Electrochimica Acta 220 (2016) 354–362

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

FeCo Alloy Nanoparticles Confined in Carbon Layers as High-activity

and Robust Cathode Catalyst for Zn-Air Battery
Pingwei Caia,b , Suqin Cia,* , Erhuan Zhanga , Ping Shaoa , Changsheng Caob ,
Zhenhai Wena,b,*
a
Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, Nanchang Hangkong University, Nanchang 330063, China
b
Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002,
China

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

Article history:
Received 18 September 2016 Highly electrocatalytic activity and strong stability towards both oxygen evolution (OER) and oxygen
Received in revised form 8 October 2016 reduction reaction (ORR) have been regarded as the critical factors in widespread application for the
Accepted 11 October 2016 renewable energy technologies. It still remains a huge challenge for developing bifunctional catalysts
Available online 13 October 2016 with low cost, efficiently electrocatalytic activity and strong stability. In this paper, FeCo alloy
nanoparticles embedded in nitrogen-doped carbon are synthesized through a simple thermal
Keywords: decomposition of Co-Fe Prussian Blue Analogue (Co-Fe PBA) in Ar atmosphere, during which the
oxygen evolution organic ligand of CN
in Co-Fe PBA provides both carbon and nitrogen sources for forming nitrogen-
oxygen reduction
doped carbon and FeCo alloy nanoparticles were formed, and thus producing a core-shell structure
FeCo alloy nanoparticles
(FeCo@NC). According to a set of electrochemical tests, the obtained FeCo@NC can function as a Janus to
Zn-air battery
drive OER and ORR with desirable activities and stabilities in alkaline media. Specifically, the FeCo@NC
presents an onset-potential of 1.45 V, a potential of 1.49 V at 10 mA cm
2, a Tafel slope of 62 mV dec
1 as
OER catalyst, and an onset potential of 0.94 V, a half-wave potential of 0.8 V as ORR catalyst. The
performance is comparable to those of precious metal based electrocatalysts, making it possible for
potential application in the renewable energy devices, especially Zn-air battery.
ã 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Increasing concerns have been raised on the growing energy
needs and environmental pollution caused by the depletion of
fossil fuels, which stimulate an intense interest in many energy
conversion and storage systems including rechargeable metal-air
batteries [1], fuel cells [2], carbon dioxide reduction [3] and full
water splitting [4]. Metal-air batteries are figured to be excellent
candidates for next generation electrical vehicles (EVs) and hybrid
electrical vehicles (HEVs) due to their highest energy density [5,6].
Whereas, the exploration of high-activity and good-stability
electrocatalysts for oxygen evolution reaction (OER) and oxygen
reduction reaction (ORR) is still the major challenge. Noble metals
* Corresponding authors at: Key Laboratory of Jiangxi Province for Persistent
Pollutants Control and Resources Recycle, Nanchang Hangkong University,
Nanchang 330063, China.
E-mail addresses: sqci@nchu.edu.cn (S. Ci), wenzhenhai@yahoo.com,
wen@fjirsm.ac.cn (Z. Wen).
based materials, i.e., Pt and RuO2, have been recognized as the best
electrocatalysts for ORR and OER, respectively. However, the high
costs and instability of these noble metals-based catalysts have
dramatically impeded their widespread application. Therefore, it is
an urgent target to develop noble-metal free bifunctional catalysts
with superior electrocatalytic activity for both OER and ORR.
Over the past years, numerous efforts have been devoted to
develop earth-abundant materials as bifunctional catalysts
towards both OER and ORR. On one hand, most noble metal free
electrocatalysts for OER reported so far are based transition-metal
oxides [7–11], phosphides [12–15], sulphides [16,17], nitrides [18],
selenides [19–23], carbides [24], and their alloys [25–27], but they
easily suffered from high over-potential, sluggish kinetics and
instability [28–30]. On the other hand, researchers found that
carbon nanomaterials (e.g. carbon nanotubes, graphene) with
heteroatom doping could be an efficient, low-cost, metal-free and
environmental alternative to Pt for ORR [31–37]. Accordingly, the
combination of transition metal-based materials and carbon
matrix was proposed to be a prospective strategy not only to

