Battery Energy - 2023 - Dong - NiCo Alloy Anchored Self Supporting Carbon Foam As A Bifunctional Oxygen Electrode For

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: [email protected] 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: [email protected] and
The demonstrated electrode fabrication approach exemplifies a facile, large‐
[email protected]
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.
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2 of 13 | DONG ET AL.
1 | INTRODUCTION surface of the carbon layer and thereby stimulating its

catalytic activity.10 In addition, heteroatom doping of
In recent years, the booming market of wearable devices carbon layers, especially nitrogen doping, can change the
and portable electronic products has dramatically promoted surface charge distribution of carbon materials and provide
the demand and development of flexible energy storage more catalytically active sites.11
devices.1 Among them, flexible solid‐state rechargeable Melamine foam (MF), an elastic material with a
transition metal−air batteries have received extensive three‐dimensional self‐supporting structure, provides a
attention, mainly because of their ultrahigh theoretical wide range of opportunities after surface modification and
energy density, safety in use, and pollution‐free manufactur- functionalizations. In particular, its conductivity and
ing.2,3 However, the current energy conversion efficiency of porosity can be manipulated as promising catalyst support
metal−air batteries is extremely low, mainly due to the by calcining at high temperatures.12–14 In this work, NiCo
sluggish kinetics of oxygen reduction reaction (ORR) and alloy particles supported on elastic nitrogen‐doped carbon
oxygen evolution reaction (OER) at the air electrode. foam were prepared by pyrolysis in an argon/hydrogen
Although the use of noble metal catalysts (such as Pt, Ru, atmosphere, where the pyrolyzed precursors were uni-
Ir, etc.) can accelerate the electrochemical reaction kinetics formly anchored by a simple thermochemical method:
of ORR and OER, the scarcity and high price of these nickel and cobalt ions were used as the metal source and
noble metal catalysts will significantly increase the cost of melamine foam as the nitrogen and carbon sources. The
metal−air batteries, which is not conducive to the develop- resultant catalyst‐loaded NiCo@SCF electrode with high
ment and large‐scale practical application of metal−air surface area, catalyst loadings, and electrical conductivity
batteries. Also, the current catalyst loading protocol relies on exhibits excellent ORR/OER bifunctional electrocatalytic
post immobilization approach in which the inherently activity under alkaline conditions. More importantly,
strong attachment of the catalyst particles to the current this self‐supporting three‐dimensional elastic melamine
collector is challenging. Moreover, it is an arduous task to foam can be free‐clipping and mechanically machined on
formulate a three‐dimensional conductive flexible frame- demand. A rechargeable zinc–air battery (ZAB) and an
work that allows effective mass transport and reactant all‐solid‐state flexible ZAB were designed and assembled
diffusion during physical deformation without multi- using NiCo@SCF as the air cathode. The excellent electrical
function. Therefore, the development of efficient and stable conductivity, high surface area, well protected, highly
low‐cost bifunctional oxygen electrodes is of great signifi- loaded catalyst nanostructure of the self‐supporting
cance for the development of flexible metal−air batteries electrode endow rechargeable ZAB with excellent energy
and has also become one of the core challenges.4 efficiency, charge−discharge performance, and cycle
Transition‐metal alloy catalysts are featured with stability. This work lays an avenue for the design and
alterable electronic transitions with different valence states, construction of cost‐effective machinable cathodes for
excellent electrical conductivity, and versatile catalytic flexible ZAB or other wearable electronic technologies.
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 2 | EXPERIMENTAL SECTION
tend to agglomerate, which leads to the reduction of
catalytically active sites. Moreover, when working for a long 2.1 | Chemicals
time in strong acid or strong alkali environment, problems
such as chemical corrosion and surface state deterioration All chemical reagents, including MF purchased from
result in degraded electrocatalytic activity. The dispersibility BASF, cobalt (II) nitrate hydrate (Co(NO3)2·6H2O, 99.9%),
and stability of alloy nanoparticles can be improved by nickel (II) nitrate hydrate (Ni(NO3)2·6H2O, 99.9%), and
compounding with carbon supports with good chemical Nafion 117 solution (5 wt.% in a mixture of lower aliphatic
stability, and the activity of alloy nanocatalysts for ORR/ alcohols and water), were purchased from Sigma‐Aldrich
OER electrocatalysis can be promoted.8,9 For example, and used without further purification. Ultrapure water
coating carbon layers on the surface of alloy nanoparticles (Millipore Milli‐Q grade) with a resistivity of 18.2 MΩ was
can be used as an efficient method for high‐performance used in all experiments.
ORR/OER bifunctional electrocatalysts. The carbon layer
