Chem. Res. Chinese Universities doi: 10.

1007/s40242-020-0199-7
Article

Facile Route to Constructing Ternary Nanoalloy Bifunctional

Oxyegn Cathode for Metal-Air Batteries

WANG Huanfeng1,2, LI Junfeng2, LI Fei2, LI Jingjing1 and XU Jijing2,3*

1. College of Chemical and Food, Zhengzhou University of Technology, Zhengzhou 450044, P. R. China;
2. State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, College of Chemistry,
Jilin University, Changchun 130012, P. R. China;
3. International Center of Future Science, Jilin University, Changchun 130012, P. R. China

Abstract Highly stable and efficient bifunctional air cathode catalyst is crucial to rechargeable metal -air batteries.
Herein, a ternary nanoalloy layer composed of noble and base metal coated on a three-dimensional porous Ni sponge
as the bifunctional cathode is synthesized through in-situ anchoring strategy, which can effectively keep the multi-
metal nanoparticles from agglomeration and improve the density of active sites and catalytic ac tivity. The prepared
catalyst displays an excellent catalytic performance with lower overpotential and long -term stability. The Zn-air
batteries with the as-prepared cathodes possess a large power density of 170 mW/cm 2, long cycling stability up to 230
cycles, and a high specific capacity of 771 mA·h/g. Furthermore, the corresponding Li-air batteries deliver a dis-
charge capacity of 22429 mA·h/g. These superior properties of the metal-air batteries can be attributed to the com-
bined influence of design and composition of electrode, which is of great significance to improve the electrochemical
catalytic activity, providing great potential of wide application in expanded rechargeable energy systems.
Keywords Metal-air battery; Bifunctional cathode; Self-standing; Nanosheet; Electrochemical performance