http://dx.doi.org/10.1016/j.electacta.2016.10.070
0013-4686/ã 2016 Elsevier Ltd. All rights reserved.
 P. Cai et al. / Electrochimica Acta 220 (2016) 354–362
improve the stability of metal-based materials [38,39], but also to
endow the hybrids with favourable electrocatalytic activity for
both OER and ORR [40,41]. However, the multi-step synthetic
procedures and high fabricating cost hindered the large scale
commercialization [42].
Herein, integrating the advantages of both alloys and nitrogen-
doped carbon, we report a simple synthetic strategy for fabricating
core-shell nanohybrids with nitrogen-doped carbon encapsulating
FeCo alloy nanoparticles (FeCo@NC). The resultant FeCo@NC not
only show excellent bifunctional catalytic propeties toward OER
and ORR with high activities, but also hold the initial performance
with good stability, due to the synergetic effect between alloy
nanoparticles and carbon shell. As a result, when applied in Zn-air
battery, the FeCo@NC air-cathode exhibits favourable performance
compared to other counterparts.
2. Experimental section
2.1. Materials
Cobalt nitrate hexahydrate (Co(NO3)26H2O, 99%), potassium
hexacyano-ferrate, potassium hexacyano-percobaltate and KOH
were purchased from Shanghai Chemical Reagents, China. Nafion
(5%) and sodium citrate was obtained from Aladdin. All of the
reagents related in this experiment were analytical grade and
directly used without further purification.
2.2. Synthesis
Synthesis of Co-Fe and Co-Co Prussian Blue Analogues (PBA):
Typically, 10 mmol of potassium hexacyano-ferrate was dissolved
in 500 ml deionized (DI) water to form a clean solution, then pour
into 500 ml solution containing 15 mmol of cobalt nitrate and
22.5 mmol of sodium citrate with continuous magnetic stirring.
After 10 min, the mixed solution was aged for another 24 h at room
temperature. Centrifugation and washed with water and absolute
ethanol for several times to remove the soluble impurities, The red
Co-Fe PBA nanocubes were obtained by drying at 70  C overnight
under vacuum. The Co-Co PBA nanocubes were prepared in the
same method expect for replacing potassium hexacyano-ferrate
with potassium hexacyano-percobaltate.
Synthesis of FeCo@NC and Co@NC-750 core-shell nanopar-
ticles: The FeCo@NC core-shell nanoparticles were prepared by
calcination the as synthesized Co-Fe PBA. In a typical method,
200 mg of obtained Co-Fe PBA were placed in a combustion boat,
transferred into a furnace and then calcinated in Ar atmosphere at
the temperature of 550, 650, 750  C for 4 h with a heating rate of
2  C min
1, denoted as FeCo@NC-550, FeCo@NC-650 and
FeCo@NC-750 respectively. The FeCo@NC core-shell nanoparticles
were obtained after cooling to ambient temperature under Ar
atmosphere naturally. The Co@NC-750 core-shell nanoparticles
were obtained by the same method except for replacing the Co-Fe
PBA with Co-Co PBA at the calcination temperature of 750  C.
Synthesis of NC-750 alloy and FeCo-750 nanoparticles:
Typically, 200 mg of as prepared FeCo@NC-750 were immersed
in 20 ml 3 M HCl, and then ultrasonication for 1 h continuously.
Centrifugation and washed with water and absolute ethanol for
several times to remove the soluble impurities. The samples
(denoted as NC-750) were obtained by drying at 70  C overnight
under vacuum. To obtain the FeCo-750 nanoparticles, 200 mg of
obtained Co-Fe PBA were placed in a combustion boat and then
transferred into a furnace and was calcinated in H2/Ar hybrid
atmosphere [43,44] at the temperature of 750  C for 4 h with a
heating rate of 2  C/min. The FeCo-750 nanoparticles were
obtained after cooling to ambient temperature under Ar atmo-
sphere naturally.
355
2.3. Characterizations
X-ray powder diffraction (XRD) patterns were performed on
X-ray diffractometer (Miniflex6000, Rigaku) at 40 kV and 15 mA
using Cu-Ka radiation (l= 1.54178 Å). The field-emission scanning
electron microscopy (FE-SEM) images were obtained on Hitachi
SU8010 at high vacuum with an acceleration voltage of 5 kV. The
transmission emission electron microscopy (TEM) was carried out
on FEI F20 microscopeat an acceleration voltage of 200 kV. X-ray
photoelectron spectra (XPS) were taken on ESCALAB 250Xi
(Thermo Scientific) XPS spectrometer with an Al Ka as the
excitation source (1486.6 eV). The C-C component may be set to a
binding energy of 284.8 eV, by default. Make sure the offset
between measured binding energy of C-C and charge correction
reference of 284.8 eV. For other elements, the binding energy were
obtained by adding or minusing the offset. Specific surface area and
pore size distribution of the products was examined by the
Brunauer-Emmett-Teller (BET) method using nitrogen adsorption
and desorption isotherms on a Micromeritics Instrument Corpo-
ration sorption analyzer (Micromeritics TriStar II 3020).
2.4. Electrochemical measurements
Briefly, 5 mg of as synthesized samples, 50 ul of 5% Nafion
solution, 30 ul of ethanol and 400 ul of DI water were added into a
microcentrifuge in sequence to form a homogeneous ink with the
assistance of ultrasonication. Then, 6 ul of the ink was dropped
onto the surface of glass carbon electrode (GCE, 3 mm and RRDE,
4 mm). The mass loading of active materials are about 0.8 mg cm
2
and 0.4 mg cm
2 respectively. All the electrochemical measure-
ments were carried out using a CHI 760E electrochemical
workstation in a three-electrode system which modified GCE,
platinum wire and Ag/AgCl in saturated KCl solution served as
working electrode, counter electrode and reference electrode
respectively. The measured potentials vs. Ag/AgCl were convert to a
reversible hydrogen electrode (RHE) based on the Equation
(ERHE = EAg/AgCl + 0.059  pH + 0.197). The data for polarization
curves and cyclic voltammograms were captured before activation
