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: jijingxu@jlu.edu.cn
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-
tages of the substrate and the active electrocatalysts, an
advanced ORR/OER bifunctional cathode catalyst would be
well achieved, which is also demonstrated by a series of recent
studies[27—29]. For instance, a high-performance, desirable bi-
functional electrocatalyst by anchoring Co3O4 nanoparticles on
nitrogen-doped carbon is achieved for rechargeable Zn-air bat-
teries, which has solved the poor electronic conductivity, ag-
gregation of metal oxide nanoparticles and improved its cata-
lytic activity owing to the synergistic effect between N-doped
carbon substrate and metal oxide[27]. Therefore, anchoring
noble metal onto the porous metal substrate with good conduc-
tivity could be an effective method to solve the noble metal
economy, poor mechanical stability, and the agglomeration of
multi-metal nanoparticles as well as the low conductivity.
Hence, constitution of a well-designed nanoengineered
metal-based cathode owning robust mechanical and chemical
stability, good conductibility and high catalytical activities,
especially for the self-standing structure with no need for
further assembly process or modification will comfortably
solve these problems for metal-air batteries.
Driven by these aspects, a construction of anchoring
nanoengineered PtRuNi layer/Ni nanosheet on Ni sponge
(PtRuNi/NiNS/NiS) for rechargeable metal-air batteries is pro-
posed. The Ni sponge obtained by pre-treating melamine foam
with electroless nickel plating is chosen as the substrate due to
its desirable porous structure and 3D framework. This inge-
nious structure guarantees the fast mass transfer for O2 and ions.
The self-standing structure is favorable to providing the conse-
quent channels for electron transporting pathways and high
specific surface area for exposed active sites. The thin PtRuNi
alloy provides an effective catalytical overlayer for cathode.
The ternary metal self-standing catalyst of PtRuNi/NiNS/NiS
exhibits more exposed active sites and better bifunctional cata-
lytic activities for both ORR and OER. The rechargeable Zn-air
batteries and Li-air batteries with PtRuNi/NiNS/NiS as the
cathode display high discharge capacity, excellent rate perfor-
mance as well as long-term stability.
2 Experimental
2.1 Materials Preparation
Tin chloride(SnCl2), palladium chloride(PdCl2), nickel
sulfate hexahydrate(NiSO4‧6H2O), sodium hypophosphite
heptahydrate(Na2H2PO2‧7H2O), sodium acetate trihydrate
(NaC2H3O2‧3H2O), sodium citrate dihydrate(Na3C6H5O7‧2H2O),
nickel nitrate hexahydrate[Ni(NO3)2‧6H2O], ruthenium chloride
(RuCl3) and potassium hexachloroplatinate(K2PtCl6) were pur-
chased from Aladdin Reagent. Thiourea[CS(NH2)2], carbamide
[CO(NH2)2], hydrochloric acid(HCl, 38%) and ethanol
(C2H5OH) were purchased from Sinopharm Chemical Reagent
Co., Ltd. Melamine foam was obtained from Changde Liyuan
Co., Ltd. All chemicals used were as originally received
without further treatment.
2.1.1 Preparation of Ni Sponge
Firstly, the metal nickel was deposited on the melamine
foam according to a best-known production method of the
commercial nickel foam via electroless nickel plating[18]. The
melamine foam was ultrasonically washed with acetone for 30
min, and dried at 80 ℃ for 12 h. Next, the melamine foam was
immersed into a 50 mL of solution containing 1.25 g of SnCl2,
1.5 mL of 38% HCl and a bit Sn for 5 min, washed with dis-
tilled water and immersed into 50 mL of solution containing
0.025 g of PdCl2 and 2 mL of 38% HCl to activate. Subse-
quently, the activated foam was rinsed with distilled water
several times. The activated foam was coated with Ni in 100
mL of Ni plating solution containing 1.5 g of NiSO4‧6H2O, 2.0
g of Na3C6H5O7‧2H2O, 1.5 g of Na2H2PO2‧7H2O, 3 g of
NaC2H3O2‧3H2O, and 0.15 mg of CS(NH2)2 at 80 ℃ for
10—50 min to obtain Ni sponge(NiS).
2.1.2 Preparation of Ni(OH)2 Nanosheet/Ni Sponge
Ni sponge(NiS), 40 mL of aqueous solution containing
0.30 g of Ni(NO3)2‧6H2O and 0.1 g of CO(NH2)2 were put into
a Teflon-lined autoclave, heated at 180 ℃ for 5—15 h in an
oven. Then the product was taken out and cooled down to room
temperature, followed by a method of ultrasonic cleaning with
deionized water and ethanol, then the obtained product was
dried at 90 ℃ for 5 h.