1 Introduction to energy storage and conversion systems[14—16], but for the

inequal transforming disadvantages caused by the structure or
With the development of energy technology, metal-air morphology damage and the poor mechanical stability during
batteries owning generally high theoretical energy density have the assembling process[17]. For instance, applying the conven-
received great attention in future clean energy. However, the tional slurry method via loading a mixture containing the elec-
poor catalytic performance toward both oxygen reduction reac- troactive materials and polymeric binder onto the current col-
tion(ORR) and oxygen evolution reaction(OER) in cathode lector, would result in an unavoidable increase in the interface
remains the major limiting factor hindering the commercial contact resistance, and thus hinder the electron transport,
application of metal-air batteries[1,2]. Some noble metals, such leading to the higher manufacturing costs of batteries[18]. Fur-
as Pt, are well recognized as the superior ORR catalysts, while thermore, small multi-metal nanoparticles, particularly base
Ru/Ir-based catalysts are favorable to catalyze the OER[3—5]. metal contained in nanoparticles are subjected to aggregation
However, the high cost has constrained their prevalent applica- during catalytic or thermal treatment, leading to the decrease of
tion in rechargeable metal-air batteries. Therefore, the noble the exposed active sites and the limited catalytic activity[19]. For
metal economy needs to be considered[6—8]. Firstly, alloying years, nanoconfinement by confining the metal nanocatalyst
noble metal with other transition metals has been proved very onto the porous substrate, such as MOFs[20] and zeolites[21,22],
efficient in decreasing the dosage of noble metal, as well as has proven to be an efficient strategy for overcoming the
enhancing the electrocatalytic performance[9—11]. A further agglomeration. However, the poor conductivity and large mass
step is to adjust the assembly process, and the size, morphology of these substrates have greatly influenced the electrode activity.
and structure of the prepared materials[12,13]. Nanostructured Nanoporous metals have been widely used as promising
materials owning particular physical and chemical properties electrocatalysts due to the large pore volume and superior con-
including large specific surface area, favorable transport ductivity of the metallic framework structure[23—26]. Besides,
properties, and confinement effects, have been widely applied the porous structure with large specific surface area is essential
———————————
*Corresponding author. Email: [email protected]
Received July 1, 2020; accepted August 21, 2020.
Supported by the National Natural Science Foundation of China(Nos.51771177, 51972141), the Project of the Education
Department of Jilin Province, China(No.JJKH20190113KJ), the Jilin Provincial Science and Technology Development Program,
China(No.20190303104SF), the Jilin Province/Jilin University Co-construction Project-Funds for New Materials, China
(No.SXGJSF2017- 3), the Science and Technology Breakthrough Plan of Henan Province, China(No.202102210242), the High
School Key Scientific Research Project of Henan Province, China(No.21A150055) and the Youth Innovation Fund Project of
Zhengzhou University of Technology, China(No.QNCXJJ2019K2).
© Jilin University, The Editorial Department of Chemical Research in Chinese Universities and Springer-Verlag GmbH
2 Chem. Res. Chinese Universities
to the air cathode of metal-air batteries. Combining the advan- foam according to a best-known production method of the
tages of the substrate and the active electrocatalysts, an commercial nickel foam via electroless nickel plating[18]. The
advanced ORR/OER bifunctional cathode catalyst would be melamine foam was ultrasonically washed with acetone for 30
well achieved, which is also demonstrated by a series of recent min, and dried at 80 ℃ for 12 h. Next, the melamine foam was
studies[27—29]. For instance, a high-performance, desirable bi- immersed into a 50 mL of solution containing 1.25 g of SnCl2,
functional electrocatalyst by anchoring Co3O4 nanoparticles on 1.5 mL of 38% HCl and a bit Sn for 5 min, washed with dis-
nitrogen-doped carbon is achieved for rechargeable Zn-air bat- tilled water and immersed into 50 mL of solution containing
teries, which has solved the poor electronic conductivity, ag- 0.025 g of PdCl2 and 2 mL of 38% HCl to activate. Subse-
gregation of metal oxide nanoparticles and improved its cata- quently, the activated foam was rinsed with distilled water
lytic activity owing to the synergistic effect between N-doped several times. The activated foam was coated with Ni in 100
carbon substrate and metal oxide[27]. Therefore, anchoring mL of Ni plating solution containing 1.5 g of NiSO4‧6H2O, 2.0
noble metal onto the porous metal substrate with good conduc- g of Na3C6H5O7‧2H2O, 1.5 g of Na2H2PO2‧7H2O, 3 g of
tivity could be an effective method to solve the noble metal NaC2H3O2‧3H2O, and 0.15 mg of CS(NH2)2 at 80 ℃ for
economy, poor mechanical stability, and the agglomeration of 10—50 min to obtain Ni sponge(NiS).
multi-metal nanoparticles as well as the low conductivity. 2.1.2 Preparation of Ni(OH)2 Nanosheet/Ni Sponge
Hence, constitution of a well-designed nanoengineered Ni sponge(NiS), 40 mL of aqueous solution containing
metal-based cathode owning robust mechanical and chemical 0.30 g of Ni(NO3)2‧6H2O and 0.1 g of CO(NH2)2 were put into
stability, good conductibility and high catalytical activities, a Teflon-lined autoclave, heated at 180 ℃ for 5—15 h in an
especially for the self-standing structure with no need for oven. Then the product was taken out and cooled down to room
further assembly process or modification will comfortably temperature, followed by a method of ultrasonic cleaning with
solve these problems for metal-air batteries. deionized water and ethanol, then the obtained product was
Driven by these aspects, a construction of anchoring dried at 90 ℃ for 5 h.