and stabilization of the working electrodes by running cyclic
voltammetry many segments.
2.4.1. OER test:
The electrochemical catalytic activity towards oxygen evolution
reaction was characterized by polarization curves using linear
sweep voltammetry (LSV) at a scan rate of 5 mV s
1 in 1 M KOH
under sustained O2 to ensure the O2/H2O equilibrium at 1.23 V vs.
RHE. Electrochemical impedance spectroscopy (EIS) were obtained
by applying an AC voltage with 5 mV amplitude in a frequency
range from 105 to 10
2 Hz and recorded at 1.505 V vs. RHE in the
same conditions. The electrical double layer specific capacitor (Cdl)
of the materials were measured from double-layer charging curves
using the cyclic voltammograms (CVs) in a small potential range at
different scan rate (2 mV s
1 to 10 mV s
1). The plot current density
against scan rate has a liner relationship and its slope is the Cdl.
RRDE voltammogrames were applied to monitor the intermediate
products (H2O2) during the process of water oxidation with a scan
rate of 5 mV s
1 and a rotation rate of 1500 rpm. Specifically, in
order to conform the reaction pathway for OER, the Pt ring
electrode potential was set as 1.505 V vs. RHE for the detection of
H2O2 oxidation in 1.0 M KOH at a potential ranging from 1.005 to
1.805 V. Stability is a key factor for the performance of OER
electrocatalysts. Herein, the stability was characterized by the
Chronoamperometry performed at 1.505 V for 20000 s which as
synthesized samples were coated on Ni foam as working electrode
with a loading mass of  0.8 mg cm
2.
356 P. Cai et al. / Electrochimica Acta 220 (2016) 354–362
2.4.2. ORR test:
The electrochemical catalytic activity towards oxygen evolution
reaction was characterized by polarization curves and voltam-
mogrames conducted on a CHI 760E electrochemical workstation
and a RDE-3A (ALS Co., Ltd) in 0.1 M KOH, and the scan rate of CVs
and LSVs was kept 50 and 5 mV s
1 respectively. The slopes of their
best linear fit lines were used to calculate the number of electrons
transformed in oxygen reduction according to K-L Eqs. (1) and (2):
1 1 1 1
¼ þ ¼
j jL jK Bv1=2
B ¼ 0:62nFC0 ðD0 Þ2=3 V
1=6
Where jL is the measured current; jK is the kinetic-limiting current
and v is the electrode rotation rate; n is the overall number of
transferred electrons in the ORR process; F is the Faradaic constant
(96485C/mol), C0 is the oxygen concentration (solubility) in 0.1 M
KOH (1.2  10
6 mol cm
3); D0 is the oxygen diffusion coefficient in
0.1 M KOH (1.90  10
5 cm2 s
1) and V is the kinematic viscosity of
the 0.1 M KOH (0.01 cm2 s
1).
For the RRDE measurements, catalyst inks and electrodes were
prepared by the same method as for RDE. The disk electrode was
scanned at a rate of 5 mV s
1, and the ring potential was constant at
1.5 V vs. RHE. The transfer number (n) were determined by the
followed equations:
Id
n¼4
Id þ Ir =N
Where Id is the disk current, and Ir is the ring current, and N is
current collection efficiency of the Pt ring. N is 0.44.
2.4.3. Zn-air battery test:
To evaluate the performance of Zn-air batteries, a home-made
battery was builted. The air electrode for Zn-air batteries included
a gas diffusion layer (GDL) on the air side and a catalyst layer (CL)
on the solution side, which can performed on the carbon paper. The
CL was made by loading catalyst ink onto the side of carbon paper
with a loading mass of 1 mg cm
2 (1 cm2) for all catalysts. A piece of
Zinc plate was used as anode and 6 M KOH containing 0.2 M zinc
acetate was used as electrolyte. The Zn-air batteries were tested in
ambient conditions. The polarization curves were obtained by LSV
technique with CHI760E electrochemical working station. The
galvanostatic discharge and charge cycling (5 min discharge and
5 min charge with the current density of 10 mA cm
2) were
performed in LAND testing system.
3. Results and discussion
The entire synthesis process is quite simple, which starts from a
co-precipitation route to synthesize crystalline Co-Fe PBA precur-
sor, followed by a thermal annealing in an Ar atmosphere, finally
leading to a core-shell structure with nitrogen-doped carbon
encapsulating FeCo alloy nanoparticles (Scheme. 1).
The morphology of PBA was characterized by the Filed-
emission scanning electron microscopy (FE-SEM), suggesting the
prepared Co-Fe PBA are cubic structure and homogeneous
distribution with an average size of ca 360 nm (Fig. 1a and S1).
The peaks on the XRD pattern of the Co-Fe PBA (Fig. S2) are well
matched to the Co3 [Fe (CN) 6]2 (H2O) 17 (simulated from 262661-
ICSD). After the thermal decomposition at 750  C in an Ar
atmosphere, the cubic morphology of Co-Fe PBA was converted
to core-shell structured FeCo@NC-750 nanoparticles (FeCo@NC-
750) with a size of about 20 nm (Fig. 1b and S3). The high-
resolution transmission emission microscopy (HRTEM) further
ð1Þ
Scheme 1. Schematic illustration on the synthesis of FeCo@NC Core-shell
ð2Þ nanoparticles.
manifests the alloy particles were encapsulated by a carbon layers
(Fig. 1c), in which the crystalline FeCo nanoparticles have a lattice
fringe space of 2.1 Å corresponding to the (110) lattice plane and
carbon layers have a lattice fringe space of 3.4 Å belonging to the
(002) lattice plane of graphite, which is consistent with the
diffraction ring of the selected area electron diffraction (SAED)
pattern (Fig. 1d). The peaks located at about 45.0 and 65.5 in the
XRD pattern of FeCo@NC-750 (Fig. 2a) were well assigned to the
(110) and (102) lattice planes of FeCo alloy (JCPDS 65-4131)
respectively. Also, there is a shoulder peak at around 25 , which is
derived from the graphite carbon layers, being consistant with
results of the lattice fringe space of (002) plane. Fig. 2b displays the
N2 adsorption-desorption isotherm curve and corresponding pore-
ð3Þ
size distribution curve for the FeCo@NC-750. According to the