prevents the alloy nanoparticles from coming into direct
contact with the electrolyte and improves the structural 2.2 | Electrode fabrication
integrity of the alloy catalyst in extended operation.
Electrons can penetrate from the alloy core to the surface Cobalt nitrate and nickel nitrate were formulated
of the carbon layer, increasing the charge density on the into solutions with a concentration of 10 mg/mL.
DONG ET AL. | 3 of 13
Twenty‐five milliliters of each of the above solutions ODdisc = 5.61 mm, ODring = 7.92 mm, IDring = 6.25 mm)
was taken, stirred, and mixed. The MF was put into the was used as the working electrode. Ag/AgCl and
beaker of the mixed solution and stirred at a tempera- Hg/HgO served as reference electrodes for evaluating
ture of 90°C for 12 h. After the reaction was completed, ORR and OER performances, respectively. The mea-
the NiCo@MF was taken out, frozen, and dried. The surements were carried out in an O 2‐saturated 0.1 M
NiCo@MF was pyrolyzed at 400°C in a tube furnace KOH electrolyte for ORR and OER. Before recording
for 2 h under an Ar/H2 atmosphere with a heating linear sweep voltammetry (LSV) for ORR and OER at
rate of 5°C per min and the content of H2 was a rate of 2 mV s −1 , dozens of cyclic voltammetry (CV)
controlled at 10% of the total gas. After that, black‐ scans were employed to achieve stable curves. The
color NiCo@SCF was obtained. The SCF was obtained electrocatalyst ink was made via mixing catalyst
by the same process that MF was pyrolyzed at 400°C in powder (4 mg), 950 μL of isopropanol, and 50 μL of
a tube furnace for 2 h under an Ar/H2 atmosphere with 5 wt.% Nafion 117 suspension in one ultrasonic bath
a heating rate of 5°C per min. The synthesis of single‐ for several hours. After that, 20 μL of the above ink
metal@SCF electrodes was consistent with the above was pipetted on the GC surface, resulting in the
process, except that only cobalt nitrate or nickel nitrate loading of 0.36 mg cm −2 . Commercial 20 wt.% Pt/C
was added as a metal ion solution in the preparation of and Ir/C were tested as benchmarks for ORR and
the precursor. OER, respectively.
The ORR reaction kinetics was evaluated via the
Koutechy−Levich (K−L) equation:
2.3 | Material characterization
1 1 1 1 1
= + = + ,
A field emission scanning electron microscope (JSM‐ J Jd Jk Bω1/2 Jk
7100F) at a working voltage of 15 kV was used to
investigate the morphology of all as‐prepared samples. where J, Jd, and Jk represent the measured, diffusion‐
Fourier transform infrared spectra (FTIR) were mea- limiting, and kinetic current density, respectively. The ω is
sured on a Bruker Vector‐22 FTIR spectrometer with a the electrode's rotational rate. B can be determined from
scan range of 400–4000 cm−1. The X‐ray photoelectron the Levich equation as follows: B = 0.2 nFCoD2/3v−1/6,
spectra (XPS) were recorded on a Kratos Axis ULTRA where n represents the number of electrons, F is the
system. Transmission electron microscopy (TEM) was Faraday constant (F = 96485 C mol−1), Co is the saturated
conducted on Philips F20 at 200 kV. High‐angle O2 concentration (1.21 × 10−6 mol cm−3), D is the diffu-
annular dark‐field scanning transmission electron sion coefficient of O2 in 0.1 M KOH (1.9 × 10−5 cm2 s−1),
microscope (HAADF‐STEM) imaging was taken and ν is the kinetic viscosity (0.01 cm2 s−1). The constant
by a probe‐corrected JEOL JEM‐ARM200F with an 0.2 is adopted when the rotation speed is expressed
acceleration voltage under 200 kV. XRD patterns were in rpm.
obtained by a Shimadzu XRD‐6000 diffractometer RRDE measurements were tested by LSV at a scan
scanning the angle range from 10° to 80° using CuKɑ rate of 5 mV s−1 at 1600 rpm, and the ring electrode
radiation (λ = 1.5418 Å). Brunauer−Emmett−Teller voltage was kept at 1.5 V versus RHE. The H2O2
(BET) surface areas were estimated from nitrogen collection coefficient (N) at the ring in RRDE experi-
adsorption/desorption isotherms in powder forms ments was 0.37. Below equations were used to calculate
using a surface area analyzer Autosorb iQ Station 1. 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
2.4 | Electrochemical measurements current (IR).
ID
All electrochemical measurements were finished in a n= ,
ID + (IR /N)
traditional three‐electrode cell using an electrochemi-
cal workstation (CHI 760D). A glassy carbon (GC)
2(IR /N)
rotating disc electrode (RDE, AFE5T050GC, Pine H2 O2 % = 100 .
Research) with an area of 0.196 cm2 and graphite rod ID + (IR /N)
were chosen as the working electrode and counter
electrode for ORR and OER measurements. To The electrochemical surface area (ECSA) of catalysts
evaluate the reaction selectivity, a rotating ring disc was obtained by the cyclic voltammetry curves in the
electrode (RRDE, AFE7R9GCPT, Pine Research, non‐faraday current region at the scan rates from 10 to
60 mV s−1. The relation between current and scan rates is profiles were recorded on the CHI 760E electrochemistry
shown in the following equation: station using LSV with a scan rate of 5 mV s−1 calibrated
with 95% iR‐compensation. The discharge power density
Ic was calculated using the data from the discharge
Cdl = ,
v polarized profiles using the following equation:
where Ic refers to the nonfaraday current; v is the scan rates. P = Ud × jd ,
where P is the discharge power density, Ud is the