nanoengineered PtRuNi layer/Ni nanosheet on Ni sponge 2.1.3 Preparation of PtRuNi/NiNS/NiS
(PtRuNi/NiNS/NiS) for rechargeable metal-air batteries is pro- The above-obtained product of Ni(OH)2 nanosheet/Ni
posed. The Ni sponge obtained by pre-treating melamine foam sponge[Ni(OH)2/NiS] was calcined at 400 ℃ for 6 h under a
with electroless nickel plating is chosen as the substrate due to mixed Ar-H2 atmosphere and the Ni nanosheet supported on Ni
its desirable porous structure and 3D framework. This inge- sponge(NiNS/NiS) was formed. Afterwards NiNS/NiS was
nious structure guarantees the fast mass transfer for O2 and ions. immersed into 2 mmol/L RuCl3 and 2 mmol/L K2PtCl6 mixture,
The self-standing structure is favorable to providing the conse- and heated in a water bath of 40 ℃ for 0.5 h, ensuring the
quent channels for electron transporting pathways and high adequate Ru-Pt deposition following the approach. After
specific surface area for exposed active sites. The thin PtRuNi purified with deionized water and dried, the obtained sample
alloy provides an effective catalytical overlayer for cathode. was treated with 4—5 h calcination at 400 ℃ under a mixed
The ternary metal self-standing catalyst of PtRuNi/NiNS/NiS Ar-H2 atmosphere, and the PtRuNi ternary alloy was formed by
exhibits more exposed active sites and better bifunctional cata- the fast atomic diffusion between the obtained noble metal
lytic activities for both ORR and OER. The rechargeable Zn-air alloy overlayer and NiNS/NiS. Loading density is (35±0.1)
batteries and Li-air batteries with PtRuNi/NiNS/NiS as the mgPtRuNi/NiNS/NiS/cm2 or 0.22 mgPtRu/cm2. To better analyze the
cathode display high discharge capacity, excellent rate perfor- electrocatalytic performance of PtRuNi/NiNS/NiS, the other
mance as well as long-term stability. two binary alloy-based cathodes(RuNi/NiNS/NiS, PtNi/NiNS/
NiS) were further synthesized similar to PtRuNi/NiNS/NiS.
2 Experimental
2.2 Materials Characterization
2.1 Materials Preparation
The microstructure, morphology and composition of the
Tin chloride(SnCl2), palladium chloride(PdCl2), nickel synthesized electrodes were characterized by means of scan-
sulfate hexahydrate(NiSO4‧6H2O), sodium hypophosphite ning electron microscopy(SEM, Hitachi S-4800), transmission
heptahydrate(Na2H2PO2‧7H2O), sodium acetate trihydrate electron microscopy(TEM, FEI Tecnai G2 S-Twin at 200 kV),
(NaC2H3O2‧3H2O), sodium citrate dihydrate(Na3C6H5O7‧2H2O), powder X-ray diffraction(PXRD, Rigaku-MiniFlex600) with
nickel nitrate hexahydrate[Ni(NO3)2‧6H2O], ruthenium chloride Cu Kα radiation, X-ray photoelectron spectroscopy(XPS) with
(RuCl3) and potassium hexachloroplatinate(K2PtCl6) were pur- an Al Kα beam. The morphology and composition of discharge
chased from Aladdin Reagent. Thiourea[CS(NH2)2], carbamide products and the discharged cathodes were also analyzed by
[CO(NH2)2], hydrochloric acid(HCl, 38%) and ethanol employing SEM and XPS.
(C2H5OH) were purchased from Sinopharm Chemical Reagent
Co., Ltd. Melamine foam was obtained from Changde Liyuan 2.3 Electrochemical Characterization
Co., Ltd. All chemicals used were as originally received
The electrochemical performance and electrochemical
without further treatment.
impedance spectroscopy(EIS) measurements were carried out
2.1.1 Preparation of Ni Sponge on an electrochemical workstation(BioLogic VMP3). The
Firstly, the metal nickel was deposited on the melamine linear sweep voltammograms(LSV) was conducted in the
 WANG Huanfeng et al. 3
three-electrode configuration with Pt foil as the counter CO(NH2)2 was heated in an oven, and Ni(OH)2 nanosheet was
electrode, PtRuNi/NiNS/NiS as the working electrode and the in-situ anchored on Ni sponge[Ni(OH)2/NiS]. Then the
reference electrode of saturated calomel electrode. Amplitude Ni(OH)2/NiS was calcined under a mixed Ar-H2 atmosphere to
of 5 mV was used for EIS measurements, and the spectra were obtain Ni nanosheet supported on NiS(NiNS/NiS), which was
collected from 1 MHz to 0.01 Hz. coated with the uniform Ru-Pt according to the redox replace-
ment of RuCl3 and PtCl62–. Eventually, PtRuNi/NiNS/NiS was
2.4 Metal-air Battery Characterization prepared via the fast atomic diffusion between the obtained
noble metal alloy overlayer and NiNS/NiS.
The as-prepared electrodes were directly assembled as ca-
As can be seen from the SEM images of the initial mela-
thodes for the performance study of the Zn-air battery. To ex-
mine foam, Ni sponge(NiS) and the as-prepared electrode in
pand their application, the Li-air batteries were also assembled
Fig.1(B)—(G), the melamine foam exhibited a porous structure
for the performance tests. Besides, the SP carbon cathode, i.e.,
and a smooth skeleton of ca. 8 µm diameter[Fig.1(B) and (E)],
a homogenous ink consisting of 80%(mass fraction) SP carbon
which ensures a fast mass transfer rate. Compared with the
mixed with 20%(mass fraction) lithiated Nafion coated onto the
melamine foam, a uniform and compact coating with rough
carbon paper, was prepared and utilized for comparation. The
surface is obtained by the electroless nickel plating[Fig.1(C)
metal-air batteries tests were carried out on a Land-CT2001A
and (F)], and the plating thickness is ca. 200 nm(Fig.S1, see the
battery-testing system at room temperature.
Electronic Supplementary Material of this paper). The low and
3 Results and Discussion high magnification SEM images of PtRuNi/NiNS/NiS shown in
Fig.1(D) and (G) display a well-distributed nanosheet growing
3.1 Structural and Morphological Characteriza- vertically and cross-linked on the foam substrate. Additionally,
tion an obvious nanosheet of PtRuNi/NiNS arranging in an orderly
manner with a diameter of ca. 1—2 µm on the skeleton of the
The whole constructing strategy for PtRuNi/NiNS/NiS is Ni sponge in Fig.S2(see the Electronic Supplementary Material
displayed in Fig.1(A). Firstly, the metal nickel was deposited of this paper) indicates that the PtRuNi/NiNS coating on the Ni
on the melamine foam through the electroless nickel plating[18]. sponge has been well synthesized.
The obtained Ni sponge(NiS) mixed with Ni(NO3)2‧6H2O and