reports, the as-synthesized sample displays a pore size distribution
at 2.5 nm and 3.7 nm, a BET surface areas of 42 m2 g
1, and a pore
volume of 0.14 cm
3 g
1.
The XPS survey spectrum of the FeCo@NC-750 is presented in
Fig. 2c, highlighting the existence of Fe, Co, C, element. It should be
noted that a strong peak at around 530.7 eV could be attributed to
the adventitious O and the forms of C-O. The presence of N doping
demonstrates N-doping reaction do occur on the carbon shell
(Fig. S4a). The high resolution XPS spectra for N 1s, Fe 2p, Co 2p are
plotted (Fig. S4b–d). To further verify our analysis, the N 1 s high-
resolution spectrum before and after argon sputtering was
collected (Fig. S4b) and the nitrogen content was constant after
the treatment. This phenomenon manifested that the nitrogen
have doped into the carbon layer since that argon sputtering
treatment could remove the background nitrogen. Especially, C 1 s
can divided into four peaks (Fig. 1f). The peak at 284.57 eV is
contributed to the signal of reference carbon [45,46]. The peaks
locked at 285.41 and 286.45 eV originate from the forms of C-O
[45,47] and CRN [48,49], respectively. The peak at 283.52 eV
indicates the formation of metallic bonds between metal and
carbon [50–52].
The electrocatalytic activity of catalysts towards OER was
characterized by the polarization cures in O2-saturated 1 M KOH
solution with the scan rate of 5 mV s
1. As shown in Fig. 3a, the
FeCo@NC-750 displays an onset potential of 1.45 V (vs. RHE), which
is lower than that of FeCo@NC-550 (1.6 V), FeCo@NC-650
(1.5 V), and is comparable to the RuO2 (1.45 V), indicating an
improved catalytic activity in FeCo@NC-750 for OER. The potentials
required for affording a current density of 10 mA cm
2 is a crucial
benchmarking for the OER [53]. The FeCo@NC-750 deliver a
current density of 10 mA cm
2 at 1.49 V, lower than that of
FeCo@NC-550 at 1.55 V, FeCo@NC-650 at 1.68 V, RuO2 at 1.53 V, and
even can beat most of the OER electrocatalysts reported previously
[17,25,30,54–56].
The catalytic kinetics for OER was reflected by Tafel slope
obtained from Tafel plot (Fig. 3b). The FeCo@NC-750 presents a
 P. Cai et al. / Electrochimica Acta 220 (2016) 354–362
Fig. 1. (a) SEM image of Co-Fe PBA, (b) TEM image, (c) HRTEM image, (d) SADE pattern of FeCo@NC-750.
much lower Tafel slope (52 mV dec
1) than that of FeCo@NC-550
(119 mV dec
1), FeCo@NC-650 (85 mV dec
1) and RuO2 (69 mV
dec
1), and also shows comparable to the previously reported OER
catalysts [57,58], demonstrating a fast OER kinetic and high activity
of FeCo@NC-750. A detailed comparisons of various OER catalysts
towards the OER activities is listed (Table S1), further manifesting
the excellent performance to catalyze OER for the FeCo@NC-750.
Stability is a crucial parameter to elevate the performance of
catalysts. The amperometric i-t curve (Fig. 3c) manifests high
stability of FeCo@NC-750, it could deliver a current density of
22 mA cm
2 and keep 88.2% of the original catalytic current after
continuous test for 6 h (Fig. S5a), which is also evidenced by the
polarization curve operated before and after stability test
(Fig. S5b). To further investigate the mechanism for OER, RRDE
was applied to monitor the intermediate (H2O2) originating from
the process of water oxidation. As shown in Fig. 3d, the ring
electrode shows a very slight enhance in current upon the testing
process, demonstrating the negligible intermediate formation and
then a desirable four-electron pathway for the OER at the
FeCo@NC-750.
In order to get a deep insight about the effect of calcination
temperature on the performance towards OER, the EIS and CVs
with different scan rate were recorded. Fig. 4a shows the Nyquist
plots of the three samples, all of them are composed of two
semicircles, which is proved by the magnified images of Nyquist
plots and the corresponding equivalent circuit (Fig. 4a inset). As
shown in Table S2, the FeCo@NC-750 exhibits a charge transfer
resistance of 91.7 ohm, smaller than that of CoFe@NC-550
357
(288.5 ohm) and FeCo@NC-650 (103.2 ohm), indicating the high
electrochemical activity of the FeCo@NC-750. The Cdl of the
samples were measured from double-layer charging curves using
the CVs at the potential range of 1.305-1.405 V (Fig. 4b and S6). The
plot current density against scan rate has a linear relationship and
its slope corresponds to the Cdl (Fig. 4c). The Cdl of the FeCo@NC-
750 is calculated to be 60 mF cm
2, which is much higher than that
of FeCo@NC-550 (1.32 mF cm
2) and FeCo@NC-650 (20.05 mF
cm
2), indicating that the FeCo@NC-750 can expose more
electroactive site and thus achieve an ultrahigh electrocatalytic
activity for OER, which is basically consistent with the result of the
BET surface area (Fig. 4d). It is noted that when the calcination
temperature increased to 850  C, the samples agglomerated with
the combustion boat, perhaps, due to some reactions occurred
between FeCo alloy and combustion boat.
It should be noted that the Co@NC-750 (Fig. S7a) synthesized
from the Co-Co PBA (Fig. S7b) exhibits an onset-potential of 1.55 V,
a potential of 1.60 V at the current density of 10 mA cm
2, a Tafel
slope of 76 mV dec
1 and a Cdl of 33.7 mF cm
2 (Fig. S8); these
parameters fall far behind those of FeCo@NC nanoparticles,
indicting the synergistic effect between Co and Fe in the
FeCo@NC-750.
Furthermore, to illustrate the synergistic effect between FeCo
alloy and Nitrogen-doped Carbon, FeCo-750 and NC-750 were
prepared adopting a similar method to prepare FeCo@NC. The
FeCo-750 and NC-750 display onset-potentials of 1.5 and 1.58 V,
and require potential of 1.57 and 1.64 V to reach a current density of
10 mA cm
2. In addition, the FeCo-750 and NC-750 show Tafel
358 P. Cai et al. / Electrochimica Acta 220 (2016) 354–362

