Research Article

Cite This: ACS Catal. 2018, 8, 8961−8969 pubs.acs.org/acscatalysis

Single Co Atoms Anchored in Porous N‑Doped Carbon for Efficient

Zinc−Air Battery Cathodes
Wenjie Zang,† Afriyanti Sumboja,‡,§ Yuanyuan Ma,†,‡ Hong Zhang,† Yue Wu,† Sisi Wu,†
Haijun Wu,† Zhaolin Liu,*,‡ Cao Guan,*,† John Wang,*,† and Stephen J. Pennycook*,†
†
Department of Materials Science and Engineering, Faculty of Engineering, National University of Singapore, Singapore 117574
‡
Institute of Materials Research and Engineering (IMRE), Agency for Science, Technology and Research (A*STAR), 2 Fusionopolis
Way, Innovis #8-13, Singapore 138634
§
Material Science and Engineering Research Group, Faculty of Mechanical and Aerospace Engineering, Institut Teknologi Bandung,
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*
S Supporting Information

ABSTRACT: Exploration of cheap, efficient, and highly durable

transition-metal-based electrocatalysts is critically important for
the renewable energy chain, including both energy storage and
energy conversion. Herein, we have developed cobalt (Co) single
atoms anchored in porous nitrogen-doped carbon nanoflake
arrays, synthesized from Co-MOF precursor and followed by
removal of the unwanted Co clusters. The well-dispersed Co
single atoms are attached to the carbon network through N−Co
bonding, where there is extra porosity and active surface area
created by the removal of the Co metal clusters. Interestingly,
compared with those electrocatalysts containing excess Co
nanoparticles, a single Co atom alone demonstrates a lower
oxygen evolution reaction (OER) overpotential and much higher
oxygen reduction reaction (ORR) saturation current, showing
that the Co metal clusters are redundant in driving both OER and ORR. Given the bifunctional electrocatalytic activity and
mechanical flexibility, the electrocatalyst assembled on carbon cloth is employed as the air cathode in a solid-state Zn−air
battery, which presents good cycling stabilities (2500 min, 125 cycles) as well as a high open circuit potential (1.411 V).
KEYWORDS: single Co atoms in carbon, oxygen reduction reaction, oxygen evolution reaction, zinc−air battery, electrocatalyst

1. INTRODUCTION For the above purpose, cobalt-based nanomaterials, such as

For the past several years, there has been a constant search for
better energy storage and conversion systems, such as
development of improved metal−air batteries, supercapacitors,
and electrocatalysts, which are crucial parts of the entire energy
chain.1−6 For metal−air batteries, such as the Zn−air battery,
ORR and OER are two significant processes that make a
determining effect on the overall efficiency of the charge and
discharge processes.7−10 Considering the low onset and half-
wave potential of ORR and high overpotential of OER in
several of the known electrocatalyts, highly efficient cathodes
are required in order to reduce the energy barrier and improve
the overall efficiency. Noble-metal-based nanomaterials with
high catalytic activity are known as among the best
electrocatalysts in terms of performance. However, their high
cost, scarcity, and poor long-term stability (in some
parameters) greatly restrict their widespread and large-scale
utilization.11−15Thus, there is an urgent need for the
development of cheap, efficient, and durable nonprecious-
metal-based electrocatalysts.
Co3O4,16−19 CoP,20−22 CoSe2,23,24 and cobalt single-atom
catalysts (Co-SAC),25−29 have attracted extensive attention
recently, owing to their low cost and generally high catalytic
activities, depending on both the type of the compounds and
their nanostructural features. Among these cobalt-based
catalysts, Co single atoms anchored in an appropriate matrix
(Co-SAC) exhibit several advantages, including high atom
utilization, high active site exposure, low-coordination, and
unique catalytic performance compared with their cobalt
nanoparticle and nanocluster counterparts.30−35 Co single
atoms can be bonded to the supporting matrix through strong
electronic and covalent interactions, subsequently forming
rather stable catalysts.32,36,37 In a couple of recent studies,
nitrogen-doped carbon nanomaterials have been selected as
the supporting matrix for Co-SAC to develop optimal Co−N4
sites, which can be active sites for oxygen adsorption and
Received: July 1, 2018
Revised: August 7, 2018
Published: August 20, 2018

© 2018 American Chemical Society 8961 DOI: 10.1021/acscatal.8b02556

ACS Catal. 2018, 8, 8961−8969
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subsequent OO bond breaking during the ORR.38,39 In
addition, as has been documented in previous studies, Co-SAC
have been studied for energy conversion, such as hydrogen
evolution,40 oxygen reduction,25,26,41,42 and hydrogenation.38
By comparison, there is little that has been done with Co single
atoms (or other metals) for energy storage.