Fig.1 Synthesis and characterization of PtRuNi/NiNS/NiS

The schematic illustration of PtRuNi/NiNS/NiS(A), SEM images of the melamine foam(B), Ni sponge(C) and PtRuNi/NiNS/NiS(D), and
the corersponding enlarged SEM images of melamine foam(E), Ni sponge(F) and PtRuNi/NiNS/NiS(G).
The mesoporous and macroporous microstructure of the and the large specific surface area ensures the abundant contact
PtRuNi/NiNS coating can be seen in Fig.2(A), which is further area at the three-phase reaction interface, which is beneficial to
verified by the N2 adsorption-desorption isotherm in Fig.2(B). achieving the high availability of exposed active sites in
The pore-size distribution data[the inset in Fig.2(B)] demon- metal-air batteries[30]. Additionally, as can be seen from the
strate the pores of PtRuNi/NiNS/NiS with a size of 10—90 nm, high-resolution TEM in Fig.2(C), the thickness of these nano-
and the specific surface area is up to 58 m2/g, much higher than sheets is ca. 4 nm. The elemental mapping in Fig.2(D) verifies
that of the previous work[11], which can be ascribed to the cha- the three metal elements of Pt, Ni, and Ru are evenly distri-
racteristic nanosheet-like structure. The particular mesoporous/ buted on PtRuNi/NiNS/NiS. The PXRD pattern[Fig.2(E)]
macroporous properties favor the rapid ions and O2 transfer, reveals three diffraction peaks emerged at 44.50°, 51.9°
4 Chem. Res. Chinese Universities
and 76.4°, which are attributed to the (111), (200) and (220) shown in Fig.2(H), the electrical conductivity of the prepared
crystalline orientations of NiNS/NiS(JCPDS No.04-0850), PtRuNi/NiNS/NiS reaches a higher value of 52.10 S/cm, which
respectively. The other peaks observed at 41.04° and 46.96° is also comparable to NiS and NiNS/NiS(Fig.S3, see the Elec-
should be assigned to the formation of PtRuNi alloy, which is tronic Supplementary Material of this paper). The superior
consistent with the XPS analysis in Fig.2(F) and (G) as well. conductive properties can be ascribed to the good conductivity
Due to the existence of the alloying effect, the XPS signal dis- of porous metal substrate. As shown in Fig.2(I), this elaborately
palys a positive shift of Pt4f(71.30 and 75.0 eV), Ru3p(462.80 constructed cathode demonstrates significant advantages as an
eV) in comparation with the corresponding binding energy of ideal oxygen cathode for metal-air batteries: high-efficient
single Pt4f7/2(70.64 eV), Pt4f5/2(74.50 eV) and Ru3p3/2(462.20 bifunctional electrocatalytical activity provided by the ternary
eV), respectively. The exact constitution of PtRuNi can hardly alloy overlayer, rapid mass transfer by the hierarchical porous
be determined because of the interference from the substrate of structure, abundant exposed active sites benefiting from the
Ni sponge through PXRD, XPS, EDX or ICP-OES analysis. high specific surface area and well electronic conductivity, high
Consequently, more suitable methods need to be developed to mechanical stability from the benefit of the self-standing struc-
determine the contents of each metal in future work. Further- ture of NiNS/NiS, and the superior chemical stability obtained
more, compared with most reported conducting materials from the typical prepared method, which have laid a firm
including polymer hydrogel[31], graphene mesh network with foundation for favorable electrochemical performance of Zn-air
Ni meshes[32], Ag nanowire on sponge[33], Ni-P-coated mela- and Li-air batteries.
mine foam[18] and graphene foam on nickel templates[34]

