Received: 30 November 2022 | Revised: 6 February 2023 | Accepted: 12 April 2023

DOI: 10.1002/bte2.20220063

RESEARCH ARTICLE

NiCo alloy‐anchored self‐supporting carbon foam

as a bifunctional oxygen electrode for rechargeable
and flexible Zn–air batteries

Mengyang Dong1 | Huai Qin Fu1 | Yiming Xu1 | Yu Zou1 | Ziyao Chen1 |
Liang Wang1 | Mengqing Hu1 | Kaidi Zhang1 | Bo Fu1 | Huajie Yin2 |
Porun Liu1 | Huijun Zhao1

1
Centre for Catalysis and Clean Energy,
School of Environment and Science, Abstract
Griffith University, Gold Coast, The design and fabrication of flexible, porous, conductive electrodes with
Queensland, Australia
2
customizable functions become the prime challenge in the development of
Key Laboratory of Materials Physics,
Centre for Environmental and Energy new‐generation wearable electronics, especially for rechargeable batteries.
Nanomaterials, Anhui Key Laboratory of Here, the NiCo bialloy particulate catalyst‐loaded self‐supporting carbon foam
Nanomaterials and Nanotechnology, CAS
framework (NiCo@SCF) as a flexible electrode has been fabricated through
Center for Excellence in Nanoscience
Institute of Solid State Physics, Chinese one facile adsorption‐pyrolysis method using a commercial melamine foam.
Academy of Sciences, Beijing, China Compared with the electrode with Pt/C and Ir/C benchmark catalysts, the
NiCo@SCF electrode exhibited superior bifunctional electrocatalytic perform-
Correspondence
Huajie Yin, Key Laboratory of Materials ance in alkaline media with a half‐wave potential of 0.906 V for oxygen
Physics, Centre for Environmental and reduction reaction, an overpotential of 286 mV at j = 10 mA cm−2 for oxygen
Energy Nanomaterials, Anhui Key
Laboratory of Nanomaterials and
evolution reaction, and stable bifunctional performance with a small
Nanotechnology, CAS Center for degradation after 20,000 voltammetric cycles. The as‐assembled aqueous
Excellence in Nanoscience Institute of zinc–air battery (ZAB) with NiCo@SCF as a self‐supporting air cathode
Solid State Physics, HFIPS, Chinese
Academy of Sciences, Beijing, China. demonstrated a high peak power density of 178.6 mW cm−2 at a current
Email: yinhj@issp.ac.cn density of 10 mA cm−2 and a stable voltage gap of 0.94 V over a 540 h
Porun Liu and Huijun Zhao, Centre for charge−discharge operation. Remarkably, the as‐assembled flexible solid‐state
Catalysis and Clean Energy, School of
ZAB with self‐supporting NiCo@SCF as the air cathode presented an engaging
Environment and Science, Griffith
University, Gold Coast Campus QLD peak power density of 80.1 mW cm−2 and excellent durability of 95 h
4222, Australia. undisrupted operation, showing promise for the design of wearable ZAB.
Email: p.liu@griffith.edu.au and
The demonstrated electrode fabrication approach exemplifies a facile, large‐
h.zhao@griffith.edu.au
scale avenue toward functional electrodes, potentially extendable to other
Funding information wearable electronics for broader applications.
Australian Research Council,
Grant/Award Numbers: DP200100965, KEYWORDS
DP230102504
electrode, flexible, metal alloy, self‐supporting, zinc–air battery

This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided
the original work is properly cited.
© 2023 The Authors. Battery Energy published by Xijing University and John Wiley & Sons Australia, Ltd.

Battery Energy. 2023;2:20220063. onlinelibrary.wiley.com/r/batteryenergy | 1 of 13