Fig. 2. (a) XRD pattern, (b) N2 adsorption isotherm and (inset) the corresponding pore size distribution, (c) survey spectra and (d) C 1 s spectra of FeCo@NC-750.

Fig. 3. (a) Polarization cures and (b) Tafel plots of FeCo@NC-550, FeCo@NC-650, FeCo@NC-750. (c) Amperometric i-t curve and (d) polarization curves of disk and ring current
on an RRDE at the rotating speed of 1500 rpm of FeCo@NC-750.

slope of 216 and 88 mV dec
1 and Cdl of 9.2 and 7.4 mF cm
2 synergistic effects between FeCo alloy and Nitrogen-doped Carbon
respectively (Fig. S9). All of the performances are inferior to those for FeCo@NC-750 electrocatalyst. Moreover, the nitrogen-doped
of FeCo@NC-750, further demonstrating the key roles and carbon in here play a key role to protect the FeCo alloy due to the
 P. Cai et al. / Electrochimica Acta 220 (2016) 354–362 359

Fig. 4. (a) EIS and (inset) magnified EIS recorded at 1.505 V. (b) CVs of FeCo@NC-750 at different scan rate from 2 to 10 mV s
1. (c) Plots of the current density at 1.32 V vs. the
scan rate and (d) N2 adsorption isotherm of FeCo@NC-550, FeCo@NC-650 and FeCo@NC-750 respectively.

formation of chemical interaction between metal and carbon, such
robust structure endows the as-developed electrocatalyst with
excellent stability.
To test the ORR electrocatalytic activity of the as-obtained
FeCo@NC-750 and control samples, CV, rotating disk electrode
(RDE) and RRDE was carried out in alkaline solution (0.1 M KOH),
respectively. The compared CVs in O2 and Ar-saturated solution are
presented in Fig. 5a, a well-defined oxygen reduction peak centred
at 0.79 V (vs. RHE) implies a good catalytic activity for FeCo@NC-
750 catalyst. The control experiments for the commercial Pt/C
catalyst (20.wt% Pt loading), FeCo@NC-650 and FeCo@NC-550
were also carried out under the same condition, as shown in Fig. 5a.
The FeCo@NC-750 shows a significantly enhanced reduction peak
current density compared with the other two FeCo@NC samples,
suggesting a higher catalytic activity. The LSV curves were
additionally recorded at a RDE in O2-saturated 0.1 M KOH at a

Fig. 5. (a) CVs in atmosphere of Ar (black line) and O2 (red line), (b) polarization cures at the speed of 1600 rpm in O2 atmosphere, (c) Tafel plots of FeCo@NC and 20% Pt/C
respectively.
360 P. Cai et al. / Electrochimica Acta 220 (2016) 354–362

scan rate of 5 mV s
1 with the rotation rate of 1600 rpm (Fig. 5b).
The FeCo@NC-750 exhibits an onset potential (0.94 V vs. RHE), a
half-wave potential of 0.80 V (vs. RHE), and a diffusion-limited
current density of 4.82 mA cm
2; these values are even comparable
to the commercial Pt/C and outperform those of FeCo@NC-650 and
FeCo@NC-550. The much smaller Tafel slope of 54.6 mV dec
1 for
FeCo@NC-750 than other comparison samples further confirm its
excellent ORR activity (Fig. 5c).
The electron-transfer number (n) can be calculated from the
slopes of Koutecky-Levich plots at various potentials. RDE
measurements were recorded from 400 rpm to 2500 rpm in O2
saturated electrolyte. Fig. S10a, d display the polarization cures and
corresponding K-L curves for Pt/C. The transfer electron number (n)
is determined to be 4 according to the Koutecky-Levich Equation,
which is in good agreement with some reports[31,37,47,59],
suggesting clearly four-electron pathway for ORR. As can be seen
in Fig. 6a, b and S10, when the potential was polarized in the more
negative position, the electron transfer number are ranged in the
region 3.38-3.79, being very close to that of the commercial Pt/C
and being higher than the other reference catalysts (Fig. 6c).
To further validate the ORR catalytic pathways upon electro-
catalysis, RRDE was conducted to determine the selectivity of the
four-electron reduction of oxygen. The disk potential was scanned
at 5 mV s
1 and the Pt ring was polarized at 1.5 V (vs. RHE) in
alkaline electrolyte. The electron-transfer numbers (n) of all the
samples at different potentials can be obtained according to disk
current (id) and ring current (ir) on the basis of the RRDE
measurements. The electron transfer number (n) was calculated to
be about 3.9 for FeCo@NC-750 according to RRDE measurements
(Fig. 6d, e), consistent with the result obtained from the Koutecky-
Levich plots, suggesting the ORR catalyzed by the FeCo@NC-750 is
dominated by a 4e reduction pathway. A detailed comparisons of
various ORR catalysts towards the ORR activities is listed (Table S3),
the excellent performance parameters further demonstrate the
favourable ORR performance of as-synthesized sample.
Fig. 6f shows the time dependent current density curves of the
FeCo@NC-750 and Pt/C electrodes at static potential of 0.7 V (vs.
RHE) in O2 saturated 0.1 M KOH, the FeCo@NC-750 electrode only
shows 13% loss of the initial current after a continuous running of
20000 s, much better than 30% current loss at the commercial Pt/C
catalyst, indicating that the FeCo@NC-750 exhibits superior
durability to Pt/C catalyst. Also, LSV curves was carried out to
test the stability of all the catalysts after i-t tests at a applied
potential for 20000 s, the FeCo@NC-750 show a negative shift of
3 mV in half-wave potential, in contrast, the Pt/C shows a negative
shift of 13 mV (Fig. S11). For the reasonable reason, the carbon layer
could not only efficiently confine the FeCo alloy nanoparticles in
limited space to avoid agglomeration, but also protect FeCo alloy
nanoparticles from corrosion of electrolyte, avoiding the process of
the dissolution and re-deposition.