2.5 | Assembly of Zn–air battery discharge voltage, and jd is the discharge current density.
Galvanostatic discharge–charge cycling tests were carried
The NiCo@SCF was machined to the appropriate thick- out on a Land CT2001 multichannel battery tester. In
ness and size, as the cathode. For the Pt/C‐Ir/C cathode, each galvanostatic cycle, the Zn–air battery was dis-
the electrocatalyst inks were prepared by ultrasonically charged for 60 min and charged for 60 min at a given
dispersing 4 mg of Pt/C‐Ir/C (1:1, mass ratio) into 1 mL of current density of 10.0 mA cm−2. The rate performance
isopropanol/H2O (1/3 v/v) solution. The air electrode was of Zn–air batteries was evaluated by galvanostatic
fabricated by dropping electrocatalyst ink onto carbon discharge at a series of the current density of 5, 10, 20,
paper and dried in the oven (an average catalyst loading of 50, 100, and back to 5 mA cm−2. The Zn–air batteries
1 mg cm−2). Then, this catalyst‐coated carbon paper was went for several cycles of galvanostatic discharge–charge
further pressed with one commercial gas‐diffusion layer at 20.0 mA cm−2. Galvanostatic discharge–charge cycling
(GDL) as the cathode. The Zn–air battery was assembled tests of FZAB were carried out on a Land CT2001
with the above cathode, one Zn foil as the anode, and 6 M multichannel battery tester. In each galvanostatic cycle,
KOH solution involving 0.2 M Zn(oAc)2 as the electrolyte. the FZAB was discharged for 30 min and charged for
The test of the assembled Zn–air battery was carried out in 30 min at a given current density of 2.0 mA cm−2.
a CT2001A battery assessment system (Wuhan LAND
Electronics Ltd.).
3 | R ES ULT S AN D DI S C US S I ON
2.6 | Flexible solid‐state zinc metal–air 3.1 | Electrode characterizations