https://doi.org/10.1002/bte2.20220063

2 of 13 | DONG
1 | INTRODUCTION
In recent years, the booming market of wearable devices
and portable electronic products has dramatically promoted
the demand and development of flexible energy storage
devices.1 Among them, flexible solid‐state rechargeable
transition metal−air batteries have received extensive
attention, mainly because of their ultrahigh theoretical
energy density, safety in use, and pollution‐free manufactur-
ing.2,3 However, the current energy conversion efficiency of
metal−air batteries is extremely low, mainly due to the
sluggish kinetics of oxygen reduction reaction (ORR) and
oxygen evolution reaction (OER) at the air electrode.
Although the use of noble metal catalysts (such as Pt, Ru,
Ir, etc.) can accelerate the electrochemical reaction kinetics
of ORR and OER, the scarcity and high price of these
noble metal catalysts will significantly increase the cost of
metal−air batteries, which is not conducive to the develop-
ment and large‐scale practical application of metal−air
batteries. Also, the current catalyst loading protocol relies on
post immobilization approach in which the inherently
strong attachment of the catalyst particles to the current
collector is challenging. Moreover, it is an arduous task to
formulate a three‐dimensional conductive flexible frame-
work that allows effective mass transport and reactant
diffusion during physical deformation without multi-
function. Therefore, the development of efficient and stable
low‐cost bifunctional oxygen electrodes is of great signifi-
cance for the development of flexible metal−air batteries
and has also become one of the core challenges.4
Transition‐metal alloy catalysts are featured with
alterable electronic transitions with different valence states,
excellent electrical conductivity, and versatile catalytic
activities. In particular, it provides surface redox centers
for O2 adsorption and activation, which can facilitate ORR/
OER electrocatalytic turnovers.5‐7 Alloy nanoparticles alone
tend to agglomerate, which leads to the reduction of
catalytically active sites. Moreover, when working for a long
time in strong acid or strong alkali environment, problems
such as chemical corrosion and surface state deterioration
result in degraded electrocatalytic activity. The dispersibility
and stability of alloy nanoparticles can be improved by
compounding with carbon supports with good chemical
stability, and the activity of alloy nanocatalysts for ORR/
OER electrocatalysis can be promoted.8,9 For example,
coating carbon layers on the surface of alloy nanoparticles
can be used as an efficient method for high‐performance
ORR/OER bifunctional electrocatalysts. The carbon layer
prevents the alloy nanoparticles from coming into direct
contact with the electrolyte and improves the structural
integrity of the alloy catalyst in extended operation.
Electrons can penetrate from the alloy core to the surface
of the carbon layer, increasing the charge density on the
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ET AL.
surface of the carbon layer and thereby stimulating its
catalytic activity.10 In addition, heteroatom doping of
carbon layers, especially nitrogen doping, can change the
surface charge distribution of carbon materials and provide
more catalytically active sites.11
Melamine foam (MF), an elastic material with a
three‐dimensional self‐supporting structure, provides a
wide range of opportunities after surface modification and
functionalizations. In particular, its conductivity and
porosity can be manipulated as promising catalyst support
by calcining at high temperatures.12–14 In this work, NiCo
alloy particles supported on elastic nitrogen‐doped carbon
foam were prepared by pyrolysis in an argon/hydrogen
atmosphere, where the pyrolyzed precursors were uni-
formly anchored by a simple thermochemical method:
nickel and cobalt ions were used as the metal source and
melamine foam as the nitrogen and carbon sources. The
resultant catalyst‐loaded NiCo@SCF electrode with high
surface area, catalyst loadings, and electrical conductivity
exhibits excellent ORR/OER bifunctional electrocatalytic
activity under alkaline conditions. More importantly,
this self‐supporting three‐dimensional elastic melamine
foam can be free‐clipping and mechanically machined on
demand. A rechargeable zinc–air battery (ZAB) and an
all‐solid‐state flexible ZAB were designed and assembled
using NiCo@SCF as the air cathode. The excellent electrical
conductivity, high surface area, well protected, highly
loaded catalyst nanostructure of the self‐supporting
electrode endow rechargeable ZAB with excellent energy
efficiency, charge−discharge performance, and cycle
stability. This work lays an avenue for the design and
construction of cost‐effective machinable cathodes for
flexible ZAB or other wearable electronic technologies.
2 | EXPERIMENTAL SECTION
2.1 | Chemicals
All chemical reagents, including MF purchased from
BASF, cobalt (II) nitrate hydrate (Co(NO3)2·6H2O, 99.9%),
nickel (II) nitrate hydrate (Ni(NO3)2·6H2O, 99.9%), and
Nafion 117 solution (5 wt.% in a mixture of lower aliphatic
alcohols and water), were purchased from Sigma‐Aldrich
and used without further purification. Ultrapure water
(Millipore Milli‐Q grade) with a resistivity of 18.2 MΩ was
used in all experiments.
2.2 | Electrode fabrication
Cobalt nitrate and nickel nitrate were formulated
into solutions with a concentration of 10 mg/mL.

DONG ET AL.
Twenty‐five milliliters of each of the above solutions
was taken, stirred, and mixed. The MF was put into the
beaker of the mixed solution and stirred at a tempera-
ture of 90°C for 12 h. After the reaction was completed,
the NiCo@MF was taken out, frozen, and dried. The
NiCo@MF was pyrolyzed at 400°C in a tube furnace
for 2 h under an Ar/H2 atmosphere with a heating
rate of 5°C per min and the content of H2 was
controlled at 10% of the total gas. After that, black‐
color NiCo@SCF was obtained. The SCF was obtained
by the same process that MF was pyrolyzed at 400°C in
a tube furnace for 2 h under an Ar/H2 atmosphere with
a heating rate of 5°C per min. The synthesis of single‐
metal@SCF electrodes was consistent with the above
process, except that only cobalt nitrate or nickel nitrate
was added as a metal ion solution in the preparation of
the precursor.
2.3 | Material characterization
A field emission scanning electron microscope (JSM‐
7100F) at a working voltage of 15 kV was used to
investigate the morphology of all as‐prepared samples.
Fourier transform infrared spectra (FTIR) were mea-
sured on a Bruker Vector‐22 FTIR spectrometer with a
scan range of 400–4000 cm−1. The X‐ray photoelectron
spectra (XPS) were recorded on a Kratos Axis ULTRA
system. Transmission electron microscopy (TEM) was
conducted on Philips F20 at 200 kV. High‐angle
annular dark‐field scanning transmission electron
microscope (HAADF‐STEM) imaging was taken
by a probe‐corrected JEOL JEM‐ARM200F with an
acceleration voltage under 200 kV. XRD patterns were
obtained by a Shimadzu XRD‐6000 diffractometer
scanning the angle range from 10° to 80° using CuKɑ
radiation (λ = 1.5418 Å). Brunauer−Emmett−Teller
(BET) surface areas were estimated from nitrogen
adsorption/desorption isotherms in powder forms
using a surface area analyzer Autosorb iQ Station 1.
2.4 | Electrochemical measurements
All electrochemical measurements were finished in a
traditional three‐electrode cell using an electrochemi-
cal workstation (CHI 760D). A glassy carbon (GC)
rotating disc electrode (RDE, AFE5T050GC, Pine
Research) with an area of 0.196 cm2 and graphite rod
were chosen as the working electrode and counter
electrode for ORR and OER measurements. To
evaluate the reaction selectivity, a rotating ring disc
electrode (RRDE, AFE7R9GCPT, Pine Research,
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| 3 of 13
ODdisc = 5.61 mm, ODring = 7.92 mm, IDring = 6.25 mm)
was used as the working electrode. Ag/AgCl and
Hg/HgO served as reference electrodes for evaluating
ORR and OER performances, respectively. The mea-
surements were carried out in an O 2‐saturated 0.1 M
KOH electrolyte for ORR and OER. Before recording
linear sweep voltammetry (LSV) for ORR and OER at
a rate of 2 mV s −1 , dozens of cyclic voltammetry (CV)
scans were employed to achieve stable curves. The
electrocatalyst ink was made via mixing catalyst
powder (4 mg), 950 μL of isopropanol, and 50 μL of
5 wt.% Nafion 117 suspension in one ultrasonic bath
for several hours. After that, 20 μL of the above ink
was pipetted on the GC surface, resulting in the
loading of 0.36 mg cm −2 . Commercial 20 wt.% Pt/C
and Ir/C were tested as benchmarks for ORR and
OER, respectively.
The ORR reaction kinetics was evaluated via the
Koutechy−Levich (K−L) equation:
1 1 1 1 1
= + = + ,
J Jd Jk Bω1/2 Jk
where J, Jd, and Jk represent the measured, diffusion‐
limiting, and kinetic current density, respectively. The ω is
the electrode's rotational rate. B can be determined from
the Levich equation as follows: B = 0.2 nFCoD2/3v−1/6,
where n represents the number of electrons, F is the
Faraday constant (F = 96485 C mol−1), Co is the saturated
O2 concentration (1.21 × 10−6 mol cm−3), D is the diffu-
sion coefficient of O2 in 0.1 M KOH (1.9 × 10−5 cm2 s−1),
and ν is the kinetic viscosity (0.01 cm2 s−1). The constant
0.2 is adopted when the rotation speed is expressed
in rpm.
RRDE measurements were tested by LSV at a scan
rate of 5 mV s−1 at 1600 rpm, and the ring electrode
voltage was kept at 1.5 V versus RHE. The H2O2
collection coefficient (N) at the ring in RRDE experi-
ments was 0.37. Below equations were used to calculate
the apparent number of electrons transferred during
ORR (n), and the percentage of peroxide released during
ORR (H2O2%), based on the disk current (ID) and ring
current (IR).
ID
n= ,
ID + (IR /N)
2(IR /N)
H2 O2 % = 100 .
ID + (IR /N)
The electrochemical surface area (ECSA) of catalysts
was obtained by the cyclic voltammetry curves in the
non‐faraday current region at the scan rates from 10 to

