You are on page 1of 10

Nano Energy 31 (2017) 541550

Contents lists available at ScienceDirect

Nano Energy
journal homepage:

NiCo2S4 nanocrystals anchored on nitrogen-doped carbon nanotubes as a MARK

highly ecient bifunctional electrocatalyst for rechargeable zinc-air

Xiaopeng Hana,c, Xiaoyu Wua, Cheng Zhonga,b, , Yida Denga, Naiqin Zhaoa,b, Wenbin Hua,b,
Tianjin Key Laboratory of Composite and Functional Materials, School of Material Science and Engineering, Tianjin University, Tianjin 300072, China
Key Laboratory of Advanced Ceramics and Machining Technology (Ministry of Education), Tianjin University, Tianjin 300072, China
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, China


Keywords: The commercial development of metal-air batteries with remarkably high theoretical energy output is largely
Metal-air batteries limited by the scarcity of low-cost and highly stable electrocatalysts with activities for oxygen reduction reaction
Nanocomposite (ORR) and oxygen evolution reaction (OER) comparable to precious metals and their alloys. Herein, a new
Metal sulde inorganic-nanocarbon coupled hybrid, homogeneous NiCo2S4 nanocrystals anchored on nitrogen-doped carbon
Nitrogen-doped carbon nanotubes
nanotubes (NiCo2S4/N-CNT), has been developed as an extremely ecient bifunctional catalyst to promote the
Bifunctional electrocatalysis
sluggish ORR and OER kinetics for advanced rechargeable zinc-air battery. It is found that the highest activity is
obtained by tailoring the crystal size of NiCo2S4 in the hybrid through tuning the construction of metal-
ammonia complexes. The optimized NiCo2S4/N-CNT nanocomposite exhibits extraordinary bifunctional
activity through half reaction testing, displaying comparable ORR activity to state-of-the-art carbon supported
platinum (Pt/C) and superior OER capability to RuO2 as well as much better durability. The resulting battery
performance in generative Zn-air system further conrms its superb eective bi-functionality for catalyzing dual
ORR and OER. Compared with those of well-known commercial Pt/C and RuO2, the synergetic NiCo2S4/N-CNT
hybrid enables signicantly reduced charge-discharge polarization (~0.63 V), enlarged energy eciency
(~67.2%) and prolonged cyclability up to 150 cycles at 10 mA cm2. The tremendously enhanced electro-
chemical behaviors arise from favorable factors including small sized, homogenous dispersed novel NiCo2S4
nanocrystals and coupling interaction between sulde spinels and underlying N-doped CNT network, which not
only provides ecient electron transfer pathway but also alters the electronic structure, thus facilitating the
oxygen electrocatalysis during the discharge-charge processes.

1. Introduction Otherwise, the insucient durability of these noble metal-based cata-

lysts still need further improvement owning to the dissolution, Ostwald
Rechargeable metal-air batteries have received increasing attention ripening, and aggregation of active species in prolonged cycle period
owing to their prominent advantages including drastically high energy [1013]. More importantly, it is extremely dicult to exploit one
density (510 folds than current lithium-ion batteries), cost eective, electrocatalyst with satisfactory activities for both ORR and the rever-
safe and environmental compatibility [1,2]. The intrinsic sluggish sible OER [14]. Thus, it is urgently imperative to design and develop
kinetics of oxygen reduction reaction (ORR) and oxygen evolution earth-abundant, corrosion-resistant and highly active bifunctional elec-
reaction (OER) occurred on the air cathode is one of the major technical trocatalysts for dual ORR and OER to build next generation rechargeable
obstacles, resulting in large battery overpotential, limited practical metal-air batteries.
energy density and poor reversibility of oxygen chemistry [35]. At Among precious-metal-free alternatives, rst-row transition metal
present, precious metals (e.g., Pt, Ru, and Ir) and their alloys are chalcogenides have been extensively investigated as ORR and OER
recognized to possess the best oxygen electrocatalytic activities, however, catalysts owning to their advantages of high abundant resources, low
their prohibitive price and rare availability bring great challenges for the cost and considerable activity [1521]. Among them, cobalt suldes
widespread practical implementation of metal-air batteries [69]. (e.g., Co3S4, Co9S8, Co1xS etc.) have attracted particular attention for

Corresponding author at: Tianjin Key Laboratory of Composite and Functional Materials, School of Material Science and Engineering, Tianjin University, Tianjin 300072, China.
E-mail addresses: (C. Zhong), (W. Hu).
Received 11 November 2016; Received in revised form 5 December 2016; Accepted 5 December 2016
Available online 06 December 2016
2211-2855/ 2016 Elsevier Ltd. All rights reserved.
X. Han et al. Nano Energy 31 (2017) 541550