2.1.3 Preparation of PtRuNi/NiNS/NiS
The above-obtained product of Ni(OH)2 nanosheet/Ni
sponge[Ni(OH)2/NiS] was calcined at 400 ℃ for 6 h under a
mixed Ar-H2 atmosphere and the Ni nanosheet supported on Ni
sponge(NiNS/NiS) was formed. Afterwards NiNS/NiS was
immersed into 2 mmol/L RuCl3 and 2 mmol/L K2PtCl6 mixture,
and heated in a water bath of 40 ℃ for 0.5 h, ensuring the
adequate Ru-Pt deposition following the approach. After
purified with deionized water and dried, the obtained sample
was treated with 4—5 h calcination at 400 ℃ under a mixed
Ar-H2 atmosphere, and the PtRuNi ternary alloy was formed by
the fast atomic diffusion between the obtained noble metal
alloy overlayer and NiNS/NiS. Loading density is (35±0.1)
mgPtRuNi/NiNS/NiS/cm2 or 0.22 mgPtRu/cm2. To better analyze the
electrocatalytic performance of PtRuNi/NiNS/NiS, the other
two binary alloy-based cathodes(RuNi/NiNS/NiS, PtNi/NiNS/
NiS) were further synthesized similar to PtRuNi/NiNS/NiS.
2.2 Materials Characterization
The microstructure, morphology and composition of the
synthesized electrodes were characterized by means of scan-
ning electron microscopy(SEM, Hitachi S-4800), transmission
electron microscopy(TEM, FEI Tecnai G2 S-Twin at 200 kV),
powder X-ray diffraction(PXRD, Rigaku-MiniFlex600) with
Cu Kα radiation, X-ray photoelectron spectroscopy(XPS) with
an Al Kα beam. The morphology and composition of discharge
products and the discharged cathodes were also analyzed by
employing SEM and XPS.
2.3 Electrochemical Characterization
The electrochemical performance and electrochemical
impedance spectroscopy(EIS) measurements were carried out
on an electrochemical workstation(BioLogic VMP3). The
linear sweep voltammograms(LSV) was conducted in the
 WANG Huanfeng et al.
three-electrode configuration with Pt foil as the counter
electrode, PtRuNi/NiNS/NiS as the working electrode and the
reference electrode of saturated calomel electrode. Amplitude
of 5 mV was used for EIS measurements, and the spectra were
collected from 1 MHz to 0.01 Hz.
2.4 Metal-air Battery Characterization
The as-prepared electrodes were directly assembled as ca-
thodes for the performance study of the Zn-air battery. To ex-
pand their application, the Li-air batteries were also assembled
for the performance tests. Besides, the SP carbon cathode, i.e.,
a homogenous ink consisting of 80%(mass fraction) SP carbon
mixed with 20%(mass fraction) lithiated Nafion coated onto the
carbon paper, was prepared and utilized for comparation. The
metal-air batteries tests were carried out on a Land-CT2001A
battery-testing system at room temperature.
3 Results and Discussion
3.1 Structural and Morphological Characteriza-
tion
The whole constructing strategy for PtRuNi/NiNS/NiS is
displayed in Fig.1(A). Firstly, the metal nickel was deposited
on the melamine foam through the electroless nickel plating[18].
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
PtRuNi/NiNS coating can be seen in Fig.2(A), which is further
verified by the N2 adsorption-desorption isotherm in Fig.2(B).
The pore-size distribution data[the inset in Fig.2(B)] demon-
strate the pores of PtRuNi/NiNS/NiS with a size of 10—90 nm,
and the specific surface area is up to 58 m2/g, much higher than
that of the previous work[11], which can be ascribed to the cha-
racteristic nanosheet-like structure. The particular mesoporous/
macroporous properties favor the rapid ions and O2 transfer,
3
CO(NH2)2 was heated in an oven, and Ni(OH)2 nanosheet was
in-situ anchored on Ni sponge[Ni(OH)2/NiS]. Then the
Ni(OH)2/NiS was calcined under a mixed Ar-H2 atmosphere to
obtain Ni nanosheet supported on NiS(NiNS/NiS), which was
coated with the uniform Ru-Pt according to the redox replace-
ment of RuCl3 and PtCl62–. Eventually, PtRuNi/NiNS/NiS was
prepared via the fast atomic diffusion between the obtained
noble metal alloy overlayer and NiNS/NiS.