Zn is the fourth most abundant metal on earth. Zn−air
batteries, exhibiting high theoretical energy density (1086 Wh
kg−1, including oxygen) and low cost, have been suggested to
be one of the most promising energy storage systems. One of
the challenges is the general lack of stable and efficient
bifunctional air electrodes, which has been a major obstacle to
their practical application.43−48 Although several powder-based
materials, such as transition metal oxides 17,49,50 and
phosphides,51,52 have been studied for rechargeable Zn−air
batteries, use of polymeric binders and conductive additives
often adds extra weight/volume to the cathode materials.53,54
These binders can also significantly reduce the catalytic
activity, enlarge the interfacial impedance, and affect the
long-term stability.55 Although Co SAC have been tested for
OER and ORR, to the best of our knowledge, there is no
report on the successful application of Co SAC to flexible Zn−
air batteries. Therefore, to improve the durability and flexibility
of Zn−air batteries, it would be of considerable interest to
grow Co SAC on a conductive matrix directly and use it as a
binder-free air cathode in Zn−air batteries.
Herein, we report a Co SA electrocatalyst assembled in
nitrogen-doped porous carbon nanoflake arrays (NC-Co SA),
which was fabricated by a facile carbonization-acidification
process using metal organic frameworks (MOF) as the
precursor material. Compared with the Co nanoparticle
counterpart (NC-Co), the NC-Co SA shows significantly
enhanced ORR and OER performance. Furthermore, for the
first time, the NC-Co SA electrocatalyst is studied as an air
cathode without any binder and additives, and it is applied to
both aqueous and solid-state Zn−air batteries. In addition to
the energy storage behavior, the device shows excellent cycling
stability and flexibility as well as a high open-circuit potential.
2. EXPERIMENTAL SECTION
2.1. Synthesis of Materials. 2.1.1. Synthesis of Co-Based
MOF Nanoflake Arrays (Co-MOF) on Carbon Cloth. First, 40
mL of 2-methylimidazole solution (0.4 M) was mixed with 40
mL of Co(NO3)2·6H2O solution (50 mM) at room temper-
ature. One piece of acidized carbon cloth (35 × 55 mm2) was
then put in the solution and retained for 4 h. Then the carbon
cloth was washed with deionized water and dried overnight at
55 °C.
2.1.2. Synthesis of Co Nanoparticles in Nitrogen-Doped
Carbon Nanoflake Arrays (NC-Co). A piece of the carbon
cloth with Co-MOF arrays was put in a ceramic boat and
transferred into a tube furnace. The sample was then annealed
in a nitrogen atmosphere at 800 °C for 4h with a ramping rate
of 1 °C min−1. When the furnace was cooled to room
temperature, the NC-Co is recovered.
2.1.3. Synthesis of NC-Co SA. A piece of carbon cloth with
NC-Co (15 × 55 mm2) was immersed in 40 mL of
concentrated hydrochloric acid (HCl, 37 wt %), and the
suspension was then stirred for 6 h by a magnetic bar to
dissolve Co metal clusters. After that, the carbon cloth with
NC-Co was washed with deionized water several times until
the PH of the solution reached 7, and then it was dried
overnight at 55 °C.
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2.2. Characterization. Scanning electron microscopy
(SEM, SUPRA 40 Zeiss) was used to study the particle
morphologies in all samples. X-ray diffraction (XRD) patterns
and X-ray photoelectron spectroscopy (XPS) data were
acquired by a Bruker D8 diffractometer and a AXIS Ultra
XPS, respectively. Scanning transmission electron microscopy
(STEM), energy-dispersive X-ray spectroscopy (EDS), and
electron energy loss spectroscopy (EELS) were conducted
using a JEOL ARM200F equipped with ASCOR aberration
corrector cold field emission gun, Gatan Quantum ER
spectrometer and Oxford X-max 100TLE SDD EDS under
acceleration voltages of 80 and 200 kV. The images at 200 kV
had improved resolutions, and no damage was observed. All
results reported here were obtained at 200 kV. Raman
spectroscopy studies were made using a LabRAM HR
Evolution Raman microscope. Inductive coupled plasma
mass spectrometry (ICP-MS) was conducted using a
PerkinElmer Optima 5300DV. Nitrogen adsorption−desorp-
tion isotherms were measured using a Micromeritics 3Flex at
77 K. The specific surface areas and pore size distribution were
calculated by the Brunauer−Emmett−Teller (BET) and
density functional theory (DFT) method, respectively.