application in oxygen electroreduction [2227]. Theoretical calcula- power density of 147 mW cm2 and energy density of 554.6 Wh kg1.
tions have already predicted that the Co9S8 catalyzed the ORR via a When employed in real rechargeable Zn-air cells, the NiCo2S4/N-CNT-
four-electron transfer pathway, which is similar to Pt surface [28]. based electrode achieves smaller ORR and OER polarization (0.63 V),
However, the experimental performance still lies far behind so far. higher energy eciency (67.2%) and several times longer operational
Recent research has demonstrated Ni doped Co-S to form thiospinel life (150 cycles) than those of precious Pt/C (0.90 V, 59.8%, 59 cycles)
compound (i.e., NixCo3xS4) can display enhanced ORR performance in and RuO2 (0.79 V, 60.5%, 44 cycles) catalysts at 10 mA cm2, respec-
comparison with binary Co-S composition [26]. Unfortunately, the tively. This study should shed light on exploring potential earth-
moderate OER capability and intrinsic limited electronic conductivity abundant candidate alternatives to promote the development of next-
still need to be overcome in order to meet the practical requirements of generation rechargeable metal-air batteries technologies.
oxygen-related regenerative metal-air technologies.
Downsizing the particles could signicantly contributes to the much 2. Experimental section
enhanced electrocatalytic eciency owning to resulted higher specic
surface area and increased active surface-atom exposure ratio [29,30], 2.1. Material synthesis
which can not only oer more interfacial active sites, but also shorten
the mass/electron transfer distance. To compensate the poor electrical A modied Hummers method was adopted to prepare the mildly
conductivity, the combination of active species and carbonaceous oxidized multi-walled CNT. In a typical synthesis, 1 g CNT was added
nanomaterials (e.g., carbon nanotube (CNT) and graphene) has been to 23 mL concentrated H2SO4 and stirred for 20 h at ambient atmo-
proven to be a promising strategy to achieve the resultant hybrids with sphere. After addition of 400 mg NaNO3 into the mixture, 1 g KMnO4
excellent electrocatalytic activity and satised stability by virtue of was then slowly added at 40 C. 3 mL deionized water was added drop
improved overall conductivity and the coupling synergetic eect by drop after continuous stirring for 30 min, followed by another
[17,19]. Furthermore, doping heteroatoms (e.g., N, P) into the carbon addition of 3 mL deionized water after 5 min. Another 5 min later,
framework could further optimizes the surface electronic structure 40 mL deionized water was subsequently added. Then after 15 min,
congurations and the adsorption/desorption behaviors towards oxy- 140 mL deionized water together with 10 mL H2O2 (30 wt%) was
gen intermediates, thus facilitating the electrocatalytic kinetic pro- added to mixture to terminate the oxidization process. Finally, the
cesses in metal-air chemistries [31,32]. CNT with mildly oxidization state were collected, washed with 5%
Based on these design principles, we herein demonstrate the hydrochloric acid and water, then lyophilized.
rational design and controllable synthesis of covalent hybrid of In a typical synthesis of NiCo2S4/N-CNT, 68 mg as-prepared mildly
NiCo2S4 nanocrystals homogeneously grown on N-doped multiwall oxidized CNT were ultrasonically dispersed in 38 mL ethanol and 2 mL
CNT (designated as NiCo2S4/N-CNT) through a facile two-step meth- deionized water mixed solvent. Then, 0.3 mmol Co(AC)24H2O and
od, which involving a formation of hydrolyzed metal precursors as the 0.15 mmol Ni(AC)24H2O were dissolved in the above 40 mL suspension
nucleation and then a simple solvothermal crystallization process to and stirred at 80 C for 2 h in water bath, followed by addition of desired
aord the resultant hybrid (Scheme 1). Interestingly, the crystal size of amount of NH3H2O. After stirring for another 2 h, 0.9 mmol thiourea
supported NiCo2S4 spinels can be easily tailored by tuning the was added to the above system. After continuous stirring for 20 h, the
nucleation degree with metal-ammonia coordination. The N-CNT reaction mixture was transferred to a 50 mL autoclave for solvothermal
matrix underlying the crystallized NiCo2S4, oers an electron transfer reaction at 170 C for 3 h. After cooling to room temperature, the
framework for active centers, connes the growth size of suldes, and prepared sample was collected by centrifugation and washed with
boosts the oxygen electrochemistry performance through the synergis- deionized water and dried by lyophilization overnight. For comparisons,
tic interaction between two components. Electrochemical half-cell tests NiCo2S4/CNT was prepared following similar procedures except without
revealed that the optimized NiCo2S4/N-CNT hybrid exhibited superior the addition of NH3H2O and bulk NiCo2S4 particle were synthesized
overall catalytic activity than bare NiCo2S4 and N-free CNT supported under the same conditions in the absence of CNT matrix.
NiCo2S4 (designated as NiCo2S4/CNT). Particularly, the NiCo2S4/N-
CNT manifests comparable ORR onset/half-wave potential (0.93 V,
2.2. Materials characterization
0.80 V) and diusion current density (3 mA cm2) compared to that of
commercial carbon supported Pt (Pt/C, 0.95 V, 0.83 V, 2.95 mA cm2),
The phase purity and micro-nanostructured morphologies of the as-
accompanied with superior long-term durability. The composite also
synthesized samples were respectively characterized by powder X-ray
renders prominent improvement in OER capability (70 mV lower than
diraction (XRD, Bruker/D8 Advanced with Cu K radiation), eld-
RuO2 to reach 10 mA cm2), rendering excellent bifunctional activity of
emission scanning electron microscopy (SEM, Hitachi S4800, 30 kV) and
about 0.80 V in alkaline medium, comparable to those of highly active
transmission electron microscopy (TEM, JEOL JEM-2100F, 200 kV)
noble-metal, transition-metal and metal-free catalysts reported so far.
equipped with an energy-dispersive spectrometer (EDS). Raman spectra
The resulting primary Zn-air battery exhibits high discharge peak
were performed using a confocal Raman microscope (DXR, Thermo-

Scheme 1. Schematic illustration of the preparation of NiCo2S4/N-CNT nanocomposite.