Fig. 6. (a) Polarization curves at the rotating speed from 400 to 2500 rpm, (b) responding K-L plots. (c) Electron transfer number (n) calculated from K-L equation at different
potential of FeCo@NC and 20% Pt/C. (d) Polarization curves of disk and ring current density on an RRDE at the rotating speed of 1500 rpm of FeCo@NC-750. (e) Electron transfer
number (n) at various potential obtained from RRDE. (f) Chronoperometric responds of FeCo@NC-750 and 20% Pt/C at 0.7 V.
 P. Cai et al. / Electrochimica Acta 220 (2016) 354–362 361

To evaluate the performance of FeCo@NC-750 as catalyst in
Zn-air batteries, a home-mad Zn-air battery was constructed, in
which a zinc plate and the FeCo@NC-750 dual functional catalyst
loaded on carbon paper were used as the anode and air-cathode
respectively, and a high open circuit voltage (OCV) of 1.38 V was
achieved (Fig. 7a). Fig. 7b shows the galvanodynamic behaviors of
the FeCo@NC-750 and Pt/C catalysts during Zn-air batteries
discharge and charge processes. Zn-air battery with FeCo@NC-
750 bifunctional catalyst air-cathode had a lower charge-discharge
voltage gap compared to the battery with a Pt/C air-cathode,
demonstrating a better rechargeability. Fig. 7c reproduces the
power density curves for Zn-air batteries with FeCo@NC-750 and
Pt/C catalysts. The maximum power density of the Zn-air battery
using FeCo@NC-750 catalyst was calculated to be 132 mW cm
2,
which is comparable to that of Pt/C (136 mW cm
2). The
galvanostatic discharge curves at 2 mA cm
2 are presented in
Fig. 7d. The battery with the FeCo@NC-750 and Pt/C air cathode
showed voltage plateaus of  1.275 V and 1.30 V, with specific
capacitors of 763 and 743 mAh g
1 respectively when normalized
to the weight of consumed zinc electrode [60]. Fig. 7e shows the
discharge-charge cycling curves at the constant current density of
10 mA cm
2 for Zn-air battery. The change of voltage gap for
FeCo@NC-750 air-cathode was lower than that of Pt/C air-cathode,
indicating the better cycling performance than that of Pt/C,
possibly, due to the core-shell structure and the protection of
carbon layer [61].
Based on the aforementioned experimental results and
discussions, the superior electrocatalytic activities and strong
stability of FeCo@NC for OER and ORR are probably contribute to
the synergetic effect from each unit: (1) the core-shell structure
could not only provide more active sites and reduce the resistance,
improving the catalytic performance, but also efficiently avoid
FeCo alloy nanoparticles agglomeration and dissolution/re-depo-
sition, maintaining the highly electrocatalytic stability; (2) the