2.3. Electrochemical Measurements. OER and ORR
activities of NC-Co and NC-Co SA catalysts were evaluated by
linear sweep voltammetry (LSV) and rotating disk electrode
(RDE) studies in O2-saturated potassium hydroxide electrolyte
(KOH, 1 M, pH = 14). RDE measurements were recorded by
an Autolab PGSTAT302N work station with the standard
three electrode system. The samples were fixed on the glassy
carbon RDE by acrylic tape, which formed the working
electrode. A platinum plate was used as the counter electrode,
and Ag/AgCl electrode acted as the reference electrode. The
disk electrode was scanned at a rate of 5 mV s−1 and all
potentials were calibrated against a reversible hydrogen
electrode (RHE), according to ERHE = EAg/AgCl (3 M KCl) +
0.059 × pH + 0.209 V. The number of electrons transferred
(n) is calculated using the Koutecky−Levich equation:
1 1 1 1 1
= + = 1/2
+
i idl ik Bω ik
B = 0.62nFACODO2/3ν−1/6
where i, idl, and ik represent the measured current, diffusion-
limiting current, and kinetic current, respectively. F is the
Faraday’s constant (98485 C mol−1), A is the electrode’s
geometric area (0.35 cm2), CO is the bulk concentration of
oxygen, DO is the diffusion coefficient of oxygen, ν is the
kinematic viscosity of the electrolyte, ω is the electrode
rotation speed. DO, CO, and v in 1 M KOH are 1.65 × 10−5
cm2 s−1, 8.3 × 10−7 mol cm−3, and 9.5 × 10−3 cm2 s−1,
respectively. The mass activity (A g−1 of catalyst) was
determined from the measured current density (mA cm−2)
and the amount of catalysts grown on carbon cloth (mA
cm−2). The turnover frequency (TOF) is calculated using the
following equation:
j*A
TOF =
4*F *n′
where j is the measured geometrical current density, n′ is the
number of moles of Co atoms on the working electrode, which
was obtained from ICP-MS.
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Figure 1. Illustration of the formation of NC-Co SAC nanoflake arrays on carbon cloth, and STEM-EELS analysis. (a) Schematic illustration of
fabrication process, local magnification of obtained materials. (b) SEM image of Co MOF. (c) STEM image of NC-Co. (d) STEM image of NC-
Co SA. (e) HAADF STEM image of Co atoms distributed across the nitrogen-doped carbonaceous support. (f) EEL spectra taken at the bright
atom in the red circle in (e) showing Co and N edges. (g) EEL spectra taken at the dark support area in the blue circle in (e) showing neither.

2.4. Assembly and Electrochemical Test of Zn−Air
Batteries. For an aqueous Zn−air battery, a Zn plate was used
as the anode and 6 M KOH consisting of 0.1 M ZnAc served
as the electrolyte. The air electrode was composed of one layer
of NC-Co SA and a layer of carbon paper (38 BC SGL
Carbon). Cycling tests were performed by a Maccor 4300
battery test system, using recurrent galvanostatic pulses for 10
min of discharge followed by 10 min of charge at 10 mA cm−2.
For comparison purposes, commercial Pt/C catalyst was used
as a reference.
To assemble the solid-state sandwich-like layered Zn−air
battery, the solid-state electrolyte was prepared by the
following process. First, 5 mL of 11.25 M KOH and 0.25 M
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ZnO were mixed with 0.5 g of acrylic acid and 0.075 g of N,N′-
methylene-bis(acrylamide). The white precipitate was filtered
out after 5 min of stirring. Next, 75 μL of 0.3 M K2S2O8
(potassium persulfate) was added into the solution, where a
small portion of the solution was poured into the acrylic well
(thickness: 1.0 mm) once the solution started to polymerize.56
Zn foil (0.5 × 3 cm2, with 0.5 × 1.5 cm2 left blank as current
collector), solid-state electrolyte, and flexible air cathode (0.5
× 1.5 cm2, adhered to 0.5 × 3 cm2 Ti mesh current collector)
were assembled first, and then two pieces of acrylic tape with
0.5 mm thickness were used to bond the device into a
rectangular shape with a thickness of 2.0 mm. Cycling tests
were performed using a Maccor 4300 battery test system, as
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Figure 2. Phase identification and surface chemical state of NC-Co SA and NC-Co. (a) XRD spectra. (b) XPS spectra of Co 2p in the sample of
NC-Co SA. (c) XPS spectra of N 1s in the sample of NC-Co SA. (d) Raman spectra.
