.30,37 Similarly the Co 2p
Zn 2p

Zn1
core-level spectra for ZCO-15/Ni and ZCO-30/Ni are presented in
Fig. 4(d). The irregular spectra displayed three peaks, which 532.10/(7.84)/[1.21]
belonged to the +2 and +3 states of Co and a satellite peak. The 533.45/(8.56)/[1.11]
satellite peaks were overlooked and +2 and +3 states were indi-
vidually deconvoluted into two peaks for the comparison of the
samples. For the Co3+ state, the spectra were tted with two spin–
XPS results of prepared ZCO-15/Ni and ZCO-30/Ni

orbit doublets of Co 2p3/2 and Co 2p1/2 states situated at 799.80/

O3

799.90 eV (Co1) and 794.75/794.50 eV (Co3) and similarly the

531.31/(10.69)/[1.20]

peaks at 780.70/780.60 eV (Co2) and 795.90/769.10 eV (Co4) for

531.77/(9.58)/[1.11]

the +2 state of Co, respectively. The binding energy difference

between the two states of +2 and +3 transitions was 15 eV,
which is well-matched with the previous research ndings.38–40
Hence, Co had +2 and +3 states in ZCO-15/Ni and ZCO-30/Ni
(Table 1).
O2

529.22/(41.21)/[1.11]
529.98/(40.24)/[1.20]

3.5 BET
To investigate the surface parameters of ZCO-15/Ni and ZCO-30/
Ni samples, N2 adsorption–desorption was studied, which are
presented in Fig. 5. The two samples exhibit type-IV isotherm
O 1s

characteristics, which indicate the mesoporous nature of the

O1

prepared samples.41 ZCO-15/Ni has the largest surface area

ZCO-15
ZCO-30
Sample

(25.61 m2 g
1) compared to ZCO-30/Ni (16.11 m2 g
1). The

Table 1

larger surface area of ZCO-15/Ni provides an active

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advantage, the ZCO-15/Ni material may have better electro-

chemical performance. Furthermore, the isotherms also
provided the pore size and distribution of the respective
composite materials, which were also estimated by the BJH
method and the results are presented in the inset of Fig. 5. From
the BJH results, the prepared composites were mesoporous.
Finally, the average pore diameter was calculated to be 48.38
and 38.66 nm for ZCO-15/Ni and ZCO-30/Ni, respectively. Based
on the above results (both morphological and surface charac-
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teristics), the ZCO-15/Ni sample may exhibit excellent electro-

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chemical properties.

3.6 Electrochemical investigation

The electrochemical performances of the ZCO-15/Ni and ZCO-
Fig. 5 N2 adsorption/desorption isotherms for ZCO-15/Ni and ZCO- 30/Ni electrodes were determined by using 3 M KOH as the
30/Ni and the inset figure shows pore size distribution curves for both electrolyte. Fig. 6(a) illustrates the assessment of characteristic
the samples. CV curves of ZCO-15/Ni and ZCO-30/Ni electrodes within the
voltage range of
0.2 to 0.7 V at a scan rate of 5 mV s
1.
Particularly, the redox peak pair in the CV curves species that
electrochemical site with better electrochemical reaction, raises the electrochemical activity of the as-prepared electrodes orig-
the effective interaction area between the electrolyte and elec- inates from the pseudocapacitive behavior that can be attrib-
trode, and reduces the ion/electron diffusion pathway distance uted primarily to the reversible fast faradaic redox reaction. The
in the electrolyte.27 Due to the small resistance, the pore volume respective redox reactions can be described by the following
of ZCO-15/Ni (0.079 cm3 g
1) is greater than that of ZCO-30/Ni equation.21,42
(0.067 cm3 g
1), which effectively enhances the diffusion of
the electrolyte into the active material.27,36 Due to this ZnCo2O4 + OH
+ H2O 4 ZnOOH + 2CoOOH + e
(1)

Fig. 6 Comparison of electrochemical performance of ZCO-15/Ni and ZCO-30/Ni electrodes. (a) CV curves obtained at 5 mV s
1, (b) Anodic
peak current density vs. square root of scan rate, (c) CD curves obtained at 0.5 A g
1, and (d) current density vs. specific capacity.

