CN115188976B - Zinc-air battery cathode catalyst and preparation method thereof - Google Patents

Zinc-air battery cathode catalyst and preparation method thereof Download PDF

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CN115188976B
CN115188976B CN202210732556.4A CN202210732556A CN115188976B CN 115188976 B CN115188976 B CN 115188976B CN 202210732556 A CN202210732556 A CN 202210732556A CN 115188976 B CN115188976 B CN 115188976B
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zinc
platinum
air
nickel
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CN115188976A (en
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毕璇璇
王荣跃
陈忠伟
王建涛
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Youyan Guangdong New Material Technology Research Institute
China Automotive Battery Research Institute Co Ltd
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Youyan Guangdong New Material Technology Research Institute
China Automotive Battery Research Institute Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite

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Abstract

The invention discloses a zinc-air battery cathode catalyst and a preparation method thereof. The catalyst consists of 1-30% of metal nano particles and 70-99% of carbon carrier material by weight percentage, wherein the metal nano particles have a core-shell structure and comprise a core formed by an alloy of three metals, a shell layer formed by a first metal and oxides of a second metal and a third metal covered on the shell layer; the first metal is one of platinum, palladium, ruthenium and iridium; the second metal and the third metal are respectively one of nickel, iron, manganese and cobalt. The invention adopts a one-pot synthesis method to synthesize metal nano particles, and prepares the nano composite catalyst through the processes of ultrasonic separation of carbon, air oxidation to remove surfactant, acid washing to form a core-shell structure, air oxidation to form surface oxide, and the like. The catalyst has high catalytic activity in the two processes of oxygen reduction and oxygen precipitation, and can effectively reduce the overpotential of the secondary zinc-air battery, thereby having high energy efficiency.