X. Han et al. Nano Energy 31 (2017) 541550

Fisher Scientic) at 532 nm excitation from an argon ion laser. Where Id, Ir, and N correspond respectively to the disk, ring currents,
Thermogravimetric tests were conducted in air atmosphere from room and current collection eciency of RRDE.
temperature to 850 C with heating rate of 10 C/min using Netzsch
STA449F3 Jupiter analyzer. The Brunauer-Emmett-Teller (BET) specic 2.4. Zn-air battery assembly
surface area was determined by using the N2 adsorption/desorption
isotherms at 77 K on an AutosorbiQ instrument (Quantachrome U.S.) The Zn-air battery was assembled by zinc plate anode, 6.0 M KOH
with a 6 h outgas at 80 C. X-ray photoelectron spectroscopy (XPS) results electrolyte with 0.2 M ZnCl2 dissolved (to ensure the reversible Zn
were collected on a Perkin Elmer PHI 1600 ESCA system. anode reaction) and air catalysts coated on carbon ber paper as the
cathode. The porous air cathode was prepared by casting catalyst ink of
2.3. Electrochemical measurements NiCo2S4/N-CNT or Pt/C (10 mg) or 3 mg RuO2 mixed with 7 mg
Vulcan carbon XC-72 in 1 mL mixture solution of deionized water/
The electrochemical performance was tested using a three-electrode ethanol (volume ratio: 4:1) and 140 l Naon on carbon ber paper
system comprising a platinum foil counter electrode, a saturated and dried at 100 C for 4 h. The average catalyst loading is about
calomel reference electrode and a catalyst-modied rotating ring-disk 1.0 mg cm2. The LAND-CT2001A testing devices were used to analyze
glass-carbon working electrode (disk diameter 5.61 mm). In a typical the battery discharge/charge performance and cycling reversibility with
procedures to prepare the working electrode, a mixture of 3 mg oxygen continuously fed to the cathode during the measurements. The
NiCo2S4 and 7 mg carbon powder (Vulcan XC-72) or 10 mg NiCo2S4/ voltage-current polarization data was performed on IviumStat work-
CNT, NiCo2S4/N-CNT was suspended in a mixed solvent containing station in oxygen atmosphere. The electrolyte was pre-purged with
0.8 mL deionized water, 0.2 mL ethanol, and 0.14 mL Naon (v/v/v high-purity O2 for at least 20 min before each test.
=4/1/0.7) to form a homogeneous catalyst ink. As for the precious
metal catalysts, 10 mg Pt/C or 3 mg RuO2 mixed with 7 mg carbon 2.5. Li-air battery assembly
were used. Then 7.0 l of the as-prepared ink was deposited onto the
GC electrode and dried at ambient condition to aord a mass loading of The non-aqueous coin-type Li-air cell was fabricated in an argon-
~ 0.248 mg cm2. The electrolyte (0.1 M KOH) was pre-purged with lled glove box (Mikrouna Super 1220/750/900) using a lithium metal
high-purity Ar or O2 for at least 30 min before each test and anode, a glass ber separator, and a catalyst-coating oxygen cathode.
maintained gas ow until the end of the tests. Electrochemical data 1 M LiTFSI (lithium bis-(triuoromethanesulfonyl)-imide) dissolved in
were performed on a IviumStat workstation accompanied with a TEGDME (tetraethylene glycol dimethyl ether) is employed as the
rotating system (PHYCHEMI). Before collecting the data, several CV electrolyte. The air cathodes were prepared by casting a homogenous
curves were scanned until the stabilized signals were observed. The ink of 90 wt% catalyst materials (NiCo2S4/N-CNT) and 10 wt% poly-
linear sweep voltammetry was scanning at a potential scan rate of vinylidene uoride (PVdF) onto the carbon paper with a catalyst
5 mV s1 and the ring potential was constant at 1.3 V vs RHE for ORR. loading of about 1 mg cm2 and then dried at 110 C in vacuum
The ORR polarization curves were subtracted the background currents overnight. The specic capacity and current density were calculated
in Ar-saturated electrolyte. The OER voltammetry were corrected with based on the amount of the catalyst. The tests were conducted in 1 atm
iR-compensation. All the potential were transferred with reference to high-purity oxygen atmosphere.
standard reversible hydrogen electrode (RHE) according to following
equation: Evs RHE = Evs SCE +0.99 V in 0.1 M KOH [33]. The electro- 3. Results and discussion
chemical surface area was determined by using the in situ method
based on the measurement of electrochemical double layer capacitance As schematically illustrated in Scheme 1, the controllable synthesis
in non-Faradaic potential region. Electrochemical impedance spectra of NiCo2S4 nanoparticles supported on N-CNT nanocomposite pro-
were measured in a frequency range of 100 kHz100 mHz at a bias ceeds through facile nucleation-crystallization two step strategy after
potential of 0.8 V vs. RHE. the CNT pre-oxidation (see experimental section for details). In the
The Koutecky-Levich plots can be constructed to analyze the ORR rst nucleation step, the mildly oxidized CNT was reacted with certain
kinetics with the following equation: amount of Co(OAc)2, Ni(OAc)2 in an ethanol/water NH4OH mixed
solvent at 80 C to form hydrolyzed metal precursors on the functional
1 1 1 1 1
= + = groups of CNT nanostructure [19]. Afterward, solvothermal treatment
I Ik Id nFAkC 0 0.62nFADO2/3
v1/6C 0w1/2 was adopted to simultaneously incorporate N into carbon framework
where I, Ik, and Id represent the measured, kinetic, and diusion- and crystallize metal suldes on the surface of N-CNT in thiourea
limiting current densities, respectively, n is the transferred electron solution, yielding the designed spinel NiCo2S4/N-CNT hybrid. The
number of oxygen reduction, F is the Faraday constant, A is the interaction between the introduced electronegative oxygen-containing
geometric electrode area (cm2), k is the rate constant of the reaction, functional groups, N dopants and the metal cations (i.e. Ni2+, Co2+)
C0 is the oxygen-saturated concentration in 0.1 M KOH, DO2 is the contributes to the homogeneous nucleation and nal anchor of formed
oxygen diusion coecient, is the kinetic viscosity of solvent, and NiCo2S4 nanocrystals [34]. In the powder X-ray diraction (XRD)
is the rotation rate in unit of rad s1. Thus, the kinetic currents used to proles of the synthesized samples (Fig. 1a), the peaks of NiCo2S4 can
t the tafel curves can be calculated on the basis of following equation: be readily assigned to the spinel NiCo2S4 (Joint Committee on Powder
Diraction Standards, JCPDS card No. 200782, space group: Fd-3 m)
I Id with divalent ions occupying tetrahedral sites and trivalent ions
Ik =
Id I occupying octahedral sites (Fig. 1b). Compared with pure NiCo2S4,
the broadened XRD diraction peaks of the hybrid indicate the
For analyzing the RRDE, the percentage of peroxide species and the
ultrane size of supported NiCo2S4 nanocrystallines, especially in the
electron transfer number (n) were determined using the following
case of NiCo2S4/N-CNT. The presence of CNT in the hybrid is
conrmed by the signicantly increased peak intensity at 2 27,
4NId which originates from the (002) graphitic diraction of carbon
NId + Ir structure (Fig. S1, Supporting Information). This is also veried by
the analysis from Raman spectra. Two characteristic peaks of the D
HO2 (%) = (1350 cm1) and G band (1590 cm1) were indentied in NiCo2S4/N-
NId + Ir CNT hybrid. The intensity ratio of D/G (ID/IG) are ca. 0.40, 0.95, and

X. Han et al. Nano Energy 31 (2017) 541550

Fig. 1. (a) XRD proles of synthesized NiCo2S4, NiCo2S4/CNT, and NiCo2S4/N-CNT samples. (b) Crystal structure of spinel NiCo2S4. (c-e) SEM and TEM images of NiCo2S4/N-CNT.
Inset in (e) displays the FFT patterns of a single nanocrystalline. (f) Elemental mapping of NiCo2S4/N-CNT.