4 of 13 | DONG
60 mV s−1. The relation between current and scan rates is
shown in the following equation:
Ic
Cdl = ,
v polarized profiles using the following equation:
where Ic refers to the nonfaraday current; v is the scan rates.
2.5 | Assembly of Zn–air battery
The NiCo@SCF was machined to the appropriate thick-
ness and size, as the cathode. For the Pt/C‐Ir/C cathode,
the electrocatalyst inks were prepared by ultrasonically
dispersing 4 mg of Pt/C‐Ir/C (1:1, mass ratio) into 1 mL of
isopropanol/H2O (1/3 v/v) solution. The air electrode was
fabricated by dropping electrocatalyst ink onto carbon
paper and dried in the oven (an average catalyst loading of
1 mg cm−2). Then, this catalyst‐coated carbon paper was
further pressed with one commercial gas‐diffusion layer
(GDL) as the cathode. The Zn–air battery was assembled
with the above cathode, one Zn foil as the anode, and 6 M
KOH solution involving 0.2 M Zn(oAc)2 as the electrolyte.
The test of the assembled Zn–air battery was carried out in
a CT2001A battery assessment system (Wuhan LAND
Electronics Ltd.).
2.6 | Flexible solid‐state zinc metal–air
battery assembly
The air electrode is processed into a size of 6 × 2.5 × 0.2 cm.
The 0.1 mm thick zinc flakes were polished and cleaned as
metal anodes. The electrolyte is a hydrogel electrolyte. The
specific production process is as follows: One gram of
polyvinyl alcohol (PVA) with a molecular weight of 19,500
was dissolved in 10 mL of hot water (95°C), continued to
heat, and stirred for 2 h. Then, 1 mL was dissolved with
0.20 M Zn(CH3COOH)2, 18.0 M KOH solution was added
to the above PVA solution, and heating and stirring were
continued. After 40 min, the resulting solution was placed
in a −20°C freezer for gelation. After 12 h, it was taken out
and thawed. The gel–thaw process was repeated three
times to obtain the desired PVA gel electrolyte. Then, the
air electrode with Nafion 117 suspension and the
metal electrode were placed on both sides of the PVA gel
electrolyte to obtain a flexible solid‐state ZAB.
2.7 | Zn–air battery test
All Zn–air battery tests were performed under an
ambient atmosphere at room temperature. The polarized
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ET AL.
profiles were recorded on the CHI 760E electrochemistry
station using LSV with a scan rate of 5 mV s−1 calibrated
with 95% iR‐compensation. The discharge power density
was calculated using the data from the discharge
P = Ud × jd ,
where P is the discharge power density, Ud is the
discharge voltage, and jd is the discharge current density.
Galvanostatic discharge–charge cycling tests were carried
out on a Land CT2001 multichannel battery tester. In
each galvanostatic cycle, the Zn–air battery was dis-
charged for 60 min and charged for 60 min at a given
current density of 10.0 mA cm−2. The rate performance
of Zn–air batteries was evaluated by galvanostatic
discharge at a series of the current density of 5, 10, 20,
50, 100, and back to 5 mA cm−2. The Zn–air batteries
went for several cycles of galvanostatic discharge–charge
at 20.0 mA cm−2. Galvanostatic discharge–charge cycling
tests of FZAB were carried out on a Land CT2001
multichannel battery tester. In each galvanostatic cycle,
the FZAB was discharged for 30 min and charged for
30 min at a given current density of 2.0 mA cm−2.
3 | R ES ULT S AN D DI S C US S I ON
3.1 | Electrode characterizations
The fabrication procedures of the NiCo@SCF catalysts
are depicted in Figure 1A. The Ni2+ and Co2+ precursors
were evenly adsorbed on the melamine foam framework
by a facile immersion method at 90°C followed by
lyophilization drying. The NiCo@SCF was obtained by
pyrolysis of the foam under an Ar/H2 mix atmosphere at
400°C. Supporting Information: Figure S1 shows the
compressibility of the NiCo@SCF electrode, and the
compressed electrode can perfectly recover from defor-
mation. In Supporting Information: Figure S2, a 200 g
weight was placed on only 0.87 g of NiCo@SCF to further
testify the elasticity of the NiCo@SCF. These tests prove
that the NiCo@SCF has strong elasticity and could be
served as the electrode for flexible devices. The SEM
images of NiCo@SCF are shown in Figure 1B,C. Notably,
the three‐dimensional structure of NiCo@SCF can be
preserved after metal loading and pyrolysis. NiCo alloys
are uniformly and abundantly distributed on individual
polygonal fibers and the triangular junction of the
NiCo@SCF framework (Figure 1D). A similar foam
structure has been preserved when no metal is loaded
onto the foam before pyrolysis (which is noted as
SCF hereafter) (Supporting Information: Figure S3).
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DONG ET AL. | 5 of 13