before. Mechanical flexibility and stability were tested by
flattening and folding of the battery alternately for five cycles.
Commercial Pt/C catalyst and NC-Co samples were used as
references.
3. RESULTS AND DISCUSSION
3.1. NC-Co SA Electrocatalyst. The schematic process for
fabrication of NC-Co SA is illustrated in Figure 1a. Initially,
two-dimensional Co MOF nanoflake arrays were synthesized
on the carbon cloth by mixing an appropriate amount of
Co(NO3)2·6H2O and 2-methylimidazole for 4 h. From the
Scanning Electron Microscopy image in Figure 1b and Figure
S1 (Supporting Information), these Co MOF precursors grew
uniformly on the carbon cloth, typically showing a triangular
shape with a smooth surface. Subsequently, the Co MOF was
carbonized in a nitrogen atmosphere at 800 °C for 4 h. During
this process, the nanoflake morphology was well retained on
carbon cloth with a mass loading of 1.56 mg cm−2, and some
Co nanoparticles had become encapsulated in carbonaceous
shells to form the NC-Co sample, as shown in Figure 1c and
Figure S2. After acid leaching treatment for 6 h, the
morphologies of NC-Co SA were well-retained. Most of the
large Co particles were removed (Figure 1d and Figure S3),
resulting in the decline of mass loading to 1.35 mg cm−2. The
N2 adsorption−desorption isotherm of NC-Co SA shows a
typical type-IV curve with a hysteresis loop, suggesting the
existence of mesopores (Figure S4). The specific surface area
and total pore volume of NC-Co SA are measured to be
319.35 m2 g−1 and 0.20 cm3 g−1, respectively, which are higher
than those corresponding values of NC-Co (268.02 m2 g−1,
0.10 cm3 g−1). Such increase of specific surface area can
accommodate more active sites for electrocatalytic reactions.
Meanwhile, as shown in Figure S5, the NC-Co SA is rich in Co
single-atom sites, which are dispersed well both in the flakes
and the ripple-like nitrogen-doped carbon shells. The EDS
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results in Figure S6 also confirm that the Co and N are
dispersed evenly in the catalyst. According to the results of
ICP-MS, the loading content of Co in NC-Co SA is 1.84 wt %,
which is much smaller than that in NC-Co (74.9 wt %),
suggesting that most Co particles were removed by the acid
leaching treatment.
To better reveal the chemical bonding of Co single atoms in
the NC-Co SA, we have employed atomic level HAADF-
STEM coupled with EELS (Figure 1e−g). When we placed the
electron beam on the bright dot (red circle in Figure 1e), both
Co and N signals were detected in the EELS, confirming the
coexistence of Co and N in the form of Co−Nx. By
comparison, when the electron beam was moved to the dark
matrix (blue circle in Figure 1e), no Co and N signals were
found. The above EELS results were also confirmed in many
areas throughout the sample, as provided in Figure S7. This
atomic level spectroscopic analysis testifies that the single-atom
sites composed of Co are coordinated with N, and there are
sufficiently stable Co−Nx sites anchored in the porous flakes,
which survived under the high voltage electron beam. The
Co−Nx coordination and Co aggregates (Co−Co coordina-
tion, small Co dots) were formed from the Co MOF precursor
during the high temperature carbonization process. Some of
the Co−Co bonds were broken, when large Co clusters were
removed by the washing of strong acid, but those Co single
atoms coordinated with N remained in the N-doped carbon
flakes.