0.87 for pristine CNT, oxidized CNT, and NiCo2S4/N-CNT (Fig. S2), nanocrystal size of 15.4 nm. The reason is that N-groups can serve as
suggesting that the abundant vacancies are introduced in graphitic favorable anchor sites for sulde nanocrystals owing to the coordina-
lattice after the oxidization treatment while the N dopants are tion eect with Ni2+, Co2+ cations, leading to a smaller NiCo2S4
embedded in the defect sites of the carbon net in NiCo2S4/N-CNT crystalline size with higher degree of nucleation on N-CNT than on
hybrid. Otherwise, the low integrated area ratios of sp3 to sp2 (Asp3/ N-free CNT [33,35]. The size dierence is also consistent with the
Asp2 =0.19, 0.15, and 0.18, respectively) are indicator of sp2 hybridiza- broadened extent of XRD peaks. What's more, the particle size
tion type carbon atoms in the synthesized samples. dramatically grows to be several hundred nanometers and aggregates
Fig. 1c presents the eld-emission scanning electron microscopy severely without the support of CNT (Fig. 2d). The clear lattice fringes
(SEM) image of NiCo2S4/N-CNT nanocomposite, which inherits the with neighboring interlayer distances of 0.29 and 0.34 nm in high-
typical morphology of CNT with average diameter of 100 nm (Fig. S1). resolution TEM (Fig. 1e) are consistent with the spacing of (311) and
Transmission electron microscopy (TEM) image (Fig. 1d) clearly (220) planes in spinel NiCo2S4. The well-dened points in correspond-
reveals that uniform NiCo2S4 nanocrystals are homogenously dispersed ing fast Fourier transform (FFT) diraction pattern (inset in Fig. 1e)
on N-doped CNT nanoarchitecture matrix without obvious detachment coincides with the Bragg diraction of cubic crystal structural symme-
and aggregation. It is found that the crystal size can be signicantly try of NiCo2S4. The energy dispersive spectroscopy (EDS) elemental
aected by dierent amounts of NH3H2O in the reaction system. The mapping demonstrates the homogeneous dispersion of various ele-
mass-average nanocrystalline size in NiCo2S4/N-CNT is about 15.4 nm ments including C, N, Ni, Co, and S in the NiCo2S4/N-CNT hybrid
when adding 0.5 mL and increased to 28.7and 46.2 nm when using (Fig. 1f), conrming the uniform distribution of NiCo2S4 deposited on
0.25 and 0 mL NH3H2O, respectively (Fig. 2a-c). Unless stated, the the nitrogen-doped carbon matrix. EDS results further revealed that
NiCo2S4/N-CNT in the following section refers to the hybrid with the atomic ratio of Ni: Co: S is approximately 1:2:4, again conrming

X. Han et al. Nano Energy 31 (2017) 541550

Fig. 2. TEM images of NiCo2S4/N-CNT with NH3H2O adding amount of 0.5 (a), 0.25 (b) and 0 mL (c). (d) SEM image of bare NiCo2S4. Inset in (a-c) shows the particle size

Fig. 3. (a) Ni 2p, (b) Co 2p XPS spectra of synthesized NiCo2S4, NiCo2S4/CNT, and NiCo2S4/N-CNT. (c) S 2p, and (d) N 1 s of NiCo2S4/N-CNT.

the formation of spinel NiCo2S4 phase (Fig. S3). The weight amount of thermogravimetric analysis (TGA) in air (Fig. S4), respectively. The
suldes are measured to be about 55.4 wt% and 53.8 wt% in the Brunauer-Emmett-Teller (BET) specic surface area of NiCo2S4/N-
synthesized NiCo2S4/CNT and NiCo2S4/N-CNT nanocomposites by CNT hybrid is determined to be 73.14 m2 g1 by N2 adsorption/

X. Han et al. Nano Energy 31 (2017) 541550

Fig. 4. (a) Cyclic Voltammograms of NiCo2S4, NiCo2S4/CNT, and NiCo2S4/N-CNT in O2-saturated 0.1 M KOH at 25 mV s1. (b) Linear voltammograms of NiCo2S4, NiCo2S4/CNT,
NiCo2S4/N-CNT, and Pt/C measured using RRDEs at 5 mV s1. (c) Corresponding percentage of peroxide (solid line) and electron transfer number (dotted line) at various potentials. (d)
K-L plots at 0.5 V. (e) Tafel plots determined from the corresponding voltammetry data. (f) Dependence of current densities as a function of scan rates at 0.8 V.

desorption measurements (Fig. S5). The type-IV isotherm with H3-

Table 1 type hysteresis loop indicates that mesopores and macropores both
Summary of electrocatalytic performance of prepared catalysts in this worka. exist in the hybrid (also see inset in Fig. S5), which can promote the
Catalyst Eonset (V) Ehalf (V) Is (mA Ik (mA Im (mA n E
catalytic reaction by providing more exposed active sites and enough
cm2) cm2) mg1) (Ej=10- tri-phase contact area to facilitate oxygen transportation and electro-
Ehalf) lyte permeation.
X-ray photoelectron spectroscopy (XPS) was performed to gain
NiCo2S4 0.77 0.64 2.16 0.03 8.71 3.37 1.04
insight into the elemental compositions and chemical oxidation states
NiCo2S4/ 0.84 0.69 2.66 0.17 10.71 3.65 0.94
CNT of NiCo2S4 compound and the interaction with carbon nanotube
NiCo2S4/ 0.93 0.80 3.00 3.20 12.10 3.82 0.80 (Fig. 3). The XPS survey spectra of NiCo2S4, NiCo2S4/CNT, and
N-CNT NiCo2S4/N-CNT reveal the presence of Ni, Co, and S with desired
Pt/C 0.95 0.83 2.95 6.90 11.90 3.90
stoichiometric ratio, in consistent with the EDS analysis (Fig. S6). In
a the Ni 2p XPS spectra (Fig. 3a), two spin-orbit doublets and two
Eonset is the onset potential, Ehalf is the half-wave potential, Is is the specic current,
Ik is the kinetic current density at 0.8 V, Im is the mass current density, E is the shakeup satellites (denoted as Sat.) are best tted by using a Gaussian
variance metric between OER current density of 10 mA cm2 and Ehalf. Is, Im, and n tting method, corresponding to characteristic peaks of Ni2+ and Ni3+.
correspond to the values at 0.5 V. The rotation rate is 400 rpm. The Co 2p spectra (Fig. 3b) can be deconvoluted into six species,

X. Han et al. Nano Energy 31 (2017) 541550

Fig. 5. (a) Chronoamperometric curves of NiCo2S4/N-CNT hybrid and Pt/C at 0.8 V vs RHE in O2-saturated 0.1 M KOH. (b) Cyclic Voltammograms of NiCo2S4/N-CNT with prolonged
cycles at 400 rpm at a scanning rate of 200 mV s1. (c) Electrocatalytic OER activity of the synthesized catalysts and the counterpart Pt/C and RuO2. (d) Comparison of OER and ORR
bifunctional activities of samples in this work with representative electrocatalysts in references. The dotted lines show the E at constant values.