F I G U R E 1 (A) Schematic illustration of the synthesis procedure for NiCo@SCF, (B, C) scanning electron microscope images of
NiCo@SCF at different magnifications. (D) Transmission electron microscopy (TEM) image, inset: dark‐field image. (E) HR‐TEM image,
(F) EDS mappings of as‐prepared NiCo@SCF.

The HR‐TEM image (Figure 1E) shows that the metal
alloy nanoparticles are coated in a small number of
carbon layers, where a large number of defect structures
and edge structures are present. The HR‐TEM image of
the particles witnesses the crystal planes with interplanar
spacings of 0.208 nm, which correspond to the (111)
plane of metallic NiCo,15 strongly suggesting a
nickel–cobalt alloy crystal structure. In addition, curved
fringes with a lattice parameter of 0.417 nm are measured
for the carbon layer, which can be attributed to the
presence of curved graphdiyne sheets.16,17 The element
distribution in the catalyst was characterized by the
corresponding HAADF‐STEM EDS spectrum, and the
results are shown in Figure 1F. Ni, Co, C, and N elements
in the catalyst are uniformly distributed throughout the
carbon foam, and the distribution of Ni/Co elements does
not overlap with the distribution of C and N elements,
indicating that the nickel–cobalt alloy exists in the form
of a structure embedded in the NiCo@SCF. From the
distribution of EDS in HAADF‐STEM in Figure 1F and
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6 of 13 | DONG ET AL.

Supporting Information: Figure S4, it can be concluded
that the atomic ratio of element content of cobalt and
nickel in the alloy is 53:47.
The characteristic peaks of the Raman spectrum
of NiCo@SCF are shown in Supporting Information:
Figure S5, in which the peak at 1388 cm−1 corresponds
to the breathing vibration (D band) of the sp2‐
hybridized carbon atoms of the benzene ring, and the
peak at 1576 cm−1 corresponds to the in‐plane stretch-
ing vibration of the sp2‐hybridized carbon atom of the
benzene ring (G band). The intensity ratio of D peak to
G peak is 0.72, indicating that the carbon has an
ordered structure. The peak at 1943 cm−1 is generally
believed to be related to the diyne bond and the peak at
2194 cm−1 corresponds to the stretching vibration of
the graphdiyne conjugated diyne, which is a charac-
teristic peak in the graphdiyne structure.17,18 However,
it is difficult to quantify its proportion over the carbon
structure due to its defective nature. As the XRD data
of NiCo@SCF shown in Figure 2A and Supporting
Information: Figure S6, the XRD patterns of prominent
diffraction peaks at 44.4°, 51.7°, and 76.1° correspond
to the (111), (200), and (220) planes of the face‐
centered cubic (fcc) nickel−cobalt alloy, respectively.19
The peak positions corresponding to the above three
diffraction peaks are slightly higher than those of pure
fcc phase element Co (PDF # 15‐0806) but slightly
lower than those of pure fcc phase element Ni (PDF #
04‐0850) (Supporting Information: Figure S6), which
strongly certifies the formation of Ni−Co solid solution
during the pyrolysis and also a certain degree of lattice
distortion.20 The broad peak at 21.3° corresponds to
the interlayer spacing of 4.17 Å, indicating a defective
carbon with the presence of graphdiyne structure.16,21
Although the existence of the NiCo@SCF framework is
confirmed, its crystallinity is poor due to the confor-
mational fluctuations of NiCo@SCF at the mesoscale.
In both FT‐IR spectra of Supporting Information:
Figure S7, the IR absorption peak at 3337 cm−1 is
attributed to stretching vibrations of secondary
amines (N−H) on the SCF surface. The absorbance at
1159 cm−1 corresponds to the C−O stretching vibration
in the melamine−formaldehyde resin. C═N stretching
mode was observed at 1548 cm−1. The peaks at 1472
and 1340 cm−1 correspond to methylene C−H bending
vibrations. The bending vibrations of the triazine ring
are shown at 810 cm−1.22
The surface chemical states of the prepared samples
were analyzed by XPS. The XPS survey scan of the
NiCo@SCF electrode has confirmed the presence of Ni,

F I G U R E 2 (A) XRD patterns of SCF and NiCo@SCF, (D) N2 adsorption−desorption isotherms of SCF and NiCo@SCF, high‐resolution
XPS spectra of (B) Ni 2p, (C) Co 2p, (E) C 1 s, and (F) N 1 s of NiCo@SCF.