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where ‘a’ and ‘b’ are variable parameters; when b ¼ 0.5, the
electrochemical process is diffusion controlled, and when b ¼ 1,
the electrochemical process is a non-diffusion-controlled
surface redox process.43 Fig. 6(b) shows that ZCO-15/Ni and
ZCO-30/Ni have anodic peaks with b estimated to be 0.61 and
0.53, respectively. These values are close to 0.5, conrming that
the redox process of the two electrodes is mainly diffusion-
controlled.44
Fig. 6(c) shows the evaluation of charge–discharge curves for
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ZC0-15/Ni and ZCO-30/Ni within a 0 to 0.5 V potential window at

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0.5 A g
1. The potential window of CV and GCD curves are

inconsistent; this is attributed to the less polarization that will
occur during charging. Thus, high voltage cannot be reached as
obtained in the CV curves. Practically, the potential–time curves
for a current density determines high charge/discharge
Fig. 7 Comparison of cyclic performance for ZCO-15/Ni and ZCO- coulombic productivity and low polarization remarkable elec-
30/Ni. trodes.28 ZCO-15/Ni exhibits a higher time response compared
to the ZCO-30/Ni electrode. The specic capacity of the ZCO-15/
Ni and ZCO-30/Ni electrodes can be calculated based on the
following formula:20,21
The impact of Ni foam on the electrochemical performance IDt
Cs ¼ (3)
is very limited to the whole electrode and hence was ignored. m
The integrated area from the CV curve of ZCO-15/Ni is signi-
where ‘Cs’ is the specic capacity in terms of C g
1, ‘I’ is the
cantly larger than that of ZCO-30/Ni, signifying a stronger
applied current, ‘Dt’ is the release time, and ‘m’ is the mass of
electrochemical reaction activity of the former. This is due to
the dynamic material. The specic capacity instead of the
the dual morphologies of the ZCO-15/Ni electrode material,
specic capacitance of the ZCO-15/Ni and ZCO-30/Ni battery-
higher surface area (25.61 m2 g
1), and larger pore size (48.38
type electrodes were calculated from the GCD curves to
nm). To additionally examine the electrochemical activity of
provide reasonable estimations of energy storage and
ZCO-15/Ni and ZCO-30/Ni, we investigated the relation between
discharge. The calculated specic capacity values at various
peak current density (i) and scan rate (v) and followed a power
current densities for both the electrodes are presented in
law.43,44
Fig. 6(d). Remarkably, the ZCO-15/Ni electrode showed a higher
i ¼ avb (2) specic capacity (650.27 C g
1 at 0.5 A g
1) compared to the
ZCO-30/Ni electrode (311.10 C g
1 at 0.5 A g
1), suggesting that

Fig. 8 Comparison of (a) Nyquist plots of ZCO-15/Ni and ZCO-30/Ni at high to low frequency regions, (b) Nyquist plots of ZCO-15/Ni and ZCO-
30/Ni at high to mid frequency regions. (c) Randles equivalent circuit model, and (d) corresponding table of EIS fitted values.

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the former electrode material exhibited good charge storage 0.5 A g
1. Aer 5000 cycles, both the grown structures showed
performance. As the current density is enhanced, the specic around 91% and 89% of the initial specic capacity. Low
capacity limit is reduced. The changes in the limit is likely internal and charge-transfer resistance was exhibited by ZCO
brought about by the expanding voltage drop and inadequate nanoowers and nanopetals on Ni form. This work provides
dynamic substances engaged with redox response at high- a new approach for the rational selection of the reaction time
temperature current density. The charge/discharge procedure for high-performance hybrid supercapacitors.
at high current density is the utilization rate of dynamic mate-
rials is low.1,23 Fig. 7 shows the cyclic performance of the ZCO-
15/Ni and ZCO-30/Ni electrodes at 1 A g
1 and shows only 9% Conflicts of interest
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and 11% loss of the initial capacity aer 5000 consecutive GCD
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The authors declare that there is no conict of interest.

cycles, respectively. The ZCO-15/Ni electrode has excellent cycle
performance compared to ZCO-30/Ni, and demonstrates
magnicent electrochemical stability and excellent application Acknowledgements
potential in battery-type supercapacitors.45
Low resistance is an important requirement for battery-type The King Saud University authors extend their appreciation to
supercapacitors in practical applications, which are used as the Deanship of Scientic Research at King Saud University for
power devices. Ionic diffusion and electron transfer details of funding this work through research group no (RG-1441-539).
the ZCO-15/Ni and ZCO-30/Ni electrodes were investigated
using EIS. Fig. 8(a) shows the Nyquist plots of ZCO-15/Ni and References
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