Fig. 6. (a) A schematic conguration of Zn-air batteries. (b) Polarization curves and corresponding power densities of NiCo2S4/N-CNT and Pt/C-based cathodes.

including pairs of tting peaks for Co2+ and Co3+, and their shakeup active, favoring the enhancement of electrocatalytic capability
satellites, respectively. These results suggest that the coexistence of [17,19]. Fig. 3c shows the core-level spectrum of the S 2p region in
mixed valence of Ni2+, Ni3+, Co2+, and Co3+ in prepared products, in NiCo2S4/N-CNT hybrid, which can be deconvoluted into four peaks
accordance with the reports for NiCo2S4 in literatures [36,37]. along with one shake-up satellite peak. The peaks centered at 163.1
Particularly, the Ni and Co 2p peaks of the composite shifted positively and 161.8 eV are assigned to S 2p1/2 and S 2p3/2, respectively. Another
to higher binding energy as compared with that of neat NiCo2S4 as a tting peak at 163.8 eV is a typical signal of a metal-sulfur bond, while
result of the migration of metal electron cloud induced by the strong the component peak located at 162.6 eV is an indicator of the presence
electronegativity of doped N and O species on N-CNT surface, of sulfur ions (S2-) in a low coordination state on the surface [36,38].
demonstrating strong covalent coupling between the spinel and The successful incorporation of N into CNT framework in NiCo2S4/N-
nanocarbon substrate [17,30]. The intimate hybridization interaction CNT was proved by N signal (Fig. S6). The detected substantial N
renders the nanocomposite highly conductive and electrochemical content is about 4.68 at% and four types of N conguration are

X. Han et al. Nano Energy 31 (2017) 541550

Fig. 7. (a) Discharge/recharge proles of rechargeable Zn-air cells based on NiCo2S4/N-CNT, Pt/C and RuO2 cathode with duration of 400 s per cycle at 10 mA cm2. Inset shows a LED
light lit by assembled Zn-air battery. (b) 1st and 150th discharge/charge curves of NiCo2S4/N-CNT electrode. (c) Voltage-current polarization data of the NiCo2S4/N-CNT, Pt/C and
RuO2 catalyst.

identied in the high-resolution N 1 s spectrum (Fig. 3d), correspond- ORR performance derived by NiCo2S4/N-CNT hybrid is closer to that
ing to pyridinic N (398.6 eV, 52.72%), pyrrolic N (399.6 eV, 26.27%), of commercial Pt/C in terms of onset/half-wave potential and reduc-
graphitic N (400.8 eV, 9.48%), and oxidized N (402.4 eV, 11.52%), tion current. The electrochemical parameters of NiCo2S4/N-CNT is
respectively. The positive peak shift is also pronounced for N species comparable to the reported activities based on precious metal-free
due to the strong interaction of C-N-transition metal [17]. These XPS catalysts [15,16,2226,29,30].
results demonstrate the successful formation of NiCo2S4 crystallo- The ORR catalytic activity was further assessed by the calculated
graphic phase with mixed metal valence and the strong covalent electron transfer number (n) and generated peroxide percentage from
coupling between sulde spinels and the underlying N-doped carbon the RRDE plots. As illustrated in Fig. 4c, the monitored n is above ~3.8
nanostructure within NiCo2S4/N-CNT hybrid. and peroxide percentage is below ~10% for NiCo2S4/N-CNT nanocom-
Half-cell testing was employed to assess the ORR and OER posite over the potential range of 0.230.83 V, much better than the
activities of synthesized compounds in alkaline electrolyte via a tri- other two comparatives. Similar to Pt/C, the NiCo2S4/N-CNT hybrid
electrode conguration. Fig. 4a shows the typical cyclic voltammo- catalyzed the ORR via an apparent 4e pathway, consistent with the
grams (CVs) in 0.1 M KOH saturated with high-purity Ar (dotted line) determination from the Koutecky-Levich curves constructed at dier-
or O2 (solid line). For NiCo2S4/N-CNT, the cathodic peak potential ent rotation rates (Fig. 4d). Higher n and lower peroxide yield again
located at 0.78 V, more positive than that of NiCo2S4/CNT (0.70 V) and suggest the enhancement of ORR kinetic properties due to the
bare NiCo2S4 (0.68 V). Thus, the NiCo2S4/N-CNT attains the better combination of NiCo2S4 nanocrystals and conductive CNT substrate.
ORR catalytic activity, which is further conrmed by the results Superior ORR performance of NiCo2S4/N-CNT is also gleaned from the
determined from rotating ring-disk electrode (RRDE). Fig. 4b displays much smaller Tafel slopes at lower overpotentials and larger kinetic
the linear sweeping voltammograms at a potential scanning rate of currents (Fig. 4e) than those measured over NiCo2S4 and NiCo2S4/CNT
5 mV s1 under rotating speed of 400 round per minute (rpm). The counterparts. Since the electrochemical active surface areas are calcu-
disk currents reect ORR electrocatalysis (currents are negligible in Ar- lated to be 25.5, 62.5, 76.0 m2 g1 for NiCo2S4, NiCo2S4/CNT and
saturated electrolyte, Fig. S7) while the ring currents are relevant to the NiCo2S4/N-CNT based on the linear correlation of current density
oxidation of generated intermediate peroxide species. Compared to versus the scan rate (Fig. 4f and S10) in double-layer capacitance
bulk NiCo2S4 (optimal additive conductive carbon amount is found to dominated potential region, the order of catalytic activities can be thus
be 70 wt%, Fig. S8), the nanocomposites exhibit lower overpotential, easily understood. Moreover, electrochemical impedance spectroscopy
higher half-wave potential and larger reduction current. As for the two measurements reveal that a much lower charge transfer resistance is
hybrids, the NiCo2S4/N-CNT is catalytically more active than NiCo2S4/ demonstrated on NiCo2S4/N-CNT than those on pure NiCo2S4 and
CNT, enabling an enhancement of onset and half-wave potential by 90 NiCo2S4/CNT (Fig. S11), further indicating faster ORR kinetic proper-
and 110 mV, respectively, and a 12.8% enlarged limiting current ties on N-doped nanocomposite.
density (Table 1). The activity gradually decreases as the size of Apart from high catalytic activity, the hybrid NiCo2S4/N-CNT
supported NiCo2S4 nanocrystals increased mainly due to reduced aords satisfactory catalytic durability. After a continuous chronoam-
active surface-atom exposure ratio (Fig. S9) [29]. Remarkably, the perometric period of 25 h, the ORR current on NiCo2S4/N-CNT can