The nanocrystalline nature of the NC-Co and NC-Co SA
were further confirmed by X-ray diffraction (Figure 2a). NC-
Co exhibited the cubic phase of Co metal (PDF no. 15-0806)
and graphitic carbon its (002) plane. After the acid leaching,
no strong Co-containing peaks could be detected in NC-Co
SA, due to the insensitivity of XRD toward single atoms. The
chemical composition of NC-Co SA was further investigated
by using XPS. The Co 2p spectra in Figure 2b exhibit two main
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Figure 3. Electrochemical characterization of the catalysts. (a) Oxygen reduction polarization curves at the rotation speed of 1600 rpm. (b) Oxygen
reduction polarization curves of NC-Co SA at different rotation speeds and corresponding Koutecky−Levich plots. (c) Oxygen evolution curves.
(d) Stability test of aqueous rechargeable Zn−air batteries using NC-Co SA and Pt/C as the air cathodes.
peaks at 778.8 and 780.34 eV with one satellite peak at 783.1
eV, and one main peak at 795.5 eV with one satellite peak at
799.19 eV. The N 1s spectra in Figure 2c can well be
deconvoluted into four peaks, which are assigned to the
pyridinic and N−Co (398.54 eV), pyrrolic (399.56 eV),
graphitic (401.06 eV), and N-oxide (402.71 eV).40 As
suggested by previous work, the graphitic N would affect the
geometric and electronic structures of the carbonaceous
matrix, whereas the pyridinic N are most likely to bond with
atomically dispersed Co atoms in the form of CoN4.38 The
binding energies of the N−Co and pyridinic N are too close to
differentiate, thus the peak at the binding energy of 398.54 eV
includes contributions both from N−Co and the pyridinic N.
This result is also in accordance with the above EELS results,
which have testified the coexistence of Co and N. Furthermore,
compared with the N spectra in NC-Co (Figure S8), the ratio
of graphitic N to pyrrolic N in NC-Co SA remains nearly
unchanged, but the ratio of N−Co to graphitic N increases
significantly. This reveals that more Co−Nx sites are exposed
on the surface of NC-Co SA than NC-Co. In addition to Co
and N, elements of C and O were also detected by XPS, as
shown in Figure S9. Raman spectra in Figure 2d show the
characteristic G and D bands of the carbon which are related to
the mesoporous carbonaceous flakes. The ID/IG ratio of NC-
Co SA is larger than that of NC-Co, which is assumed to be
due to the high density of pores and defects (such as vacancies
and edge sites) in NC-Co SA. Such abundant defects are
believed to enhance the ORR and OER catalytic activities. The
peak centered at 675 cm−1 in NC-Co is ascribed to the metallic
Co,43,57 whereas it is absent in the sample of NC-Co SA. This
result indicates the removal of Co large aggregates in NC-Co
SA after acidification, which is consistent with the above XRD
and STEM data.
3.2. Electrochemical Evaluation of NC-Co SA for ORR
and OER Activities. N-Coordinated Co sites, which exhibit a
similar chemical environment of CoN4 in the Co porphyrin
structure, are believed to be the active sites for ORR activity.58
Carbon flakes with high level of porosity and high density of
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defects are also crucial for accommodation of these active sites.
To elucidate the activity of Co−Nx coordination, linear sweep
voltammetry (LSV) measurements of NC-Co SA, NC-Co and
commercial Pt/C were performed at different rotation speeds
in 1 M KOH solution (Figure 3a,b). As shown in Figure 3a,
although the onset potential (Eonset) and half wave potential
(E1/2) of NC-Co SA (Eonset = 1.00 V, E1/2= 0.87 V, vs RHE)
are quite close to those of NC-Co (Eonset= 1.02 V, E1/2= 0.86
V, vs RHE), its saturation current at 0.60 V (vs RHE) can
reach 10.38 mA cm−2, which is dramatically larger than that of
NC-Co (6.93 mA cm−2) and Pt/C (8.52 mA cm−2). Its mass
activity at 0.9 V (vs RHE) can reach 1.25 A g−1, which is also
higher than that of NC-Co (1.09 A g−1). This suggests that
highly porous carbon flakes with a high density of Co−Nx
active sites in NC-Co SA facilitate oxygen adsorption and
subsequent OO bond breaking during the ORR reaction. By
contrast, the large Co particles existing in NC-Co are inactive
and play an insignificant role in boosting ORR activity. The
ORR LSV curves of NC-Co SA under different rotation speeds
and corresponding Koutechky−Levich (K−L) plots are
illustrated in Figure 3b. The K−L plots show a good linear
relationship between i−1 and ω−0.5 under three different
voltages. According to the K−L equation, the electron transfer
number per oxygen molecule (n) is calculated to be ≈4.07,
suggesting a preferable four electron pathway for the ORR.