battery assembly
The fabrication procedures of the NiCo@SCF catalysts
The air electrode is processed into a size of 6 × 2.5 × 0.2 cm. are depicted in Figure 1A. The Ni2+ and Co2+ precursors
The 0.1 mm thick zinc flakes were polished and cleaned as were evenly adsorbed on the melamine foam framework
metal anodes. The electrolyte is a hydrogel electrolyte. The by a facile immersion method at 90°C followed by
specific production process is as follows: One gram of lyophilization drying. The NiCo@SCF was obtained by
polyvinyl alcohol (PVA) with a molecular weight of 19,500 pyrolysis of the foam under an Ar/H2 mix atmosphere at
was dissolved in 10 mL of hot water (95°C), continued to 400°C. Supporting Information: Figure S1 shows the
heat, and stirred for 2 h. Then, 1 mL was dissolved with compressibility of the NiCo@SCF electrode, and the
0.20 M Zn(CH3COOH)2, 18.0 M KOH solution was added compressed electrode can perfectly recover from defor-
to the above PVA solution, and heating and stirring were mation. In Supporting Information: Figure S2, a 200 g
continued. After 40 min, the resulting solution was placed weight was placed on only 0.87 g of NiCo@SCF to further
in a −20°C freezer for gelation. After 12 h, it was taken out testify the elasticity of the NiCo@SCF. These tests prove
and thawed. The gel–thaw process was repeated three that the NiCo@SCF has strong elasticity and could be
times to obtain the desired PVA gel electrolyte. Then, the served as the electrode for flexible devices. The SEM
air electrode with Nafion 117 suspension and the images of NiCo@SCF are shown in Figure 1B,C. Notably,
metal electrode were placed on both sides of the PVA gel the three‐dimensional structure of NiCo@SCF can be
electrolyte to obtain a flexible solid‐state ZAB. preserved after metal loading and pyrolysis. NiCo alloys
are uniformly and abundantly distributed on individual
polygonal fibers and the triangular junction of the
2.7 | Zn–air battery test NiCo@SCF framework (Figure 1D). A similar foam
structure has been preserved when no metal is loaded
All Zn–air battery tests were performed under an onto the foam before pyrolysis (which is noted as
ambient atmosphere at room temperature. The polarized SCF hereafter) (Supporting Information: Figure S3).
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 presence of curved graphdiyne sheets.16,17 The element
alloy nanoparticles are coated in a small number of distribution in the catalyst was characterized by the
carbon layers, where a large number of defect structures corresponding HAADF‐STEM EDS spectrum, and the
and edge structures are present. The HR‐TEM image of results are shown in Figure 1F. Ni, Co, C, and N elements
the particles witnesses the crystal planes with interplanar in the catalyst are uniformly distributed throughout the
spacings of 0.208 nm, which correspond to the (111) carbon foam, and the distribution of Ni/Co elements does
plane of metallic NiCo,15 strongly suggesting a not overlap with the distribution of C and N elements,
nickel–cobalt alloy crystal structure. In addition, curved indicating that the nickel–cobalt alloy exists in the form
fringes with a lattice parameter of 0.417 nm are measured of a structure embedded in the NiCo@SCF. From the
for the carbon layer, which can be attributed to the distribution of EDS in HAADF‐STEM in Figure 1F and
Supporting Information: Figure S4, it can be concluded diffraction peaks are slightly higher than those of pure
that the atomic ratio of element content of cobalt and fcc phase element Co (PDF # 15‐0806) but slightly
nickel in the alloy is 53:47. lower than those of pure fcc phase element Ni (PDF #
The characteristic peaks of the Raman spectrum 04‐0850) (Supporting Information: Figure S6), which
of NiCo@SCF are shown in Supporting Information: strongly certifies the formation of Ni−Co solid solution
Figure S5, in which the peak at 1388 cm−1 corresponds during the pyrolysis and also a certain degree of lattice
to the breathing vibration (D band) of the sp2‐ distortion.20 The broad peak at 21.3° corresponds to
hybridized carbon atoms of the benzene ring, and the the interlayer spacing of 4.17 Å, indicating a defective
peak at 1576 cm−1 corresponds to the in‐plane stretch- carbon with the presence of graphdiyne structure.16,21
ing vibration of the sp2‐hybridized carbon atom of the Although the existence of the NiCo@SCF framework is
benzene ring (G band). The intensity ratio of D peak to confirmed, its crystallinity is poor due to the confor-
G peak is 0.72, indicating that the carbon has an mational fluctuations of NiCo@SCF at the mesoscale.
ordered structure. The peak at 1943 cm−1 is generally In both FT‐IR spectra of Supporting Information:
believed to be related to the diyne bond and the peak at Figure S7, the IR absorption peak at 3337 cm−1 is
2194 cm−1 corresponds to the stretching vibration of attributed to stretching vibrations of secondary
the graphdiyne conjugated diyne, which is a charac- amines (N−H) on the SCF surface. The absorbance at
teristic peak in the graphdiyne structure.17,18 However, 1159 cm−1 corresponds to the C−O stretching vibration
it is difficult to quantify its proportion over the carbon in the melamine−formaldehyde resin. C═N stretching
structure due to its defective nature. As the XRD data mode was observed at 1548 cm−1. The peaks at 1472
of NiCo@SCF shown in Figure 2A and Supporting and 1340 cm−1 correspond to methylene C−H bending
Information: Figure S6, the XRD patterns of prominent vibrations. The bending vibrations of the triazine ring
diffraction peaks at 44.4°, 51.7°, and 76.1° correspond are shown at 810 cm−1.22
to the (111), (200), and (220) planes of the face‐ The surface chemical states of the prepared samples
centered cubic (fcc) nickel−cobalt alloy, respectively.19 were analyzed by XPS. The XPS survey scan of the
The peak positions corresponding to the above three 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.
Co, N, C, and O on the surface (Supporting Information: 3.2 | Electrochemical performance