Description

Zinc-air battery cathode catalyst and preparation method thereof
Technical Field
The invention relates to the field of metal-air batteries, in particular to the technical field of zinc-air batteries which use zinc as an anode, air as a cathode and water-based liquid or solid electrolyte, and particularly relates to a zinc-air battery cathode catalyst and a preparation method thereof.
Background
The zinc-air battery is a novel secondary battery which is rapidly developed in the last ten years, has the advantages of high energy density (1353 Wh/kg), safe use process of the battery (water-based electrolyte can be used), low-cost and nontoxic electrode materials (less than $100kW -1h-1), simple preparation process and the like, and has very high application value and development prospect in the emerging large-scale energy storage fields of electric automobiles, energy storage grids and the like (chem.Sci., 2019, 10, 8924; adv.Mater.,2017, 29, 1604685).
Zinc-air cells are generally composed of the following components: zinc metal anode, membrane diaphragm, porous air cathode with supported catalyst, and strong alkaline electrolyte. When the battery is discharged, oxygen in the air enters a porous air cathode and is reduced to OH - on the surface of the catalyst; meanwhile, the zinc metal anode is oxidized to Zn (OH) 4 2- and further reacted to ZnO. The reactions of the zinc-air cell are as follows:
Anode: zn+4OH -→Zn(OH)4 2-+2e-
Zn(OH)4 2-→ZnO+H2O+2OH-
And (3) cathode: o 2+4e-+2H2O→4OH-
Total reaction: 2Zn+O 2 to 2ZnO
Initial zinc-air cell reports began in 1878 when a platinum-based catalyst cathode was used, and the primary cell discharge was completed (French Pat.,127069, 1878). Commercial zinc-air primary batteries began to enter the market in 1932 (US Pat.,1899615, 1933.), with early primary zinc-air batteries having very high energy densities (200-500 Wh kg -1), but very low power outputs. In recent years, research on secondary batteries of zinc-air batteries has been greatly increased, but the energy density of secondary zinc-air batteries is always unsatisfactory, and generally only 35Wh kg -1 is reached. The reason for this is mainly because the cathode reaction of the cell involves a multi-electron process, which is very slow in kinetics, resulting in polarization of the electrodes and very little current generation. Meanwhile, the zinc metal positive electrode also faces the problems of dendrite growth and the like, so that the zinc air battery is poor in circularity and stability.
The reaction efficiency of the cathode of a zinc-air cell is critical in determining the overall cell performance. In order to be able to achieve the purpose of recharging, the reaction at the cathode of the secondary zinc-air cell must be reversible. I.e., in the course of discharge, oxygen reduction reaction occurs; during charging, an oxygen evolution reaction occurs. Since both processes involve multiple electron processes, the reaction kinetics are slow, bringing too low a current and too high an overpotential. In this environment, the electrocatalyst supported on the gas diffusion layer is critical to accelerate the oxygen reduction and oxygen evolution reactions, determining the work density, energy efficiency and cycle life of the overall cell reaction. Commercial platinum metal catalysts have long been considered typical bifunctional catalysts in zinc-air cells (chem. Rev.,2016, 116, 3594-3657.), but the high platinum metal loading in commercial platinum carbon catalysts results in excessive zinc-air cell cost. Second, commercial platinum catalysts have good catalytic performance during oxygen reduction, but lower performance during oxygen evolution. For this reason, iridium carbon catalysts have been developed as oxygen evolution process catalysts, typically in combination with commercial platinum carbon catalysts, but iridium is a more expensive metal than platinum, and the combination of both results in not only a further increase in cost, but also occupation of each other's active sites, resulting in a decrease in the catalytic activity of the catalyst for a certain reaction. At present, due to the cost problem of the noble metal catalyst, the development of the non-noble metal catalyst is gradually increased, and the battery cost can be effectively reduced by using the non-noble metal catalyst, but the catalytic performance cannot be compared with that of the noble metal catalyst and the stability can be reduced. Thus, the search for a balance of performance and cost is critical to the selection of cathode catalysts for zinc-air batteries.
Although commercial platinum carbon or iridium carbon catalysts have high catalytic activity for oxygen reduction and oxygen evolution in zinc-air batteries, there are many problems with their use. 1) The noble metal loading is high, and the use cost is too high; 2) The stability is poor, and as the commercial catalyst is not fully optimized, the catalyst nano particles are easy to agglomerate in the cyclic application process, and the active sites are lost, so that the stability is reduced; 3) The shape controllability of the nanoparticle catalyst is poor, the particle size is not uniform, and the catalytic activity effect is influenced; 4) The single catalyst can not simultaneously meet the high-efficiency catalysis of the oxygen reduction process and the oxygen precipitation process, and can only have higher catalytic activity on one process, and the two processes simultaneously occupy active sites in the reaction of the other process, so that the catalytic activity of the two processes is reduced.
U.S. patent: the preparation of platinum nickel nanoparticle catalysts with multi-layered platinum shell layers is mentioned in U.S. Pat. No. 9,246,177 B2: one-step reactions are mentioned in US 10,833,332 B2 for the preparation of platinum nickel nanoparticles and a large scale catalyst preparation process is proposed. However, these patents do not mention the preparation and use of bifunctional catalysts useful in zinc air cells.