However, for the NC-Co sample, n is only 2.75 (Figure S10).
Such a big difference is attributed to the agglomeration of Co
particles and the low content of Co−Nx active sites, reducing
the capacity for oxygen adsorption and mass transport of ionic
species. After acid leaching, most Co particles are removed,
and a large number of Co−Nx sites are exposed on the surface
of NC-Co SA to absorb oxygen molecules and promote the
electron transfer. As for the OER catalytic activities shown in
Figure 3c, when the current density reaches 10 mA cm−2, the
NC-Co SA presents a lower overpotential (360 mV) than that
of NC-Co (401 mV), showing its promising OER activity. The
double layer capacitance in Figure S11 further testifies that the
NC-Co SA has a larger active surface area than that of NC-Co.
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Figure 4. Performance of flexible solid-state rechargeable Zn−air batteries. (a) Mechanical flexibility and stability tests with continuous mechanical
alternation between flat and bent states. (b) Photograph of the three Zn−air batteries assembled with a minimum open circuit voltage of ≈4.232 V
measured by a voltammeter. (c) Photograph of 6 LEDs powered by two assembled Zn−air batteries with different bending angles (0°, 90°, 180°).
(d) Discharge and charge polarization curves. (e) Power−current density curves. (f) Comparison of the cycling stabilities in both bent and flat
states.

Furthermore, we have calculated the difference between the
OER voltage at 10 mA/cm2 and ORR half-wave potential (ΔE
= Ei=10 − E1/2). The smaller the ΔE value, the better the
catalyst performance as a reversible oxygen electrode.43 We
found that ΔE of NC-Co SA (0.72 V) is significantly smaller
than that of NC-Co (0.77 V). The larger TOF of NC-Co SA
compared to NC-Co also suggests a faster ORR and OER
kinetic rate (Figure S12). Based on the above experimental
results, the superior bifunctional activity of NC-Co SA can be
ascribed to the following features. First, a large number of Co−
Nx active sites can promote oxygen adsorption and mass
transport of ionic species. Second, the porous carbonaceous
flakes with large surface area accommodate a large number of
exposed active site that facilitate the reactions. Third, the
existence of N in the mesoporous carbon support can induce
uneven charge distribution, so the positively charged carbon
atoms are favorable to adsorb oxygen species. In contrast, for
the sample of NC-Co, although its Co content is higher than
the NC-Co SA, most Co−Co sites exist in the interior Co
aggregates and cannot be exposed to the electrolyte, thus they
will be useless for promoting the ORR activities.
Having proven the superior ORR and OER catalytic
properties of NC-Co SA, we assembled two aqueous Zn−air
batteries using NC-Co SA and Pt/C as the air cathodes, and
we then compared their catalytic stability by alternating 10 min
of discharge and 10 min of charge, as shown in Figure 3d. The
battery using NC-Co SA as the cathode did not show any
obvious voltage change under 570 charge/discharge cycles
(equal to 180 h), which was more stable than the battery using
Pt/C with 325 cycles (equal to 108 h), presenting the excellent
cycling stability of the former. The morphologies of NC-Co SA
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after cycling (Figure S13) reveal that the overall structure of
the nitrogen-doped carbon nanoflake arrays is well retained on
the carbon cloth after the long-term charging−discharging
process, suggesting that the Co single atoms remain stable in
the nanoflakes.
3.3. NC-Co SA as Air Cathode for the Flexible Solid-
State Zn−Air Batteries. Bifunctional electrocatalysts for
ORR and OER are highly desirable and important for metal−
air batteries. Considering the excellent ORR and OER
performance of flexible NC-Co SA, we have used our sample
as a binder-free air cathode and assembled a flexible solid-state
Zn−air battery with Zn foil anode, to test the flexibility and
stability performance (see the experimental section for details).