Figure S8). Detailed analysis of different elements as
shown in Figure 2B is the high‐resolution Ni 2p spectrum. The electrocatalytic performance of as‐fabricated Ni-
Among them, the peaks at 855.9 and 873.7 eV correspond Co@SCF for ORR was tested in alkaline media (0.1 M
to metallic elemental Ni. Two satellite peaks centered KOH). As shown in the LSV curves under alkaline
at 864.1 and 883.9 eV were observed in the Ni 2p conditions in Figure 3A, the initial onset potential (E0)
XPS spectrum of [email protected] Figure 2C shows a and half‐wave potential (E1/2) of NiCo@SCF are 1.01 and
high‐resolution Co 2p XPS spectrum, with peak splitting 0.906 V, respectively, much better than SCF (E0 = 0.861 V,
results similar to Ni 2p. The peaks at 777.8, 779.5, 782.6, E1/2 = 0.61 V) and also exceed those of the electrode with
and 786.2 eV correspond to metal elemental Co, Co3+, commercial Pt/C catalysts (E0 = 0.985 V, E1/2 = 0.878 V).
high‐spin Co2+ ion vibration peaks, and satellite peaks, As shown in Figure 3B, the Tafel slopes of SCF,
respectively, in which the metallic Co species occupies NiCo@SCF, and electrodes with 20 wt.% Pt/C catalysts
dominates the Co 2p spectrum.20,24 The above results echo were measured to be 375.6, 74.4, and 83.1 mVdec−1,
the crystal structure characterizations, further confirming respectively. NiCo@SCF has the smallest Tafel slope,
the formation of NiCo alloy structure. Figure 2E shows the which is due to the highest limiting current density of
high‐resolution C ls XPS spectra of NiCo@SCF, which can NiCo@SCF, further demonstrating the fast oxygen diffu-
be fitted into five peaks. The peaks at 284.7, 285.6, 286.5, sion. The much more positive E0 and E1/2 as well as
287.6, and 289.3 eV correspond to sp2 C–C, sp C–C, C–O, the larger Tafel slopes of SCF in comparison to the
C═N, and C═O,21,25 confirming the existence of N‐doped NiCo@SCF counterpart have strongly elucidated that
carbon material structures. The peaks at 398.8, 399.9, the NiCo alloy particles act as the dominant active sites
400.9, and 404.5 eV of high‐resolution N 1 s XPS spectra in for the ORR on the NiCo@SCF sample. The rotating
Figure 2F correspond to pyridine nitrogen, pyrrolic ring disk electrode (RRDE) test technique was used to
nitrogen, graphitic nitrogen, and N‐oxide, respectively.26,27 further explore the H2O2 yield and electron transfer
It can be seen that the nitrogen in NiCo@SCF samples is number (n) of different samples during the ORR
mainly composed of pyridine nitrogen and graphitic process. As shown in Figure 3C, in the potential range
nitrogen. The pyridinic nitrogen dopants in graphdiyne‐ of 0.2–0.65 V versus RHE, the H2O2 yield of the sample
based carbon materials could contribute to the ORR/OER NiCo@SCF is lower than 3.3%, indicating a dominant
electrocatalytic activity of the electrode.21,28–31 four‐electron transfer ORR process. The calculated n is
Generally, the specific surface area of the catalyst about 3.88, which is even higher than the electrode with
determines the number of exposed catalytic active sites, a commercial Pt/C catalyst (3.76). The electron transfer
and a high specific surface area is an essential number calculated by the K–L equation responding to
factor affecting the catalytic performance. Therefore, LSV curves of NiCo@SCF in an O2‐saturated solution of
the specific surface area and pore size distribution of the 0.1 M KOH at different rotation speeds is 3.87 (Support-
samples were analyzed. Figure 2D shows the N2 ing Information: Figures S10 and S11), which is similar
adsorption−desorption test curves of SCF and to the result obtained by the above calculation method,
NiCo@SCF. The N2 adsorption–desorption isotherms indicating that the reaction is an efficient four‐electron
of NiCo@SCF are of type II and type IV, and there is an transfer process.
H4‐type hysteresis loop. The multipoint Brunauer−Em- The OER catalytic performance of different samples
mett−Teller (BET) method was used to calculate the in alkaline media is also evaluated. As the LSV curves
specific surface area of SCF and NiCo@SCF, which are shown in Figure 3D, at a current density of 10 mA cm−2
104.5 and 271.2 m2 g−1, respectively. The higher specific (Ej=10), the OER overpotential of NiCo@SCF is only
surface area of the NiCo@SCF electrode is beneficial to 286 mV. Under the same test conditions, the over-
expose more electrocatalytic active sites, which can improve potential of NiCo@SCF is 44 mV lower than that of the
its catalytic activity. From the analysis of the pore size commercial Ir/C catalyst, indicating that the NiCo@SCF
distribution curve (Supporting Information: Figure S9), it sample has excellent OER electrocatalytic activity. The
can be seen that compared with SCF, the NiCo@SCF OER reaction kinetics of different samples were evalu-
sample has sharp pore distribution peaks at 10–13 nm, ated by the slope of the Tafel plots. It can be seen from
indicating that the NiCo@SCF has mesopore structure Figure 3E that the sample NiCo@SCF has the smallest
besides macropores. Hierarchical pores promote mass Tafel slope, indicating excellent OER catalytic kinetics,
transportation, gas diffusion, and the contact of catalytic which originated from the abundant catalytic active sites,
active sites with the electrolyte, which facilitates the high specific surface area, and better electron transport
transport of catalytically relevant protons and enhances synergy of the NiCo@SCF samples. The poor OER
the electrocatalytic activity.32,33 activity of the SCF electrode has been confirmed by the
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 are shown in Supporting Information: Figure S14,
(146 mV decade−1). The difference (ΔE) between the respectively. After 50,000 s, the relative current density
half‐wave potential of ORR and the corresponding of NiCo@SCF remained at 91% and 89% of its initial
potential of OER at a current density of 10 mA cm−2 is values for ORR and OER, respectively, while the Pt/C
usually used to evaluate whether a catalyst has excellent counterpart maintained at 80% and Ir/C maintained at
ORR/OER bifunctional catalytic activity. The smaller ΔE 76% of the initial values. This result can fully prove that
indicates that the catalyst has excellent ORR/OER the bifunctional electrode has excellent stability, which
bifunctional electrocatalytic activity in the same electro- could probably be linked to the carbon shell on the NiCo
lyte. Therefore, the ORR/OER bifunctional LSV curves of alloy catalyst surface.