As can be seen from the SEM images of the initial mela-
mine foam, Ni sponge(NiS) and the as-prepared electrode in
Fig.1(B)—(G), the melamine foam exhibited a porous structure
and a smooth skeleton of ca. 8 µm diameter[Fig.1(B) and (E)],
which ensures a fast mass transfer rate. Compared with the
melamine foam, a uniform and compact coating with rough
surface is obtained by the electroless nickel plating[Fig.1(C)
and (F)], and the plating thickness is ca. 200 nm(Fig.S1, see the
Electronic Supplementary Material of this paper). The low and
high magnification SEM images of PtRuNi/NiNS/NiS shown in
Fig.1(D) and (G) display a well-distributed nanosheet growing
vertically and cross-linked on the foam substrate. Additionally,
an obvious nanosheet of PtRuNi/NiNS arranging in an orderly
manner with a diameter of ca. 1—2 µm on the skeleton of the
Ni sponge in Fig.S2(see the Electronic Supplementary Material
of this paper) indicates that the PtRuNi/NiNS coating on the Ni
sponge has been well synthesized.
and the large specific surface area ensures the abundant contact
area at the three-phase reaction interface, which is beneficial to
achieving the high availability of exposed active sites in
metal-air batteries[30]. Additionally, as can be seen from the
high-resolution TEM in Fig.2(C), the thickness of these nano-
sheets is ca. 4 nm. The elemental mapping in Fig.2(D) verifies
the three metal elements of Pt, Ni, and Ru are evenly distri-
buted on PtRuNi/NiNS/NiS. The PXRD pattern[Fig.2(E)]
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)
crystalline orientations of NiNS/NiS(JCPDS No.04-0850),
respectively. The other peaks observed at 41.04° and 46.96°
should be assigned to the formation of PtRuNi alloy, which is
consistent with the XPS analysis in Fig.2(F) and (G) as well.
Due to the existence of the alloying effect, the XPS signal dis-
palys a positive shift of Pt4f(71.30 and 75.0 eV), Ru3p(462.80
eV) in comparation with the corresponding binding energy of
single Pt4f7/2(70.64 eV), Pt4f5/2(74.50 eV) and Ru3p3/2(462.20
eV), respectively. The exact constitution of PtRuNi can hardly
be determined because of the interference from the substrate of
Ni sponge through PXRD, XPS, EDX or ICP-OES analysis.
Consequently, more suitable methods need to be developed to
determine the contents of each metal in future work. Further-
more, compared with most reported conducting materials
including polymer hydrogel[31], graphene mesh network with
Ni meshes[32], Ag nanowire on sponge[33], Ni-P-coated mela-
mine foam[18] and graphene foam on nickel templates[34]
shown in Fig.2(H), the electrical conductivity of the prepared
PtRuNi/NiNS/NiS reaches a higher value of 52.10 S/cm, which
is also comparable to NiS and NiNS/NiS(Fig.S3, see the Elec-
tronic Supplementary Material of this paper). The superior
conductive properties can be ascribed to the good conductivity
of porous metal substrate. As shown in Fig.2(I), this elaborately
constructed cathode demonstrates significant advantages as an
ideal oxygen cathode for metal-air batteries: high-efficient
bifunctional electrocatalytical activity provided by the ternary
alloy overlayer, rapid mass transfer by the hierarchical porous
structure, abundant exposed active sites benefiting from the
high specific surface area and well electronic conductivity, high
mechanical stability from the benefit of the self-standing struc-
ture of NiNS/NiS, and the superior chemical stability obtained
from the typical prepared method, which have laid a firm
foundation for favorable electrochemical performance of Zn-air
and Li-air batteries.

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
fast mass transfer and larger active area for the catalysts
because of the addition of different metals[35]. Galvanostatic
discharge curves in Fig.4(C) displayed the potential plains of
PtRuNi/NiNS/NiS of 1.38, 1.35, 1.32, 1.28, 1.24, 1.20 and 1.16
V at 2, 5, 10, 20, 30, 40 and 50 mA/cm2, respectively. Ama-
zingly, no evident change is observed in the voltage plateau of
1.37 V at 2 mA/cm2 after a cycle of different discharge current
densities, indicating the excellent rate capability of PtRu-
Ni/NiNS/NiS, which might be attributed to the hierarchically
porous structure, large specific surface, ultrathin nanosheet and
close-connection of active materials to the conductive sub-
strates, facilitating electron transport from the nanosheet to the
metallic substrates. The specific capacities of the battery
composed of PtRuNi/NiNS/NiS were up to ca. 813, 798 and
771 mA·h/gZn at different current densities of 10, 20, and 40
mA/cm2, respectively[Fig.4(D)]. Furthermore, the mechanical
rechargeablility of Zn-batteries was investigated. With the in-
creasingly consumed Zn in the discharging process, the zinc
plate and KOH electrolyte were refilled in the battery system to
recovery the battery. As can be seen from Fig.4(E), the battery
could be recharged for three consecutive cycles maintaining
similar performance on the same PtRuNi/NiNS/NiS electrode,
suggesting its excellent mechanical rechargeability, which
might be ascribed to its superior structural stability and chemi-
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.