Fig.2 TEM image(A), N2 adsorption-desorption isotherm(B) and the pore-size distribution(inset),

high-magnification TEM image(C), elemental mappings of Pt, Ni, and Ru(D) as well as PXRD
patterns of PtRuNi/NiNS/NiS(E), XPS spectra of Pt4f(F), and Ru3p(G) for PtRuNi/NiNS/NiS, the
electrical conductivity of PtRuNi/NiNS/NiS and other reported conducting materials(H), and the
working mechanism of PtRuNi/NiNS/NiS(I)
KOH electrolyte under O2 or Ar-saturated atomsphere, respec-
3.2 Electrochemical Performance tively. Fig.3(A) displays apparent oxygen reduction peaks for
the three kinds of alloy-based catalysts in O2-saturated state.
To investigate the bifunctional catalytic performance,
The peaks, however, disappeared when the solution was under
PtRuNi/NiNS/NiS, RuNi/NiNS/NiS and PtNi/NiNS/NiS are
the Ar-saturated state in Fig.S4(see the Electronic Supplemen-
measured in 1 mol/L KOH solution as the working electrode.
tary Material of this paper), suggesting the pronounced ORR
ORR polarization curves of all samples were tested in 1 mol/L
 WANG Huanfeng et al. 5
catalytic activity of the prepared samples, which is benefited tion intermediates on the surface of catalyst with the assistance
from the design strategy for overcoming the agglomeration of of the interaction of the third metal[35,36]. The almost constant
multi-metal nanoparticles. Furthermore, the significantly higher current density over continuous 50 h in Fig.3(B) suggests the
current density of PtRuNi/NiNS/NiS at the potential of 0.4 V long-term durability of PtRuNi/NiNS/NiS, and the ultrasmall
compared with that of the other two catalysts demonstrates potential variation after 1000 cycles(Fig.S5, Electronic Sup-
more active sites of PtRuNi/NiNS/NiS for ORR, which could plementary Material of this paper) further demonstrates the
be ascribed to the weakening adsorption of suppressing reac- superior cycle stability of PtRuNi/NiNS/NiS.