X. Han et al. Nano Energy 31 (2017) 541550

Table 2
Comparison of key performance parameters for rechargeable Zn-air batteries extracted from literature.

Air catalyst Mass loading Zn electrode Voltage polarization Cycling condition Stability Reference
(mg cm2) electrolyte

NiCo2S4/N-CNT 1.0 Zn foil 0.63 V @ j=10 mA cm2; 10 mA cm2, 400 s per 150 cycles; polarization This work
6 M KOH + 0.2 0.80 V @ j=20 mA cm2 cycle period increased 0.06 V at the
ZnCl2 end

MnO2/CNT composite 0.5 Zn plate ~1.1 V @ j=10 mA cm2 ~8 mA cm2, 600 s per 50 cycles; polarization Electrochim. Acta, 69
6 M KOH cycle period increased ~0.4 V at the (2012) 295300.

Co3O4/MnO2 2.0 Zn plate ~0.80 V @ j=10 mA cm2 15 mA cm2, 420 s per 60 cycles; polarization Nanoscale, 5 (2013)
6 M KOH cycle period increased ~0.3 V at the 46574661.

LaNiO3/N-CNT 0.72 Zn plate ~1.2 V @ j=20 mA cm2 ~17.6 mA cm2, 600 s 75 cycles; polarization Nano Lett., 12 (2012)
6 M KOH per cycle period increased 0.10.2 V at 19461952.
the end

CoO/N-CNT + NiFe 1.0/5.0 Zn foil ~0.69 V @ j=10 mA cm2 10 mA cm2, 200 s per 60 cycles; negligible Nat. Commun., 4 (2013)
LDH 6 M KOH + cycle period voltage change at the 1805.
0.2 M Zn(AC)2 end

a-MnO2-LaNiO3/CNTs Zn foil 0.746 V @ j=20 mA cm2 20 mA cm2, 600 s per 75 cycles; polarization RSC Adv., 4 (2014)
6 M KOH + cycle period increased ~0.11 V at the 4608446092.
0.4 M ZnO end

Nanostructured Zn plate 0.70 V @ j=20 mA cm2 ~20 mA cm2, 300 s per 50 cycles; polarization Nanoscale, 6 (2014)
NiCo2O4 6 M KOH cycle period increased ~0.2 V at the 31733181.

CoMn2O4/N-rGO Zn plate ~0.7 V @ j=10 mA cm2 20 mA cm2, 300 s per 100 cycles; polarization Electrochem. Commun.,
6 M KOH cycle period increased ~0.2 V at the 41 (2014) 5963.

Co3O4 nanodisks 1.50 Zn plate ~0.9 V @ j= 10 mA cm2; ~17.6 mA cm2, 600 s 60 cycles; negligible Electrochem. Commun.,
6 M KOH ~1.1 V @ j=20 mA cm2 per cycle period voltage change at the 43 (2014) 109112.

La2NiO4 Zn powder ~0.8 V @ j=20 mA cm2 ~25 mA cm2, 150 s per 20 cycles; polarization ACS Appl. Mater.
6 M KOH cycle period increased 0.4 V at the Interfaces, 5 (2013)
end 99029907.

LaNiO3/rGO 10.1 mg Zn plate ~0.8 V @ j=10 mA cm2; ~25 mA cm2, 3600 s per 97 cycles; negligible RSC Adv., 6 (2016)
6 M KOH ~0.98 V @ j=25 mA cm2 cycle period voltage change at the 8638686394.

still maintain > 88.5%, signicantly higher than the case of benchmark CaMnO3 microsphere [40], E > 1.14 V; NixOy/N-doped C [41],
Pt/C (72.8%) (Fig. 5a). The prolonged CVs further conrmed the long- E =0.93 V; Co3O4/N-doped C [42], E =1.02 V), and non-metal
term catalytic cyclability. After extended 12,000 cycles at 400 rpm, the materials (e.g., S-doped graphene/CNT [43], E =1.00 V; P-doped g-
shape of the CV curves remains almost unchanged, in a shape contrary C3N4 [44], E =0.94 V) (Fig. 5d). The detailed comparison of key
to that of Pt/C (Fig. 5b and S12). The morphology of the NiCo2S4/N- performance parameters is presented in Table S1. The superb catalytic
CNT catalyst is essentially preserved after repeated CV cycles, whereas activity and reversibility of the hybrid possibly contribute to several
the Pt nanoparticles in Pt/C exfoliate and agglomerate severely (Fig. factors: (1) the small size and high dispersed nanocrystallines with
S13), suggesting remarkable electrochemical robustness of the nano- considerable intrinsic catalytic activity facilitate the activation and
composite contributed by rm attachment between the durable CNT dissociation of molecular O2 [45,46]; (2) the enhanced overall electrical
framework and the NiCo2S4 nanocrystallines. Furthermore, in the conductivity beneted from the rm contact in the in-situ fabricated
context of developing ORR-OER bifunctional catalysts, the NiCo2S4/ spinel and CNT hybrid; (3) the coupling synergetic eect between the
N-CNT hybrid exhibits remarkable activity towards catalyzing OER, suldes and the CNT substrate functionalized with nitrogen groups
rendering an apparently larger OER currents and lower evolution alters the electron cloud structure and optimizes the adsorption/
potential as compared with other catalysts and even the RuO2 (Fig. 5c). desorption behaviors of oxygen-related species, which has been
The variance metrics (E= Ej=10-Ehalf), where Ej=10 is the operating demonstrated to signicantly favors the oxygen-involved electrocata-
potential to deliver a OER current density of 10 mA cm2 and is related lysis processes [30,33].
to a 10% ecient solar fuel synthesis, are traditionally employed to The superior bifunctional ORR/OER capability and durability of
evaluate the overall oxygen electrode activity and reversibility. The NiCo2S4/N-CNT motivated us to investigate its feasibility in realistic
smaller the E value is, the closer the electrode is to an ideal primary and rechargeable Zn-air battery devices. The battery conguration
reversible oxygen cathode. Accordingly, the NiCo2S4/N-CNT displays consisted of a Zn plate as the anode and the prepared NiCo2S4/N-CNT
a E value of 0.80 V, lower than that of NiCo2S4 (1.04 V) and supported on carbon paper as the air cathode (Fig. 6a and S14). The battery
NiCo2S4/CNT (0.94 V) and also comparable to the most active electro- had an high open-circuit voltage of 1.49 V (Fig. S15) and exhibited a
catalysts reported so far including precious metal (e.g., Pt/C [39], E current density of ~107 mA cm2 at voltage of 1.0 V, which is close to that
=1.16 V; Ir/C [39], E =0.92 V), transition-metal oxides (e.g., of Pt/C (Fig. 6b). The peak power density reached 147 mW cm2 at 0.77 V.