with the pristine PtRuNi/NiNS/NiS according to the PXRD
pattern after 50 discharge-charge cycles in Fig.4(H), also con-
firming its durability and high structural stability. All these
results demonstrate the better ORR and OER bifunctional elec-
trocatalytic activity and high stability of PtRuNi/NiNS/NiS
than the other two binary metal catalysts in rechargeable Zn-air
batteries. Additionally, multiple Zn-air batteries with PtRu-
Ni/NiNS/NiS cathode can be integrated into series circuits to
convene particular energy needs for various practical applica-
tions. As shown in Fig.4(I), two series of Zn-air batteries with
PtRuNi/NiNS/NiS cathode can generate an open-circuit voltage
of 2.88 V to illuminate a red LED light, which is also consistent
with the voltage value from the discharge curves in Fig.4(B),
demonstrating the practical application potential of PtRu-
Ni/NiNS/NiS.
3.4 Li-air Batteries Performance
To verify the universality of the as-prepared electrode, the
electrochemical properties of the PtRuNi/NiNS/NiS-based
Li-air batteries were investigated in tetraethylene glycol dime-
thylether[Fig.5(A)]. For a definite comparison, the conven-
tional SP carbon was also utilized as the cathode for Li-air
batteries. Fig.5(B) shows the first discharge-charge voltage
curves of the Li-air batteries with SP carbon and PtRuNi/
NiNS/NiS cathodes at 100 mA/g. The overpotential is merely
0.40 V, and the energy efficiency is up to 87.5%, indicating the
superb ORR/OER electrocatalytic activity for PtRuNi/NiNS/
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)
4 Conclusions
A promising bifunctional cathode for Zn-air batteries and
Li-air batteries with outstanding electrochemical activity and
7
deliver a super high discharge capacity of 22429 mA h/gPtRuNi at
the curren density of 100 mA/g[Fig.5(C)], almost three times as
high as the SP carbon cathode(7921 mA·h/g), much better than
those of other reported carbon-free cathodes[39—42], indicating
that the structural merit of the highly porous metal-based
nanosheet self-standing structure could provide enough availa-
ble space to store the generated discharge products, which is
corresponding to the SEM images and the PXRD patterns of
the discharged SP carbon and PtRuNi/NiNS/NiS cathodes. The
mass transfer path is gradually blocked by plentiful discharged
products attached on the surface of the SP carbon cathode
(Fig.S7, see the Electronic Supplementary Material of this
paper), resulting in the discharge termination. On the contrary,
the loose and porous structure is obvious and the discharged
products of Li2O2 verified by the corresponding PXRD are
grown on the skeleton of the PtRuNi/NiNS/NiS cathode(Fig.S8,
see the Electronic Supplementary Material of this paper).
Galvanostatic discharge measurements in Fig.5(D) revealed the
superior rate capability of PtRuNi/NiNS/NiS, there appeared
almost no apparent potential decay over 1 h discharging even at
a high current density of 1000 mA/g, indicating the fast mass
transfer of O2 and Li+ flow into/departure from the cathode.
Additionally, the Li-air batteries with PtRuNi/NiNS/NiS
cathode performed a much longer stability of 136 cycles at a
limited capacity of 1000 mA·h/g, by contrast, the SP carbon
cathode exhibited merely 32 cycles[Fig.5(E)], demonstrating
high reversibility and rechargeability of PtRuNi/NiNS/
NiS-based Li-air batteries.
cycle stability is presented according to a facile construction
for ternary alloy nanosheet supported on Ni sponge(PtRuNi/
NiNS/NiS) through in-situ anchoring method, which can
effectively keep the nano-alloy from agglomeration during the
8 Chem. Res. Chinese Universities
prepared process. Due to the combination of anchoring method,
Ni sponge with high conductivity, ultrathin nanosheet structure
with large specific surface area and noble metal-base metal
ternary alloy with high catalytic activity, PtRuNi/NiNS/NiS
displays efficient ORR/OER bifunctional electrocatalytic
activity and long durability. Based on these superiorities, the
Zn-air batteries and Li-air batteries with the as-prepraed
PtRuNi/NiNS/NiS cathodes exhibit high discharge capacity,
superior rate capability, as well as excellent cycling stability,
suggesting that this nanosheet-like, self-standing, reversible
oxygen electrode holds great potential in practical application
of electrochemical energy storage devices and other sustainable
energy technologies.
Electronic Supplementary Material
Supplementary material is available in the online version
of this article at http://dx.doi.org/10.1007/s40242-020-0199-7.
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