DONG ET AL.
Co, N, C, and O on the surface (Supporting Information:
Figure S8). Detailed analysis of different elements as
shown in Figure 2B is the high‐resolution Ni 2p spectrum.
Among them, the peaks at 855.9 and 873.7 eV correspond
to metallic elemental Ni. Two satellite peaks centered
at 864.1 and 883.9 eV were observed in the Ni 2p
XPS spectrum of NiCo@SCF.23 Figure 2C shows a
high‐resolution Co 2p XPS spectrum, with peak splitting
results similar to Ni 2p. The peaks at 777.8, 779.5, 782.6,
and 786.2 eV correspond to metal elemental Co, Co3+,
high‐spin Co2+ ion vibration peaks, and satellite peaks,
respectively, in which the metallic Co species occupies
dominates the Co 2p spectrum.20,24 The above results echo
the crystal structure characterizations, further confirming
the formation of NiCo alloy structure. Figure 2E shows the
high‐resolution C ls XPS spectra of NiCo@SCF, which can
be fitted into five peaks. The peaks at 284.7, 285.6, 286.5,
287.6, and 289.3 eV correspond to sp2 C–C, sp C–C, C–O,
C═N, and C═O,21,25 confirming the existence of N‐doped
carbon material structures. The peaks at 398.8, 399.9,
400.9, and 404.5 eV of high‐resolution N 1 s XPS spectra in
Figure 2F correspond to pyridine nitrogen, pyrrolic
nitrogen, graphitic nitrogen, and N‐oxide, respectively.26,27
It can be seen that the nitrogen in NiCo@SCF samples is
mainly composed of pyridine nitrogen and graphitic
nitrogen. The pyridinic nitrogen dopants in graphdiyne‐
based carbon materials could contribute to the ORR/OER
electrocatalytic activity of the electrode.21,28–31
Generally, the specific surface area of the catalyst
determines the number of exposed catalytic active sites,
and a high specific surface area is an essential
factor affecting the catalytic performance. Therefore,
the specific surface area and pore size distribution of the
samples were analyzed. Figure 2D shows the N2
adsorption−desorption test curves of SCF and
NiCo@SCF. The N2 adsorption–desorption isotherms
of NiCo@SCF are of type II and type IV, and there is an
H4‐type hysteresis loop. The multipoint Brunauer−Em-
mett−Teller (BET) method was used to calculate the
specific surface area of SCF and NiCo@SCF, which are
104.5 and 271.2 m2 g−1, respectively. The higher specific
surface area of the NiCo@SCF electrode is beneficial to
expose more electrocatalytic active sites, which can improve
its catalytic activity. From the analysis of the pore size
distribution curve (Supporting Information: Figure S9), it
can be seen that compared with SCF, the NiCo@SCF
sample has sharp pore distribution peaks at 10–13 nm,
indicating that the NiCo@SCF has mesopore structure
besides macropores. Hierarchical pores promote mass
transportation, gas diffusion, and the contact of catalytic
active sites with the electrolyte, which facilitates the
transport of catalytically relevant protons and enhances
the electrocatalytic activity.32,33
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| 7 of 13
3.2 | Electrochemical performance
The electrocatalytic performance of as‐fabricated Ni-
Co@SCF for ORR was tested in alkaline media (0.1 M
KOH). As shown in the LSV curves under alkaline
conditions in Figure 3A, the initial onset potential (E0)
and half‐wave potential (E1/2) of NiCo@SCF are 1.01 and
0.906 V, respectively, much better than SCF (E0 = 0.861 V,
E1/2 = 0.61 V) and also exceed those of the electrode with
commercial Pt/C catalysts (E0 = 0.985 V, E1/2 = 0.878 V).
As shown in Figure 3B, the Tafel slopes of SCF,
NiCo@SCF, and electrodes with 20 wt.% Pt/C catalysts
were measured to be 375.6, 74.4, and 83.1 mVdec−1,
respectively. NiCo@SCF has the smallest Tafel slope,
which is due to the highest limiting current density of
NiCo@SCF, further demonstrating the fast oxygen diffu-
sion. The much more positive E0 and E1/2 as well as
the larger Tafel slopes of SCF in comparison to the
NiCo@SCF counterpart have strongly elucidated that
the NiCo alloy particles act as the dominant active sites
for the ORR on the NiCo@SCF sample. The rotating
ring disk electrode (RRDE) test technique was used to
further explore the H2O2 yield and electron transfer
number (n) of different samples during the ORR
process. As shown in Figure 3C, in the potential range
of 0.2–0.65 V versus RHE, the H2O2 yield of the sample
NiCo@SCF is lower than 3.3%, indicating a dominant
four‐electron transfer ORR process. The calculated n is
about 3.88, which is even higher than the electrode with
a commercial Pt/C catalyst (3.76). The electron transfer
number calculated by the K–L equation responding to
LSV curves of NiCo@SCF in an O2‐saturated solution of
0.1 M KOH at different rotation speeds is 3.87 (Support-
ing Information: Figures S10 and S11), which is similar
to the result obtained by the above calculation method,
indicating that the reaction is an efficient four‐electron
transfer process.
The OER catalytic performance of different samples
in alkaline media is also evaluated. As the LSV curves
shown in Figure 3D, at a current density of 10 mA cm−2
(Ej=10), the OER overpotential of NiCo@SCF is only
286 mV. Under the same test conditions, the over-
potential of NiCo@SCF is 44 mV lower than that of the
commercial Ir/C catalyst, indicating that the NiCo@SCF
sample has excellent OER electrocatalytic activity. The
OER reaction kinetics of different samples were evalu-
ated by the slope of the Tafel plots. It can be seen from
Figure 3E that the sample NiCo@SCF has the smallest
Tafel slope, indicating excellent OER catalytic kinetics,
which originated from the abundant catalytic active sites,
high specific surface area, and better electron transport
synergy of the NiCo@SCF samples. The poor OER
activity of the SCF electrode has been confirmed by the
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8 of 13 | DONG ET AL.