NiCo@SCF in the O2‐saturated 0.1 M KOH electrolyte The ECSA of the NiCo@SCF sample was assessed by
were tested and the results are shown in Figure 3F. The calculating the Cdl values (Supporting Information:
ΔE value of NiCo@SCF is 0.61 V versus RHE. After Figure S12). The NiCo@SCF sample exhibits a higher Cdl
20,000 cycles, ΔE still maintains a small value (0.631 V). (10.9 mF cm−2) than that of Pt/C‐Ir/C (9.7 mF cm−2),
It can be seen from the LSV curves that the performance indicating that the abundant heterostructures, oxygen
attenuation of ORR and OER is very small, the half‐wave vacancies, and unique porous structure of nanoparticles
potential of ORR is reduced by 9 mV, and the Ej=10 of increase the ECSA and create more active sites. Since the
OER is attenuated by 12 mV. Chronoamperometric robustness of the NiCo@SCF electrode material gradually
responses for ORR of NiCo@SCF and Pt/C in O2‐ deteriorated when the temperature was above 600°C, the
saturated 0.1 M KOH solution at 0.6 V, OER of NiCo@SCF electrode materials were not suitable as an
NiCo@SCF and Ir/C in 0.1 M KOH solution at 1.55 V electrode for zinc−air batteries (whether it was an aqueous
system or a solid‐state system ZAB), so comparing the ORR sample NiCo@SCF was much higher, and Co2+ was
performance of samples pyrolyzed from 300°C to 600°C (as revealed to be beneficial to enhance ORR/OER activity.34
shown in Supporting Information: Figure S13A), the half‐ Compared to sample Ni@SCF, the content of Ni2+ was
wave potentials of NiCo@SCF‐300, NiCo@SCF‐400, also significantly increased, indicating that Ni2+ occupies
NiCo@SCF‐500, and NiCo@SCF‐600 were 0.71, 0.906, a large part of the sample surface, which is conducive to
0.86, and 0.898 V respectively. There was no obvious OER activity.35 And the metallic states of Co and Ni were
difference in the ORR performance of the NiCo@SCF found in the XPS spectra; the occurrence of electron
pyrolyzed at 400°C–600°C compared with the half‐wave redistribution after NiCo@SCF vacancy configuration,
potential; however, the NiCo@SCF electrode material which may actively tune the energy band and
pyrolyzed at 400°C showed better kinetic properties. electronic structure of nanomaterials, and the electron
Moreover, the mass activities of four samples are shown redistribution may lead to charge transfer from NiCo to
in Supporting Information: Figure S13B; the NiCo@SCF‐ N‐doped carbon to form electron‐rich N‐doped carbon
400 has the highest mass activity among them, which and electron‐deficient NiCo species. The electrocatalytic
shows that a certain degree of carbonization is beneficial to performance of as‐fabricated Co@SCF, Ni@SCF, and
improve electrical conductivity, thereby promoting catalytic NiCo@SCF for ORR was tested in alkaline media (0.1 M
performance. KOH). As shown in the LSV curves under alkaline
The roles of elemental and compositional information conditions in Supporting Information: Figure S22A, the
of metals in the composite catalysts were investigated. As half‐wave potential (E1/2) of Co@SCF and Ni@SCF is
the XRD data of Co@SCF, Ni@SCF, and NiCo@SCF 0.822 and 0.84 V, respectively, much worse than
shown in Supporting Information: Figure S15, compared NiCo@SCF (E1/2 = 0.906 V). The OER catalytic perform-
to the three main peaks of NiCo@SCF, the peak positions ance of different samples in alkaline media is also
of Co@SCF are slightly lower, indicating that those peaks evaluated. As the LSV curves shown in Supporting
correspond to pure fcc phase element Co (PDF # 15‐ Information: Figure S22B, at a current density of
0806). On the contrary, peaks of Ni@SCF are slightly 10 mA cm−2 (Ej=10), the OER overpotentials of Co@SCF
higher than those of NiCo@SCF, corresponding to pure and Ni@SCF are 455 and 461 mV, much higher than that
fcc phase element Ni (PDF # 04‐0850), certifying the of the overpotential of NiCo@SCF (286 mV), indicating
formation of Ni–Co solid solution during the pyrolysis that the NiCo@SCF sample has the most excellent OER
and also a certain degree of lattice distortion of electrocatalytic activity.
NiCo@SCF. The SEM images of Co@SCF are shown in The excellent ORR/OER bifunctional electrocatalytic
Supporting Information: Figure S16. Notably, there are activity of NiCo@SCF samples in the same electrolyte is
no obvious alloy particles like the sample NiCo@SCF on attributed to the following points: (1) Ni and Co elements in
the carbon skeleton, and insufficient loadings may lead the alloy undergo electronic transitions between different
to poor bifunctional electrocatalytic performance. This valence states, providing redox centers for the adsorption
can be seen in Figure S17 that the particle distribution of and activation of O2, and enhance the electrocatalytic
cobalt elements is extremely rare. At the same time, it activity of ORR;36‐38 (2) NiCo@SCF has a large specific
can be seen from Supporting Information: Figures S18 surface area, which is beneficial to reduce agglomeration of
and S19 that in the synthesized Ni@SCF, there are a nanoparticles, expose more active sites, and facilitate the
large number of aggregated metal particles on the carbon electrocatalysis‐related proton transport; (3) The well‐
skeleton. This aggregation phenomenon is not conducive preserved conductive network of carbon promotes the
to the exposure of catalytic sites and also leads to rapid transport of electrons, and a large amount of nitrogen
deficient catalytic performance. In Supporting Informa- doping can increase the surface charge density, thereby
tion: Figure S20, the high‐resolution Co 2p spectrum of enhancing the electrocatalytic activity of [email protected]‐42
Co@SCF is shown. The peaks at 777.8, 780.9, 784.8, The catalytic reaction kinetics are improved, resulting in
and 788.6 eV correspond to metal elemental Co, Co3+, higher ORR/OER electrocatalytic activity.
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 3.3 | Battery performance
Ni@SCF in Supporting Information: Figure S21, the
peaks at 855.6 and 874.0 eV correspond to metallic The above electrocatalytic performance tests certified
elemental Ni. The contents of different metal valence that the NiCo@SCF material exhibited excellent
states corresponding to different XPS subpeaks of three bifunctional ORR/OER electrocatalytic activity. To fur-
samples are shown in Supporting Information: Table S1. ther evaluate the performance of electrocatalysts in