Fig. 7. (a) Photograph of home-made Zn-air battery with an open circuit voltage of 1.38 V, (b) Charge-discharge polarization curves; (c) Power density curves; (d)
Galvanostatic discharge curves at 2 mA cm
2; (e) Galvanostatic discharge-charge cycling curves at 10 mA cm-2 of Zn-air batteries with the FeCo@NC-750 and 20% Pt/C as
catalyst respectively.
362 P. Cai et al. / Electrochimica Acta 220 (2016) 354–362
nitrogen doping could induce the change of charge distribution
and then produce high density of defects, which can be served as
active sites to accelerate OER and ORR; (3) the formation of metal
carbides (MCx), as active species, could also promote the catalytic
activity of ORR. Besides, the FeCo nanoparticles could catalysis the
graphization of carbon, enhancing the conductivity. Nevertheless,
all these possible scenarios still call for further in-depth
mechanistic investigation.
4. Conclusions
In summary, we have synthesized FeCo@NC core-shell nano-
particles as excellent bifunctional electrocatalysts toward OER and
ORR in alkaline solution by thermal decomposition of CoFe-PBA in
an Ar atmosphere. The organic ligand of CN
provide both carbon
and nitrogen source for forming nitrogen-doped carbon, which
could efficiently protect the FeCo alloy and thus obtained a robust
structure. Besides, the large BET surface, the synergetic effect from
each unit, and the core-shell nanostructure of FeCo@NC could
afford highly density active sites and reduce the electrochemical
resistance and then endow it with electrocatalytic activity for OER
and ORR. The multiple advantages in the as-developed FeCo@NC,
including facile synthetic strategy, low cost, and excellent catalytic
performance, may open up a new avenue to develop promising
electrocatalyst for ORR and OER involved application. Furthermore,
the excellent Zn-air battery performance with superior stability,
may hold the possibility for large-scale application in practice.
Acknowledgements
This work was supported by the National Natural Science
foundation of China (21566025), the Natural Science Foundation of
Jiangxi Province (20152ACB21019), the Graduate Student Innova-
tion Foundation of Nanchang Hangkong University (YC2015018),
start-up funding from FJIRSM-CAS. Z.H.W. is also thankful for the
award of “The Recruitment Program of Global Youth Experts”.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.
electacta.2016.10.070.
References
[1] Z.L. Wang, D. Xu, J.J. Xu, X.B. Zhang, Chem. Soc. Rev. 43 (2014) 7746–7786.
[2] R. Bashyam, P. Zelenay, Nature 443 (2006) 63–66.
[3] I. Castro-Rodriguez, K. Meyer, J. Am. Chem. Soc. 127 (2005) 11242–11243.
[4] Y. Meng, W. Song, H. Huang, Z. Ren, S.Y. Chen, S.L. Suib, J. Am. Chem. Soc. 136
(2014) 11452–11464.
[5] P.G. Bruce, S.A. Freunberger, L.J. Hardwick, J.-M. Tarascon, Nature materials 11
(2012) 19–29.
[6] J.B. Goodenough, Accounts Chem. Res. 46 (2012) 1053–1061.
[7] H. Hu, B. Guan, B. Xia, X.W. Lou, J. Am. Chem. Soc. 137 (2015) 5590–5595.
[8] B. Li, Y. Liang, X. Yang, Z. Cui, S. Qiao, S. Zhu, Z. Li, K. Yin, Nanoscale 7 (2015)
16704–16714.
[9] T.Y. Ma, S. Dai, M. Jaroniec, S.Z. Qiao, J. Am. Chem. Soc. 136 (2014) 13925–13931.
[10] M.H. Seo, H.W. Park, D.U. Lee, M.G. Park, Z. Chen, ACS Catalysis 5 (2015)
4337–4344.
[11] Y. Jin, H. Wang, J. Li, X. Yue, Y. Han, P.K. Shen, Y. Cui, Adv. Mater. 28 (2016)
3785–3790.
[12] J. Ryu, N. Jung, J.H. Jang, H.-J. Kim, S.J. Yoo, ACS Catalysis 5 (2015) 4066–4074.
[13] L.-A. Stern, L. Feng, F. Song, X. Hu, Energy & Environ. Sci. 8 (2015) 2347–2351.
[14] M. Ledendecker, S. Krick Calderón, C. Papp, H.P. Steinrück, M. Antonietti, M.
Shalom, Angew. Chem. Int. ed. 127 (2015) 12538–12542.
[15] C.-C. Hou, S. Cao, W.-F. Fu, Y. Chen, ACS applied materials & interfaces 7 (2015)
28412–28419.
[16] N. Cheng, Q. Liu, A.M. Asiri, W. Xing, X. Sun, Journal of Materials Chemistry A 3
(2015) 23207–23212.
[17] L.-L. Feng, G. Yu, Y. Wu, G.-D. Li, H. Li, Y. Sun, T. Asefa, W. Chen, X. Zou, J. Am.
Chem. Soc. 137 (2015) 14023–14026.
[18] P. Chen, K. Xu, Z. Fang, Y. Tong, J. Wu, X. Lu, X. Peng, H. Ding, C. Wu, Y. Xie,
Angew. Chem. Int. ed. 127 (2015) 14923–14927.
[19] C. Tang, N. Cheng, Z. Pu, W. Xing, X. Sun, Angew. Chem. Int. ed. 54 (2015)