F I G U R E 3 (A) Linear sweep voltammetry (LSV) curves of SCF, NiCo@SCF, and Pt/C in an O2‐saturated 0.1 M KOH solution at a sweep
rate of 5 mV s−1 at 1600 rpm for the oxygen reduction reaction (ORR). (B) Corresponding Tafel plots for the LSV in (A). (C) Calculated
number of transfers and H2O2 yield. (D) LSV curves of SCF, NiCo@SCF, and Ir/C in O2‐saturated solution at a sweep rate of 5 mV s−1 at
1600 rpm for oxygen evolution reaction (OER). (E) Corresponding Tafel plots for the LSV in (D). (F) Overall LSV curves of NiCo@SCF
before and after 20,000 cycles.

high overpotential (765 mV) and high Tafel slope
(146 mV decade−1). The difference (ΔE) between the
half‐wave potential of ORR and the corresponding
potential of OER at a current density of 10 mA cm−2 is
usually used to evaluate whether a catalyst has excellent
ORR/OER bifunctional catalytic activity. The smaller ΔE
indicates that the catalyst has excellent ORR/OER
bifunctional electrocatalytic activity in the same electro-
lyte. Therefore, the ORR/OER bifunctional LSV curves of
NiCo@SCF in the O2‐saturated 0.1 M KOH electrolyte
were tested and the results are shown in Figure 3F. The
ΔE value of NiCo@SCF is 0.61 V versus RHE. After
20,000 cycles, ΔE still maintains a small value (0.631 V).
It can be seen from the LSV curves that the performance
attenuation of ORR and OER is very small, the half‐wave
potential of ORR is reduced by 9 mV, and the Ej=10 of
OER is attenuated by 12 mV. Chronoamperometric
responses for ORR of NiCo@SCF and Pt/C in O2‐
saturated 0.1 M KOH solution at 0.6 V, OER of
NiCo@SCF and Ir/C in 0.1 M KOH solution at 1.55 V
are shown in Supporting Information: Figure S14,
respectively. After 50,000 s, the relative current density
of NiCo@SCF remained at 91% and 89% of its initial
values for ORR and OER, respectively, while the Pt/C
counterpart maintained at 80% and Ir/C maintained at
76% of the initial values. This result can fully prove that
the bifunctional electrode has excellent stability, which
could probably be linked to the carbon shell on the NiCo
alloy catalyst surface.
The ECSA of the NiCo@SCF sample was assessed by
calculating the Cdl values (Supporting Information:
Figure S12). The NiCo@SCF sample exhibits a higher Cdl
(10.9 mF cm−2) than that of Pt/C‐Ir/C (9.7 mF cm−2),
indicating that the abundant heterostructures, oxygen
vacancies, and unique porous structure of nanoparticles
increase the ECSA and create more active sites. Since the
robustness of the NiCo@SCF electrode material gradually
deteriorated when the temperature was above 600°C, the
NiCo@SCF electrode materials were not suitable as an
electrode for zinc−air batteries (whether it was an aqueous