Fig.3 LSV curves of ORR(A), ORR chronoamperometric response of PtRuNi/NiNS/NiS at 0.75 V(B),
LSV curves of OER at 10 mV/s(C), OER Tafel plots(D), OER polarization curves of PtRu-
Ni/NiNS/NiS before and after 1000 potential cycles(E) and the durability of PtRuNi/NiNS/NiS
during OER at 1.55 V(F)
To elucidate the OER performance, the LSV tests were activity. Besides, the ion and charge transport ability for the
investigated. The onset potential is an important index of merit electrocatalysts was also critical to ensure high electrocatalysis
for evaluating the OER catalytic activity of the prepared cata- activity, which was measured by EIS. The smaller semicircular
lysts. Fig.3(C) displays the OER polarization curve of the three diameter of PtRuNi/NiNS/NiS in Fig.S6(Electronic Supple-
catalysts. The lower onset potential and higher current of mentary Material of this paper) indicates the lower resistance
PtRuNi/NiNS/NiS among the three catalysts demonstrate its during OER and better interfacial charge transfer kinetics,
higher OER activity, which might be ascribed to more reaction which could be possibly explained by the continuous fast elec-
sites of the alloy nanoparticles caused by the crystal type and tron transportation and high conductivity, corresponding to the
structural variation of the third metal[37], besides, the results BET results. All the above results suggest this nanosheet-like
also verify that the catalysts with Ru metallic element exhibit self-standing oxygen electrode exhibits good bifunctional elec-
excellent electrocatalytical activity for OER. Tafel slopes were trocatalytic activity, long-term stability, and good electronic
calculated based on the LSV curves to further estimate the conductivity, confirming its valuable application potential for
reaction kinetics. The smaller Tafel slope of PtRuNi/NiNS/NiS metal-air batteries.
revealed in Fig.3(D) indicates the excellent kinetics for OER
activity. Furthermore, the potential deviation between the cor- 3.3 Zn-air Batteries Performance
responding potential delivering a current density of 10 mA/cm2
Based on the good bifunctional ORR/OER performance of
during OER and a half-wave voltage during ORR can be effec-
PtRuNi/NiNS/NiS, its feasibility under real battery work condi-
tively adopted to benchmark the overall bifunctional activity
tion is evaluated in assembly metal-air batteries. The actural
and reversibility of the cathode[38]. The PtRuNi/NiNS/NiS is
battery performance was studied by constructing a conventional
proved to be an excellent reversible cathode with a smaller
Zn-air battery, which is made up of anode with zinc plate,
potential deviation value of 0.72 V. To further evaluate the
cathode with PtRuNi/NiNS/NiS and electrolyte with 6 mol/L
OER stability of PtRuNi/NiNS/NiS, 1000 continuous cycling
KOH aqueous solution[Fig.4(A)]. The discharge curves and
tests were also performed. As shown in Fig.3(E), there ap-
power density of PtRuNi/NiNS/NiS in Fig.4(B) revealed an
peared similar performance after 1000 cycles to the initial one
open circuit voltage of 1.46 V, and a maximum current density
from the polarization curves of PtRuNi/NiNS/NiS. Additionally,
of ca. 520 mA/cm2, encouragingly, a much higher power
the minor decline of the current density occurred over 75 h in
density of ca. 170 mW/cm2 can be delivered in comparation
Fig.3(F) further demonstrates its high durability and strong
6 Chem. Res. Chinese Universities
with the other two cathodes, which should be derived from the metallic substrates. The specific capacities of the battery
fast mass transfer and larger active area for the catalysts composed of PtRuNi/NiNS/NiS were up to ca. 813, 798 and
because of the addition of different metals[35]. Galvanostatic 771 mA·h/gZn at different current densities of 10, 20, and 40
discharge curves in Fig.4(C) displayed the potential plains of mA/cm2, respectively[Fig.4(D)]. Furthermore, the mechanical
PtRuNi/NiNS/NiS of 1.38, 1.35, 1.32, 1.28, 1.24, 1.20 and 1.16 rechargeablility of Zn-batteries was investigated. With the in-
V at 2, 5, 10, 20, 30, 40 and 50 mA/cm2, respectively. Ama- creasingly consumed Zn in the discharging process, the zinc
zingly, no evident change is observed in the voltage plateau of plate and KOH electrolyte were refilled in the battery system to
1.37 V at 2 mA/cm2 after a cycle of different discharge current recovery the battery. As can be seen from Fig.4(E), the battery
densities, indicating the excellent rate capability of PtRu- could be recharged for three consecutive cycles maintaining
Ni/NiNS/NiS, which might be attributed to the hierarchically similar performance on the same PtRuNi/NiNS/NiS electrode,
porous structure, large specific surface, ultrathin nanosheet and suggesting its excellent mechanical rechargeability, which
close-connection of active materials to the conductive sub- might be ascribed to its superior structural stability and chemi-
strates, facilitating electron transport from the nanosheet to the cal stability.