Compared with the sample Co@SCF, the Co2+ of the practical energy device tests, in this work, the
NiCo@SCF was machined into a rectangular shape density (178.6 mW cm−2) of NiCo@SCF‐assembled ZAB
suitable as a self‐supporting cathode for an aqueous is more than double of the Pt‐Ir/C‐assembled ZAB
rechargeable ZAB (Supporting Information: Figure S23). (87.3 mW cm−2). The NiCo@SCF‐assembled ZAB was
As shown in Figure 4A, the LSV curves and correspond- subjected to discharge tests at different current densities,
ing power density curves of aqueous ZAB cells are and the results are shown in Figure 4B. After two 10 h
prepared with NiCo@SCF and Pt/C‐Ir/C@carbon paper, cycles, the discharge process with the maximum current
respectively. It can be observed that the peak power 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.
returns to 5 mA cm−2 of the third cycle, compared with image (Supporting Information: Figure S25), and the NiCo
the first cycle, the discharge platform remains at 1.227 V, alloy particles on its framework were also observed in TEM
which is 98.8% of the initial value. Even when comparing (Supporting Information: Figure S26A,B). In particular, the
the first cycle with the third cycle when the current grain size of NiCo alloy particles after the charge/discharge
density is under 50 mA cm−2, the discharge platform can stability test was reduced probably due to the electro-
be maintained at 1.065 V, which is 95.7% of the initial chemical reconstruction, as shown in the HRTEM image
value. The specific capacity calculated by normalizing the (Supporting Information: Figure S26C,D). In addition, the
mass of consumed Zn by performing constant voltage uniform distribution of NiCo‐alloy particles on the SCF
discharge tests at potential platforms corresponding to framework is evident in the EDS mapping results
current densities of 20 mA cm−2 for a long time until the (Supporting Information: Figure S27). Supporting Informa-
zinc flakes are exhausted (Figure 4C), which was tion: Figure S28 shows the XPS high‐resolution spectrum of
755 mAh gZn−1, indicating that the ZAB assembled with the sample after the cycle test. Supporting Information:
NiCo@SCF has excellent discharge stability and dis- Figure S28A,B correspond to the Ni 2p and Co 2p XPS
charge efficiency, which originated from the efficient and spectra, respectively, and it is evident that there are
stable ORR electrocatalytic performance of NiCo@SCF. amounts of Ni and Co elements representing the
The structural stability of the NiCo@SCF as an air valence state of the alloy in the subpeaks. As the C ls
electrode was further assessed in a long‐term charge and XPS spectrum shown in Supporting Information:
discharge test, as shown in Figure 4D,E. After 540 h of Figure S28C, the subpeaks from 284 to 290 eV are
charge–discharge (current density of 10 mA cm−2), the consistent with the five subpeaks as aforementioned
charge and discharge voltage gap of the NiCo@SCF and shown in Figure 2E. Compared with the peak in
assembled ZAB finally reached 0.94 V, and the Figure 2F, the relative content of pyrrolic‐N and
charge–discharge plateau hardly changed. This stability graphitic‐N decreases, while the content of pyridinic‐N
exceeds that of most aqueous ZAB assembled from NiCo increases relatively in Supporting Information: Figure S28D,
alloy‐based catalysts (Supporting Information: Tables S2 which is also consistent with the literature mentioned above
and S3). Considering the excellent performance and that the performance of ORR/OER is determined by
flexibility feature of the NiCo@SCF, it was further pyridinic‐N in nitrogen doping electrocatalysts, which is
assembled into flexible solid‐state ZAB (FSZAB) as an one of the main factors. The above results strongly indicate
emerging technology for flexible energy storage applica- that NiCo@SCF is endowed with outstanding structural
tions (Figure 4F). As shown in Figure 4G, the resultant robustness and high cycling stability that is essential to the
FSZAB with a self‐supporting NiCo@SCF cathode is delivery of efficient and steady ORR/OER electrocatalytic
capable of recharge under a stable charge and discharge performance. The robust, efficient NiCo@SCF herein
voltage gap of 0.805 V, which can be bent to different exemplifies a useful electrode in rechargeable FSZAB and
angles after prolonged cycling. Compared with some next‐generation wearable electronic devices.
recently published alloy‐based bifunctional electrocata-
lysts (Supporting Information: Tables S4 and S5), the
NiCo@SCF‐assembled FSZAB exhibited a relatively high 4 | CONCLUSION
power density value of 80.1 mW cm−2 and displayed a
stable charge/discharge voltage gap of 0.8 V, which was In conclusion, NiCo bialloy particles have been successfully
95 h more than that at the current density of 2 mA cm−2 anchored onto the carbonized MF framework (NiCo@SCF)
(Figure 4H,I). These results have verified that NiCo@SCF via a facile thermal conversion approach using commercially
catalysts are promising self‐supporting electrodes in re- available low‐cost melamine foam. The resultant self‐
chargeable FSZAB and wearable devices, which will pave supporting, machinable, porous NiCo@SCF electrode
the way to more economically viable, cost‐effective, and showed excellent ORR/OER bifunctional activity, providing
durable smart energy systems. a new idea for designing other non‐precious‐metal‐based
To further investigate the structural robustness, the electrodes. More importantly, the rechargeable Zn–air
spent NiCo@SCF was retrieved from the FSZAB after a battery assembled with the NiCo@SCF electrode manifested
95 h charge/discharge stability test and subjected to an appreciable charge–discharge performance with a steady
structural characterization. The XRD data in Supporting voltage gap. The unique self‐supporting NiCo@SCF elec-
Information: Figure S24 shows that the three main peaks trode will have many potential applications, providing more
that indicate the crystal face of the NiCo alloy still maintain possibilities for the design and manufacturing of mass‐
the original spectrum, indicating that the overall structure producible, cost‐effective, and wearable‐type Zn–air batteries.
has been effectively preserved. The flexible framework of The demonstrated strategy can be readily extended to other
NiCo@SCF remained intact as confirmed in the SEM wearable devices for wider applications.
ACKNOWLEDGMENTS highly‐efficient multi‐functional electrocatalysis for