X. Han et al. Nano Energy 31 (2017) 541550

By normalized to the mass of consumed Zn metal, the specic discharge References

capacity of NiCo2S4/N-CNT is 431.1 mAh g1, corresponding to a high
energy density of 554.6 Wh kg1 (Fig. S16). Furthermore, the NiCo2S4/N- [1] P.G. Bruce, S.A. Freunberger, L.J. Hardwick, J.M. Tarascon, Nat. Mater. 11 (2012)
CNT composite enables assembled rechargeable Zn-air battery with lower 1929.
[2] R.G. Cao, J.S. Lee, M.L. Liu, J. Cho, Adv. Energy Mater. 2 (2012) 816829.
discharge/charge overpotential (0.63 V) and exceptional rechargeability [3] M.K. Debe, Nature 486 (2012) 4351.
(150 cycles) (Fig. 7a and S17) in sharp comparison with those cells [4] M.H. Shao, Q.W. Chang, J.P. Dodelet, R. Chenitz, Chem. Rev. 116 (2016)
catalyzed by Pt/C (0.90 V, 59 cycles) and RuO2 ( 0.79V, 44 cycles) at 35943657.
[5] F.Y. Cheng, J. Chen, Chem. Soc. Rev. 41 (2012) 21722192.
10 mA cm2. A LED light was continuously lit for more than 12 h by two [6] Z.L. Wang, D. Xu, J.J. Xu, X.B. Zhang, Chem. Soc. Rev. 43 (2014) 77467786.
series NiCo2S4/N-CNT-based Zn-air batteries (inset in Fig. 7a), indicating [7] G. Jiang, H. Zhu, X. Zhang, B. Shen, L. Wu, S. Zhang, G. Lu, Z. Wu, S. Sun, ACS
the high capacity density. Otherwise, as shown in Fig. 7b, for NiCo2S4/N- Nano 9 (2015) 1101411022.
[8] S.M. Alia, S. Pylypenko, K.C. Neyerlin, D.A. Cullen, S.S. Kocha, B.S. Pivovar, ACS
CNT, the initial overpotential is 0.63 V, corresponding to a round-trip Catal. 4 (2014) 26802686.
eciency (discharge end voltage divided by charge end voltage) of 67.2%. [9] S.J. Guo, S. Zhang, S.H. Sun, Angew. Chem. Int. Ed. 52 (2013) 85268544.
After 150 cycles, the polarization increases to 0.69 V, leading to a voltaic [10] S.G. Chen, Z.D. Wei, X.Q. Qi, L.C. Dong, Y.G. Guo, L.J. Wan, Z.G. Shao, L. Li, J.
Am. Chem. Soc. 134 (2012) 1325213255.
eciency reduced by only 2.1% (65.1%). In sharp contrast, the voltage gap
[11] Y. Zhu, W. Zhou, Y. Chen, J. Yu, X. Xu, C. Su, M.O. Tad, Z. Shao, Chem. Mater. 27
of Pt/C and RuO2 shows larger increments after dozens of cycles, implying (2015) 30483054.
their limited rechargeability (Fig. S18). Actually, the rechargeable battery [12] X.P. Han, F.Y. Cheng, T.R. Zhang, J.G. Yang, Y.X. Hu, J. Chen, Adv. Mater. 26
catalyzed by the composite delivers similar discharge-recharge behaviors to (2014) 20472051.
[13] N. Cheng, M.N. Banis, J. Liu, A. Riese, X. Li, R. Li, S. Ye, S. Knights, X. Sun, Adv.
the present highest-performing ORR electrode of Pt/C and OER electrode Mater. 27 (2015) 277281.
of RuO2 (Fig. 7c), further conrming the excellent bifunctional capability, in [14] T. Maiyalagan, K.A. Jarvis, S. Therese, P.J. Ferreira, A. Manthiram, Nat. Commun.
accordance with the results from half-reaction tests. Moreover, when 5 (2014) 3949.
[15] J. Suntivich, H.A. Gasteiger, N. Yabuuchi, H. Nakanishi, J.B. Goodenough, Y. Shao-
NiCo2S4/N-CNT-based cell repeatedly discharged/recharged even at Horn, Nat. Chem. 3 (2011) 546550.
20 mA cm2 for 8 h cycling period (Fig. S19), almost no signicant [16] F.Y. Cheng, J. Shen, B. Peng, Y.D. Pan, Z.L. Tao, J. Chen, Nat. Chem. 3 (2011)
degradation can be observed on both the discharge and charge segments. 7984.
[17] C. Li, X. Han, F. Cheng, Y. Hu, C. Chen, J. Chen, Nat. Commun. 6 (2015) 7345.
Otherwise, the spinel composite-based non-aqueous lithium-air cells could [18] T.Y. Ma, S. Dai, M. Jaroniec, S.Z. Qiao, J. Am. Chem. Soc. 136 (2014)
deliver high capacity and considerable cyclability to dozens of cycles (Fig. 1392513931.
S20). These results illustrate the eective applicability of NiCo2S4/N-CNT [19] Y.Y. Liang, H.L. Wang, J.G. Zhou, Y.G. Li, J. Wang, T. Regier, H.J. Dai, J. Am.
Chem. Soc. 134 (2012) 35173523.
as air cathode catalysts for metal-air batteries, especially in the rechargeable [20] M.-R. Gao, X. Cao, Q. Gao, Y.-F. Xu, Y.-R. Zheng, J. Jiang, S.-H. Yu, ACS Nano 8
form. The key battery performance parameters presented here are among (2014) 39703978.