Fig.4 Schematic of Zn-air battery(A), polarization plots and power density with different catalysts(B), discharge
specific capacity(C) and galvanostatic discharge plots(D) of PtRuNi/NiNS/NiS-based Zn-air batteries,
long-term stability for mechanically rechargeable Zn-air batteries at 30 mA/cm2(E), charge and discharge
polarization curves of PtRuNi/NiNS/NiS, PtNi/NiNS/NiS and RuNi/NiNS/NiS cathodes(F), cycle perfor-
mance of PtRuNi/NiNS/NiS-based Zn-air batteries at 10 and 20 mA/cm2 with 1800 s per cycle(G) and the
corresponding PXRD patterns of PtRuNi/NiNS/NiS before and after 50 cycles at 20 mA/cm2(H), and LED
powered by two Zn-air batteries serially coupled with PtRuNi/NiNS/NiS(I)
The rechargeable Zn-air batteries were further investigated enhanced volatic efficiency and a superior rechargeability of
by adding 0.2 mol/L Zn acetate into the above-mentioned elec- PtRuNi/NiNS/NiS-based Zn-air batteries. Furthermore, after
trolyte. A lower charge-discharge overpotential of PtRuNi/ 230 discharge/charge cycles(115 h), only small voltage gap is
NiNS/NiS(0.98 V) is observed at a current density of 20 observed in Fig.4(G), demonstrating a high cycling stability for
mA/cm2 in Fig.4(F), much lower than that of RuNi/NiNS/NiS PtRuNi/NiNS/NiS-based rechargeable Zn-air battery. And the
(1.42 V) or PtNi/NiNS/NiS(1.32 V), indicating a much composition of cathode appears almost no change compared
 WANG Huanfeng et al. 7
with the pristine PtRuNi/NiNS/NiS according to the PXRD deliver a super high discharge capacity of 22429 mA h/gPtRuNi at
pattern after 50 discharge-charge cycles in Fig.4(H), also con- the curren density of 100 mA/g[Fig.5(C)], almost three times as
firming its durability and high structural stability. All these high as the SP carbon cathode(7921 mA·h/g), much better than
results demonstrate the better ORR and OER bifunctional elec- those of other reported carbon-free cathodes[39—42], indicating
trocatalytic activity and high stability of PtRuNi/NiNS/NiS that the structural merit of the highly porous metal-based
than the other two binary metal catalysts in rechargeable Zn-air nanosheet self-standing structure could provide enough availa-
batteries. Additionally, multiple Zn-air batteries with PtRu- ble space to store the generated discharge products, which is
Ni/NiNS/NiS cathode can be integrated into series circuits to corresponding to the SEM images and the PXRD patterns of
convene particular energy needs for various practical applica- the discharged SP carbon and PtRuNi/NiNS/NiS cathodes. The
tions. As shown in Fig.4(I), two series of Zn-air batteries with mass transfer path is gradually blocked by plentiful discharged
PtRuNi/NiNS/NiS cathode can generate an open-circuit voltage products attached on the surface of the SP carbon cathode
of 2.88 V to illuminate a red LED light, which is also consistent (Fig.S7, see the Electronic Supplementary Material of this
with the voltage value from the discharge curves in Fig.4(B), paper), resulting in the discharge termination. On the contrary,
demonstrating the practical application potential of PtRu- the loose and porous structure is obvious and the discharged
Ni/NiNS/NiS. products of Li2O2 verified by the corresponding PXRD are
grown on the skeleton of the PtRuNi/NiNS/NiS cathode(Fig.S8,
3.4 Li-air Batteries Performance see the Electronic Supplementary Material of this paper).
Galvanostatic discharge measurements in Fig.5(D) revealed the
To verify the universality of the as-prepared electrode, the
superior rate capability of PtRuNi/NiNS/NiS, there appeared
electrochemical properties of the PtRuNi/NiNS/NiS-based
almost no apparent potential decay over 1 h discharging even at
Li-air batteries were investigated in tetraethylene glycol dime-
a high current density of 1000 mA/g, indicating the fast mass
thylether[Fig.5(A)]. For a definite comparison, the conven-
transfer of O2 and Li+ flow into/departure from the cathode.
tional SP carbon was also utilized as the cathode for Li-air
Additionally, the Li-air batteries with PtRuNi/NiNS/NiS
batteries. Fig.5(B) shows the first discharge-charge voltage
cathode performed a much longer stability of 136 cycles at a
curves of the Li-air batteries with SP carbon and PtRuNi/
limited capacity of 1000 mA·h/g, by contrast, the SP carbon
NiNS/NiS cathodes at 100 mA/g. The overpotential is merely
cathode exhibited merely 32 cycles[Fig.5(E)], demonstrating
0.40 V, and the energy efficiency is up to 87.5%, indicating the
high reversibility and rechargeability of PtRuNi/NiNS/
superb ORR/OER electrocatalytic activity for PtRuNi/NiNS/
NiS-based Li-air batteries.
NiS-based Li-air batteries. Furthermore, the Li-air batteries can

Fig.5 Schematic of Li-air battery(A), first discharge-charge profiles of Li-air batteries at 100 mA/g(B),
discharge specific capacity of the Li-air batteries at a current density of 100 mA/g(C), rate capability
of the Li-air cells at different current densities(D), and discharge terminal voltage versus the cycle
numbers of the Li-air batteries at 100 mA/g and a fixed capacity of 1000 mA·h/g(E)
cycle stability is presented according to a facile construction
4 Conclusions for ternary alloy nanosheet supported on Ni sponge(PtRuNi/
NiNS/NiS) through in-situ anchoring method, which can
A promising bifunctional cathode for Zn-air batteries and
effectively keep the nano-alloy from agglomeration during the
Li-air batteries with outstanding electrochemical activity and
8 Chem. Res. Chinese Universities
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