This work was financially supported by the Australian CO2RR, ORR and Zn‐air battery. J Mater Chem A. 2019;
Research Council Discovery Projects (DP200100965, 7(25):15271‐15277.
12. Shi H, Yue M, Zhang CJ, et al. 3D flexible, conductive, and
DP230102504) and Griffith University Postdoctoral
recyclable Ti3C2Tx MXene‐Melamine foam for high‐areal‐
Fellowship.
capacity and long‐lifetime alkali‐metal anode. ACS Nano.
2020;14(7):8678‐8688.
CONFLI CT OF I NTER EST STATEMENT 13. Liu Z, Li N, Zhao H, et al. Regulating the active species of Ni
The authors declare no conflict of interest. (OH)2 using CeO2: 3D CeO2/Ni(OH)2/carbon foam as an
efficient electrode for the oxygen evolution reaction. Chem Sci.
DATA A VAILABILITY S TATEMENT 2017;8(4):3211‐3217.
14. Park SK, Chung DY, Ko D, Sung YE, Piao Y. Three‐
The data that support the findings of this study are
dimensional carbon foam/N‐doped graphene@MoS2 hybrid
available in the Supporting Information Material of this
nanostructures as effective electrocatalysts for the hydrogen
article. evolution reaction. J Mater Chem A. 2016;4(33):12720‐12725.
15. Feng D, Yang H, Wang Q, Guo X. Preparation and
ORCID characteristic of three‐dimensional NiCo alloy/carbon com-
Mengyang Dong https://orcid.org/0000-0002- posite monoliths with well‐defined macropores and mesos-
2224-1943 tructured skeletons. J Mater Sci. 2019;54(6):4719‐4731.
Huajie Yin https://orcid.org/0000-0002-9036-9084 16. He J, Wang N, Cui Z, et al. Hydrogen substituted graphdiyne
as carbon‐rich flexible electrode for lithium and sodium ion
Porun Liu http://orcid.org/0000-0002-0046-701X
batteries. Nat Commun. 2017;8(1):1172.
Huijun Zhao https://orcid.org/0000-0002-3028-0459 17. Zhou J, Gao X, Liu R, et al. Synthesis of graphdiyne nanowalls
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Received: 30 November 2022 | Revised: 6 February 2023 | Accepted: 12 April 2023

NiCo alloy‐anchored self‐supporting carbon foam

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

1 | INTRODUCTION surface of the carbon layer and thereby stimulating its

where Ic refers to the nonfaraday current; v is the scan rates. P = Ud × jd ,

where P is the discharge power density, Ud is the

2.6 | Flexible solid‐state zinc metal–air 3.1 | Electrode characterizations

Co, N, C, and O on the surface (Supporting Information: 3.2 | Electrochemical performance

ACKNOWLEDGMENTS highly‐efficient multi‐functional electrocatalysis for

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