the best rechargeable Zn-air system reported in literatures (Table 2). Other [21] S. Chen, S.Z. Qiao, ACS Nano 7 (2013) 1019010196.
[22] Y. Xu, Y. Hao, G. Zhang, X. Jin, L. Wang, Z. Lu, X. Sun, Part. Part. Syst. Char. 33
eorts are still underway to address other problems such as the corrosion of
(2016) 569575.
Zn anode and electrolyte carbonation before practical Zn-air batteries are [23] S. Dou, L. Tao, J. Huo, S.Y. Wang, L.M. Dai, Energy Environ. Sci. 9 (2016)
made. 13201326.
[24] X.C. Cao, X.J. Zheng, J.H. Tian, C. Jin, K. Ke, R.Z. Yang, Electrochim. Acta 191
(2016) 776783.
4. Conclusions [25] H.L. Wang, Y.Y. Liang, Y.G. Li, H.J. Dai, Angew. Chem. Int. Ed. 50 (2011)
In summary, we have demonstrated controllable synthesis of a new [26] Q. Liu, J. Jin, J. Zhang, ACS Appl. Mater. Interfaces 5 (2013) 50025008.
[27] M.S. Faber, R. Dziedzic, M.A. Lukowski, N.S. Kaiser, Q. Ding, S. Jin, J. Am. Chem.
nanocomposite material-NiCo2S4 nanocrystallines strongly coupled Soc. 136 (2014) 1005310061.
with nitrogen-doped carbon nanotubes and its employment as electro- [28] R.A. Sidik, A.B. Anderson, J. Phys. Chem. C 110 (2006) 936941.
catalyst in both ORR/OER half reactions and practical Zn-air batteries. [29] J. Du, C. Chen, F. Cheng, J. Chen, Inorg. Chem. 54 (2015) 54675474.
[30] Z.Q. Liu, H. Cheng, N. Li, T.Y. Ma, Y.Z. Su, Adv. Mater. 28 (2016) 37773784.
The in-situ generated NiCo2S4/N-CNT hybrid manifests excellent [31] K.P. Gong, F. Du, Z.H. Xia, M. Durstock, L.M. Dai, Science 323 (2009) 760764.
bifunctional activity and long-term stability and reversibility, which [32] H. Fei, R. Ye, G. Ye, Y. Gong, Z. Peng, X. Fan, E.L. Samuel, P.M. Ajayan, J.M. Tour,
are comparable or even superior to the well-known noble metal ACS Nano 8 (2014) 1083710843.
[33] Y.Y. Liang, Y.G. Li, H.L. Wang, J.G. Zhou, J. Wang, T. Regier, H.J. Dai, Nat. Mater.
catalysts. The outstanding performance could be attributed to the
10 (2011) 780786.
homogenous and nanoscaled NiCo2S4 spinel crystallines with remark- [34] H. Xia, C. Hong, B. Li, B. Zhao, Z. Lin, M. Zheng, S.V. Savilov, S.M. Aldoshin, Adv.
able intrinsic activity and coupling synergism between two components Funct. Mater. 25 (2015) 627635.
[35] F.A. Cotton, G. Wikinson, C.A. Murillo, Advanced Inorganic Chemistry, Wiley,
as well as the N doping CNT altering the surface electron conguration
for oxygen adsorption/activation and providing network for ecient [36] A. Sivanantham, P. Ganesan, S. Shanmugam, Adv. Funct. Mater. 26 (2016)
electron transfer. This study should enlighten the rational design and 46614672.
controllable synthesis of functional chalcogenides/carbon composites [37] L. Shen, J. Wang, G. Xu, H. Li, H. Dou, X. Zhang, Adv. Energy Mater. 5 (2015)
and highlight their promising application in rechargeable metal-air [38] W. Wei, L. Mi, S. Cui, B. Wang, W. Chen, ACS Sustain. Chem. Eng. 3 (2015)
batteries and regenerative fuel cells. 27772785.
[39] Y. Gorlin, T.F. Jaramillo, J. Am. Chem. Soc. 132 (2010) 1361213614.
[40] X.P. Han, T.R. Zhang, J. Du, F.Y. Cheng, J. Chen, Chem. Sci. 4 (2013) 368376.
Acknowledgements [41] J. Masa, W. Xia, I. Sinev, A. Zhao, Z. Sun, S. Grtzke, P. Weide, M. Muhler,
W. Schuhmann, Angew. Chem. Int. Ed. 53 (2014) 85088512.
We thank the nancial support from the National Natural Science [42] G. Li, X. Wang, J. Fu, J. Li, M.G. Park, Y. Zhang, G. Lui, Z. Chen, Angew. Chem. Int.
Ed. 55 (2016) 49774982.
Foundation of China (51602216 and 51472178), National Key [43] A.M. El-Sawy, I.M. Mosa, D. Su, C.J. Guild, S. Khalid, R. Joesten, J.F. Rusling,
Research and Development Program (2016YFB0700205), and Tianjin S.L. Suib, Adv. Energy Mater. 6 (2016) 1501966.
Natural Science Foundation (16JCYBJC17600). [44] T.Y. Ma, J. Ran, S. Dai, M. Jaroniec, S.Z. Qiao, Angew. Chem. Int. Ed. 54 (2015)
[45] C. Jeyabharathi, S. Senthil Kumar, G.V.M. Kiruthika, K.L.N. Phani, Angew. Chem.
Appendix A. Supporting information Int. Ed. 122 (2010) 29872990.
[46] W. Chen, S.W. Chen, Angew. Chem. Int. Ed. 48 (2009) 43864389.
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.nanoen.2016.12.008.