DONG ET AL.
system or a solid‐state system ZAB), so comparing the ORR
performance of samples pyrolyzed from 300°C to 600°C (as
shown in Supporting Information: Figure S13A), the half‐
wave potentials of NiCo@SCF‐300, NiCo@SCF‐400,
NiCo@SCF‐500, and NiCo@SCF‐600 were 0.71, 0.906,
0.86, and 0.898 V respectively. There was no obvious
difference in the ORR performance of the NiCo@SCF
pyrolyzed at 400°C–600°C compared with the half‐wave
potential; however, the NiCo@SCF electrode material
pyrolyzed at 400°C showed better kinetic properties.
Moreover, the mass activities of four samples are shown
in Supporting Information: Figure S13B; the NiCo@SCF‐
400 has the highest mass activity among them, which
shows that a certain degree of carbonization is beneficial to
improve electrical conductivity, thereby promoting catalytic
performance.
The roles of elemental and compositional information
of metals in the composite catalysts were investigated. As
the XRD data of Co@SCF, Ni@SCF, and NiCo@SCF
shown in Supporting Information: Figure S15, compared
to the three main peaks of NiCo@SCF, the peak positions
of Co@SCF are slightly lower, indicating that those peaks
correspond to pure fcc phase element Co (PDF # 15‐
0806). On the contrary, peaks of Ni@SCF are slightly
higher than those of NiCo@SCF, corresponding to pure
fcc phase element Ni (PDF # 04‐0850), certifying the
formation of Ni–Co solid solution during the pyrolysis
and also a certain degree of lattice distortion of
NiCo@SCF. The SEM images of Co@SCF are shown in
Supporting Information: Figure S16. Notably, there are
no obvious alloy particles like the sample NiCo@SCF on
the carbon skeleton, and insufficient loadings may lead
to poor bifunctional electrocatalytic performance. This
can be seen in Figure S17 that the particle distribution of
cobalt elements is extremely rare. At the same time, it
can be seen from Supporting Information: Figures S18
and S19 that in the synthesized Ni@SCF, there are a
large number of aggregated metal particles on the carbon
skeleton. This aggregation phenomenon is not conducive
to the exposure of catalytic sites and also leads to
deficient catalytic performance. In Supporting Informa-
tion: Figure S20, the high‐resolution Co 2p spectrum of
Co@SCF is shown. The peaks at 777.8, 780.9, 784.8,
and 788.6 eV correspond to metal elemental Co, Co3+,
high‐spin Co2+ ion vibration peaks, and satellite peaks,
respectively, in which the metallic Co species dominates
the Co 2p spectrum. Among the peaks of Ni 2p of
Ni@SCF in Supporting Information: Figure S21, the
peaks at 855.6 and 874.0 eV correspond to metallic
elemental Ni. The contents of different metal valence
states corresponding to different XPS subpeaks of three
samples are shown in Supporting Information: Table S1.
Compared with the sample Co@SCF, the Co2+ of the
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| 9 of 13
sample NiCo@SCF was much higher, and Co2+ was
revealed to be beneficial to enhance ORR/OER activity.34
Compared to sample Ni@SCF, the content of Ni2+ was
also significantly increased, indicating that Ni2+ occupies
a large part of the sample surface, which is conducive to
OER activity.35 And the metallic states of Co and Ni were
found in the XPS spectra; the occurrence of electron
redistribution after NiCo@SCF vacancy configuration,
which may actively tune the energy band and
electronic structure of nanomaterials, and the electron
redistribution may lead to charge transfer from NiCo to
N‐doped carbon to form electron‐rich N‐doped carbon
and electron‐deficient NiCo species. The electrocatalytic
performance of as‐fabricated Co@SCF, Ni@SCF, and
NiCo@SCF for ORR was tested in alkaline media (0.1 M
KOH). As shown in the LSV curves under alkaline
conditions in Supporting Information: Figure S22A, the
half‐wave potential (E1/2) of Co@SCF and Ni@SCF is
0.822 and 0.84 V, respectively, much worse than
NiCo@SCF (E1/2 = 0.906 V). The OER catalytic perform-
ance of different samples in alkaline media is also
evaluated. As the LSV curves shown in Supporting
Information: Figure S22B, at a current density of
10 mA cm−2 (Ej=10), the OER overpotentials of Co@SCF
and Ni@SCF are 455 and 461 mV, much higher than that
of the overpotential of NiCo@SCF (286 mV), indicating
that the NiCo@SCF sample has the most excellent OER
electrocatalytic activity.
The excellent ORR/OER bifunctional electrocatalytic
activity of NiCo@SCF samples in the same electrolyte is
attributed to the following points: (1) Ni and Co elements in
the alloy undergo electronic transitions between different
valence states, providing redox centers for the adsorption
and activation of O2, and enhance the electrocatalytic
activity of ORR;36‐38 (2) NiCo@SCF has a large specific
surface area, which is beneficial to reduce agglomeration of
nanoparticles, expose more active sites, and facilitate the
electrocatalysis‐related proton transport; (3) The well‐
preserved conductive network of carbon promotes the
rapid transport of electrons, and a large amount of nitrogen
doping can increase the surface charge density, thereby
enhancing the electrocatalytic activity of NiCo@SCF.39‐42
The catalytic reaction kinetics are improved, resulting in
higher ORR/OER electrocatalytic activity.
3.3 | Battery performance
The above electrocatalytic performance tests certified
that the NiCo@SCF material exhibited excellent
bifunctional ORR/OER electrocatalytic activity. To fur-
ther evaluate the performance of electrocatalysts in
practical energy device tests, in this work, the
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10 of 13 | DONG ET AL.

NiCo@SCF was machined into a rectangular shape
suitable as a self‐supporting cathode for an aqueous
rechargeable ZAB (Supporting Information: Figure S23).
As shown in Figure 4A, the LSV curves and correspond-
ing power density curves of aqueous ZAB cells are
prepared with NiCo@SCF and Pt/C‐Ir/C@carbon paper,
respectively. It can be observed that the peak power
density (178.6 mW cm−2) of NiCo@SCF‐assembled ZAB
is more than double of the Pt‐Ir/C‐assembled ZAB
(87.3 mW cm−2). The NiCo@SCF‐assembled ZAB was
subjected to discharge tests at different current densities,
and the results are shown in Figure 4B. After two 10 h
cycles, the discharge process with the maximum current
density reaching 100 mA cm−2, when the current density

F I G U R E 4 (A) Polarization and power density of aqueous ZAB with the NiCo@SCF electrode and Pt/C–Ir/C as electrocatalysts. (B)
Discharge profiles of the aqueous zinc–air battery (ZAB) with the NiCo@SCF catalyst at various current densities. (C) Discharge curves of
aqueous ZAB with NiCo@SCF and Pt/C–Ir/C catalysts at a current density of 20 mA cm−2. (D, E) Cycle performances of aqueous ZAB with
the NiCo@SCF catalyst at a current density of 10 mA cm−2. (F) Schematic depicts the structure of assembled FSZAB. (G) Constant current
charge–discharge curves of FSZAB with the NiCo@SCF catalyst with different bending degrees. (H) Polarization and power density of
FSZAB with NiCo@SCF. (I) Cycle performances of FSZAB with the NiCo@SCF catalyst at a current density of 2 mA cm−2.