To the best of our knowledge, no literature has reported the
application of Co single-atom electrocatalysts in metal−air
batteries until now. The mechanical flexibility and stability of
NC-Co SA, NC-Co, and Pt/C were tested by flattening and
folding the batteries alternately per five cycles (see details in
Figure S14), as shown in Figure 4a. Compared with the Pt/C
and NC-Co, the NC-Co SA can withstand larger mechanical
change and exhibit less voltage change as well as better cycling
stability (up to 600 min) under continuous charging and
discharging processes. In addition to the excellent mechanical
stability, the battery with the NC-Co SA cathode can generate
a high open-circuit potential, up to 1.41 V (as shown in Figure
4b, 4.232 V for three NC-Co SA batteries in series), which was
much better than that of Pt/C cathode (1.27 V), previously
reported Fe-single-atom cathode (1.35 V) and Co-particle-
based cathode.43,59 Such high open circuit potential also
remained stable under 90° and 180° bending angles (Figure
S15). The device with two batteries connected in series was
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capable of lighting up six light emitting diodes (LEDs) in both
flat and bent states, showing a promising practical usage for
flexible electronics (Figure 4c). The charging−discharging
performance is shown by the polarization curves in Figure 4d.
When the current density reaches 10 mA cm−2, the voltage
gaps of NC-Co SA (0.45 V in flat states and 0.51 V in bent
states) are much smaller than those of NC-Co (1.140 V in flat
states and 0.52 V in bent states), demonstrating better
charging−discharging abilities. Figure 4e shows the power
density-current density curves for the solid state Zn−air
batteries. The NC-Co SA in its flat state shows a maximal
current density of 31.0 mA cm−2 and a peak power density of
20.9 mW cm−3, which are also better than those of NC-Co
(24.7 mA cm−2, 16.9 mW cm−3). In addition, we compared the
long-term cycling stabilities of batteries using NC-Co SA, NC-
Co, and Pt/C as air electrodes in both flat and bent states, as
shown in Figure 4f. The battery with NC-Co SA cathode
showed very stable charging−discharging potentials for 2500
min (125 cycles, one cycle for 20 min) in its flat state and 2200
min (110 cycles) in its bent state, outperforming the batteries
with NC-Co cathode (48 cycles in bent and flat states) and Pt/
C cathode (56 cycles in its flat state and 13 cycles in its bent
state). These results indicate that the NC-Co SA electro-
catalyst developed in the present work has great potential for
rechargeable Zn−air battery applications.
4. CONCLUSIONS
In summary, a mechanically flexible electrocatalyst NC-Co SA
comprising Co single atoms anchored in porous nitrogen-
doped carbon flakes was synthesized by a carbonization-
acidification process from Co-MOF precursor. The well-
dispersed Co single atoms were stably attached to the N-doped
carbon flakes through chemical bonding with N during the
carbonization process. Compared with Co nanoparticles grown
on NC, the NC-Co SA electrocatalyst with high density of
Co−Nx active sites demonstrates a lower OER overpotential
and much higher ORR saturation current, showing that the Co
metal clusters are redundant in driving both OER and ORR.
Benefiting from the excellent bifunctional activity, the flexible
NC-Co SA electrocatalyst was used as binder-free air cathodes
for the Zn−air batteries, which delivered a high open circuit
potential of 1.411 V with excellent cycling stabilities in both
flat and bent states. The single-atom catalysts show great
promise for the development of non-noble-metal-based
electrocatalysts for flexible energy conversion and storage
devices.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.8b02556.
Morphology of Co-MOF, NC-Co, and NC-Co SA
studied using SEM, HAADF-STEM, EDS, and EELS
analysis of NC-Co SA, N2 adsorption−desorption
isotherms and XPS results of NC-Co and NC-Co SA;
electrochemical test; and battery test of NC-Co SA
(PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: msegc@nus.edu.sg.
*E-mail: zl-liu@imre.a-star.edu.sg.
8967
Research Article
*E-mail: msewangj@nus.edu.sg.
*E-mail: steve.pennycook@nus.edu.sg.
ORCID
Wenjie Zang: 0000-0003-0604-9131
Afriyanti Sumboja: 0000-0002-7389-4442
Yue Wu: 0000-0003-2874-8267
Haijun Wu: 0000-0002-7303-379X
Cao Guan: 0000-0002-4468-7970
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This project of supported by the Ministry of Education
(Singapore), grant number: MOE 2015-T2-2-094, conducted
at the National University of Singapore. Z.L. acknowledges the
financial support from Advanced Energy Storage Research
Programme (IMRE/12-2P0503 and IMRE/12-2P0504), In-
stitute of Materials Research and Engineering of the A*STAR,
Singapore.
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8969 DOI: 10.1021/acscatal.8b02556

ACS Catal. 2018, 8, 8961−8969