9351–9355.
[20] G.F. Chen, T.Y. Ma, Z.Q. Liu, N. Li, Y.Z. Su, K. Davey, S.Z. Qiao, Adv. Funct. Mater.
26 (2016) 3314–3323.
[21] L. Liang, H. Cheng, F. Lei, J. Han, S. Gao, C. Wang, Y. Sun, S. Qamar, S. Wei, Y. Xie,
Angew. Chem. Int. ed. 54 (2015) 12004–12008.
[22] I.H. Kwak, H.S. Im, D.M. Jang, Y.W. Kim, K. Park, Y.R. Lim, E.H. Cha, J. Park, ACS
applied materials & interfaces 8 (2016) 5327–5334.
[23] Z. Pu, Y. Luo, A.M. Asiri, X. Sun, ACS applied materials & interfaces 8 (2016)
4718–4723.
[24] K. Xu, H. Ding, H. Lv, P. Chen, X. Lu, H. Cheng, T. Zhou, S. Liu, X. Wu, C. Wu, Adv.
Mater. 28 (2016).
[25] S. Chen, J. Duan, M. Jaroniec, S.Z. Qiao, Angew. Chem. Int. ed. 52 (2013)
13567–13570.
[26] S. Ci, S. Mao, Y. Hou, S. Cui, H. Kim, R. Ren, Z. Wen, J. Chen, J. Mater. Chem. A 3
(2015) 7986–7993.
[27] Y. Feng, H. Zhang, Y. Zhang, X. Li, Y. Wang, ACS applied materials & interfaces 7
(2015) 9203–9210.
[28] S. Chen, J. Duan, M. Jaroniec, S.Z. Qiao, Adv. Mater. 26 (2014) 2925–2930.
[29] J. Zhang, Z. Zhao, Z. Xia, L. Dai, Nat. Nanotechnol. 10 (2015) 444–452.
[30] T.Y. Ma, S. Dai, M. Jaroniec, S.Z. Qiao, Angew. Chem. Int. ed. 53 (2014)
7281–7285.
[31] X. Li, G. Liu, B.N. Popov, J. Power Sources 195 (2010) 6373–6378.
[32] W. Wei, H. Liang, K. Parvez, X. Zhuang, X. Feng, K. Mullen, Angew. Chem. Int. ed.
53 (2014) 1570–1574.
[33] J. Liang, Y. Jiao, M. Jaroniec, S.Z. Qiao, Angew. Chem. Int. ed. 51 (2012)
11496–11500.
[34] Y.J. Sa, C. Park, H.Y. Jeong, S.H. Park, Z. Lee, K.T. Kim, G.G. Park, S.H. Joo, Angew.
Chem. Int. ed. 53 (2014) 4102–4106.
[35] L. Dai, Y. Xue, L. Qu, H.J. Choi, J.B. Baek, Chem. Rev. 115 (2015) 4823–4892.
[36] V. Nallathambi, J.-W. Lee, S.P. Kumaraguru, G. Wu, B.N. Popov, J. Power Sources
183 (2008) 34–42.
[37] Z. Wen, S. Ci, Y. Hou, J. Chen, Angew. Chem. Int. ed. 53 (2014) 6496–6500.
[38] M.-R. Gao, X. Cao, Q. Gao, Y.-F. Xu, Y.-R. Zheng, J. Jiang, S.-H. Yu, ACS Nano 8
(2014) 3970–3978.
[39] M. Gong, Y. Li, H. Wang, Y. Liang, J.Z. Wu, J. Zhou, J. Wang, T. Regier, F. Wei, H.
Dai, J. Am. Chem. Soc. 135 (2013) 8452–8455.
[40] X. Li, Y. Fang, X. Lin, M. Tian, X. An, Y. Fu, R. Li, J. Jin, J. Ma, Journal of Materials
Chemistry A 3 (2015) 17392–17402.
[41] D.U. Lee, J.Y. Choi, K. Feng, H.W. Park, Z. Chen, Advanced Energy Materials 4
(2014).
[42] Y. Yang, Z. Lun, G. Xia, F. Zheng, M. He, Q. Chen, Energy & Environ. Sci. 8 (2015)
3563–3571.
[43] S. Adak, L.L. Daemen, M. Hartl, D. Williams, J. Summerhill, H. Nakotte, J. Solid
State Chem. 184 (2011) 2854–2861.
[44] Q. Song, X. Wang, L. Lu, X. Yang, Thermochim Acta 150 (1989) 185–192.
[45] Z. Song, T. Lin, L. Lin, S. Lin, F. Fu, X. Wang, L. Guo, Angew. Chem. Int. ed. 55
(2016) 2773–2777.
[46] X. Zhang, X. Xie, H. Wang, J. Zhang, B. Pan, Y. Xie, J. Am. Chem. Soc. 135 (2012)
18–21.
[47] Y. Hou, Z. Wen, S. Cui, S. Ci, S. Mao, J. Chen, Adv. Funct. Mater. 25 (2015)
872–882.
[48] H. Gao, S. Yan, J. Wang, Y.A. Huang, P. Wang, Z. Li, Z. Zou, Phys. Chem. Chem.
Phys. 15 (2013) 18077–18084.
[49] C. Li, X. Yang, B. Yang, Y. Yan, Y. Qian, Mater Chem. Phys. 103 (2007) 427–432.
[50] J.B. Kim, B. Jang, H.-J. Lee, W.S. Han, D.-J. Lee, T.E. Hong, S.-H. Kim, Mater. Lett.
168 (2016) 218–222.
[51] D. Lopez, W. Schreiner, S. De Sánchez, S. Simison, Appl. Surf. Sci. 207 (2003)
69–85.
[52] P. Arod, S. Shivashankar, RSC Advances 5 (2015) 59463–59471.
[53] C.C. McCrory, S. Jung, J.C. Peters, T.F. Jaramillo, J. Am. Chem. Soc. 135 (2013)
16977–16987.
[54] C. Tang, H.S. Wang, H.F. Wang, Q. Zhang, G.L. Tian, J.Q. Nie, F. Wei, Adv. Mater. 27
(2015) 4516–4522.
[55] Y. Li, P. Hasin, Y. Wu, Adv. Mater. 22 (2010) 1926–1929.
[56] J.X. Feng, H. Xu, Y.T. Dong, S.H. Ye, Y.X. Tong, G.R. Li, Angew. Chem. Int. ed. 128
(2016) 3758–3762.
[57] X. Zhou, Z. Xia, Z. Zhang, Y. Ma, Y. Qu, Journal of Materials Chemistry A 2 (2014)
11799–11806.
[58] J. Wang, D. Gao, G. Wang, S. Miao, H. Wu, J. Li, X. Bao, Journal of Materials
Chemistry A 2 (2014) 20067–20074.
[59] Z. Wen, S. Ci, F. Zhang, X. Feng, S. Cui, S. Mao, S. Luo, Z. He, J. Chen, Adv. Mater. 24
(2012) 1399–1404.
[60] Q. Liu, Y. Wang, L. Dai, J. Yao, Adv. Mater. 28 (2016) 3000–3006.
[61] G. Li, X. Wang, J. Fu, J. Li, M.G. Park, Y. Zhang, G. Lui, Z. Chen, Angew. Chem. Int.
ed. 55 (2016) 4977–4982.