DONG ET AL.
returns to 5 mA cm−2 of the third cycle, compared with
the first cycle, the discharge platform remains at 1.227 V,
which is 98.8% of the initial value. Even when comparing
the first cycle with the third cycle when the current
density is under 50 mA cm−2, the discharge platform can
be maintained at 1.065 V, which is 95.7% of the initial
value. The specific capacity calculated by normalizing the
mass of consumed Zn by performing constant voltage
discharge tests at potential platforms corresponding to
current densities of 20 mA cm−2 for a long time until the
zinc flakes are exhausted (Figure 4C), which was
755 mAh gZn−1, indicating that the ZAB assembled with
NiCo@SCF has excellent discharge stability and dis-
charge efficiency, which originated from the efficient and
stable ORR electrocatalytic performance of NiCo@SCF.
The structural stability of the NiCo@SCF as an air
electrode was further assessed in a long‐term charge and
discharge test, as shown in Figure 4D,E. After 540 h of
charge–discharge (current density of 10 mA cm−2), the
charge and discharge voltage gap of the NiCo@SCF
assembled ZAB finally reached 0.94 V, and the
charge–discharge plateau hardly changed. This stability
exceeds that of most aqueous ZAB assembled from NiCo
alloy‐based catalysts (Supporting Information: Tables S2
and S3). Considering the excellent performance and
flexibility feature of the NiCo@SCF, it was further
assembled into flexible solid‐state ZAB (FSZAB) as an
emerging technology for flexible energy storage applica-
tions (Figure 4F). As shown in Figure 4G, the resultant
FSZAB with a self‐supporting NiCo@SCF cathode is
capable of recharge under a stable charge and discharge
voltage gap of 0.805 V, which can be bent to different
angles after prolonged cycling. Compared with some
recently published alloy‐based bifunctional electrocata-
lysts (Supporting Information: Tables S4 and S5), the
NiCo@SCF‐assembled FSZAB exhibited a relatively high
power density value of 80.1 mW cm−2 and displayed a
stable charge/discharge voltage gap of 0.8 V, which was
95 h more than that at the current density of 2 mA cm−2
(Figure 4H,I). These results have verified that NiCo@SCF
catalysts are promising self‐supporting electrodes in re-
chargeable FSZAB and wearable devices, which will pave
the way to more economically viable, cost‐effective, and
durable smart energy systems.
To further investigate the structural robustness, the
spent NiCo@SCF was retrieved from the FSZAB after a
95 h charge/discharge stability test and subjected to
structural characterization. The XRD data in Supporting
Information: Figure S24 shows that the three main peaks
that indicate the crystal face of the NiCo alloy still maintain
the original spectrum, indicating that the overall structure
has been effectively preserved. The flexible framework of
NiCo@SCF remained intact as confirmed in the SEM
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| 11 of 13
image (Supporting Information: Figure S25), and the NiCo
alloy particles on its framework were also observed in TEM
(Supporting Information: Figure S26A,B). In particular, the
grain size of NiCo alloy particles after the charge/discharge
stability test was reduced probably due to the electro-
chemical reconstruction, as shown in the HRTEM image
(Supporting Information: Figure S26C,D). In addition, the
uniform distribution of NiCo‐alloy particles on the SCF
framework is evident in the EDS mapping results
(Supporting Information: Figure S27). Supporting Informa-
tion: Figure S28 shows the XPS high‐resolution spectrum of
the sample after the cycle test. Supporting Information:
Figure S28A,B correspond to the Ni 2p and Co 2p XPS
spectra, respectively, and it is evident that there are
amounts of Ni and Co elements representing the
valence state of the alloy in the subpeaks. As the C ls
XPS spectrum shown in Supporting Information:
Figure S28C, the subpeaks from 284 to 290 eV are
consistent with the five subpeaks as aforementioned
and shown in Figure 2E. Compared with the peak in
Figure 2F, the relative content of pyrrolic‐N and
graphitic‐N decreases, while the content of pyridinic‐N
increases relatively in Supporting Information: Figure S28D,
which is also consistent with the literature mentioned above
that the performance of ORR/OER is determined by
pyridinic‐N in nitrogen doping electrocatalysts, which is
one of the main factors. The above results strongly indicate
that NiCo@SCF is endowed with outstanding structural
robustness and high cycling stability that is essential to the
delivery of efficient and steady ORR/OER electrocatalytic
performance. The robust, efficient NiCo@SCF herein
exemplifies a useful electrode in rechargeable FSZAB and
next‐generation wearable electronic devices.
4 | CONCLUSION
In conclusion, NiCo bialloy particles have been successfully
anchored onto the carbonized MF framework (NiCo@SCF)
via a facile thermal conversion approach using commercially
available low‐cost melamine foam. The resultant self‐
supporting, machinable, porous NiCo@SCF electrode
showed excellent ORR/OER bifunctional activity, providing
a new idea for designing other non‐precious‐metal‐based
electrodes. More importantly, the rechargeable Zn–air
battery assembled with the NiCo@SCF electrode manifested
an appreciable charge–discharge performance with a steady
voltage gap. The unique self‐supporting NiCo@SCF elec-
trode will have many potential applications, providing more
possibilities for the design and manufacturing of mass‐
producible, cost‐effective, and wearable‐type Zn–air batteries.
The demonstrated strategy can be readily extended to other
wearable devices for wider applications.

12 of 13 | DONG
ACKNOWLEDGMENTS
This work was financially supported by the Australian
Research Council Discovery Projects (DP200100965,
DP230102504) and Griffith University Postdoctoral
Fellowship.
CONFLI CT OF I NTER EST STATEMENT
The authors declare no conflict of interest.
DATA A VAILABILITY S TATEMENT
The data that support the findings of this study are
available in the Supporting Information Material of this
article.
ORCID
Mengyang Dong https://orcid.org/0000-0002-
2224-1943
Huajie Yin https://orcid.org/0000-0002-9036-9084
Porun Liu http://orcid.org/0000-0002-0046-701X
Huijun Zhao https://orcid.org/0000-0002-3028-0459
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SU PPOR T ING INF OR MATI ON
Additional supporting information can be found online
in the Supporting Information section at the end of this
article.
How to cite this article: Dong M, Fu HQ, Xu Y,
et al. NiCo alloy‐anchored self‐supporting carbon
foam as a bifunctional oxygen electrode for
rechargeable and flexible Zn–air batteries. Battery
Energy. 2023;2:20220063. doi:10.1002/bte2.20220063