Disclosure of Invention
The invention aims to provide a cathode catalyst for a zinc-air battery, which has high catalytic activity in the two processes of oxygen reduction and oxygen precipitation, and can effectively reduce the overpotential of a secondary zinc-air battery, so that the catalyst has high energy efficiency.
The invention further aims to provide a preparation method of the zinc-air battery cathode catalyst, which is simple in process and high in repeatability, and can be used for preparing the high-efficiency and stable secondary zinc-air battery catalyst.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A zinc-air battery cathode catalyst, which consists of 1-30% of metal nano particles and 70-99% of carbon carrier material by weight percentage, wherein the metal nano particles have a core-shell structure, and comprise a core formed by an alloy of three metals, a shell formed by a first metal, and oxides of a second metal and a third metal covered on the shell; the first metal is one of platinum, palladium, ruthenium and iridium; the second metal and the third metal are respectively one of nickel, iron, manganese and cobalt.
Preferably, the content of the metal nanoparticles is 10% to 30%, and more preferably 20%.
Preferably, in the core-shell structure, the thinner the platinum atomic layer thickness is, the lower the platinum content is used, and the lower the cost is. The thinner the platinum atomic layer, the more easily the underlying alloy affects the catalytic activity of Pt, making Pt have the properties of an alloy catalyst. Thus, the thickness of the shell layer is 1 to 4 atomic layers, preferably 1 to 3 atomic layers, and more preferably 1 to 2 atomic layers.
In the core-shell structure, the surface area coverage of the oxide on the shell layer is 0.1 to 90%, preferably 10 to 60%, and more preferably 20 to 40%.
Preferably, the first metal is platinum, the second metal is nickel, and the third metal is iron. In the metal nano particles, the nickel accounts for 30-50 atomic percent in the three metals, and is more preferably 40-50 atomic percent; the atomic percentage of iron is preferably 1 to 10%, more preferably 5 to 10%. The catalyst consists of a platinum nickel iron alloy core, a platinum shell and an iron oxide nanoparticle coated core-shell structure. Wherein, when the atomic percent of platinum and nickel in the platinum-nickel-iron alloy core is equal to 1:1, the platinum-nickel alloy core shows higher catalytic performance in the oxygen reduction process, and the cost is reduced when the atomic percent of platinum is lower than 50 percent. Wherein iron is oxidized to form iron oxide during annealing, the coverage is not too high, otherwise the platinum shell active sites are covered to affect the catalytic performance, so the lower content of 5-10% is preferable.
The preparation method of the zinc-air battery cathode catalyst comprises the following steps:
(1) Mixing precursors corresponding to three metals with an organic solvent, a reducing agent and a surfactant, heating under the protection of inert gas to prepare ternary alloy nano particles, centrifugally cleaning, and loading the ternary alloy nano particles on a carbon carrier;
(2) Surfactant removal by high temperature annealing: annealing at 150-600 deg.c for 5min-20 hr under the protection of air, inert atmosphere or reducing atmosphere;
(3) Forming a core-shell structure by acid washing: pickling with 0.1-1M sulfuric acid, nitric acid or perchloric acid for 1min-20 hr;
(4) Oxide is formed on the shell surface by thermal oxidation in air: heating in air at 40-300 deg.C for 1min-20h.
In the step (1), three metal precursor solutions comprise acetylacetone salt, acetate, nitrate and the like corresponding to metal ions, reducing agents with the functions of tetradecanediol, oleylamine and the like are added, the surfactant is oleylamine and oleic acid, and the temperature is heated to 200-1000 ℃, preferably 200-600 ℃, more preferably 300 ℃ for 0.5-10 hours, preferably 1 hour.
In the step (2), the surfactant is preferably removed by annealing in air at 170-250 ℃ for 5min-20h, and more preferably annealing for 30min. The surface active agent on the surface of the ternary metal material can be removed by annealing under the condition, the morphology of the ternary metal material is not affected, the incomplete removal of the surface active agent can be caused by the excessively low temperature and the excessively short annealing time, and the surface composition of the catalyst can be affected by the excessively high temperature and the excessively long annealing time; or annealing for 5min-20H, more preferably 4H at 350-600 ℃ under the protection of H 2/Ar mixed atmosphere. The surface composition, structure, morphology and metal oxidation degree of the material can be adjusted by annealing under different atmospheres, and the catalytic performance can be different due to different surface compositions.
In the step (3), the thickness of the platinum shell layer is determined by the time of pickling, metal ions such as nickel and iron on the surface of the nano particles are dissolved in the acid, and platinum is not dissolved, so that the platinum shell is obtained. If the thickness of the platinum shell is increased correspondingly under the condition of longer pickling time, the catalyst may show catalytic activity similar to that of platinum, and the platinum shell does not form an atomic layer due to shorter time, so that a completely covered platinum shell structure cannot be formed. Therefore, in the step (3), the pickling time is preferably 1h.
In the step (4), heating is preferably performed at 150 to 200℃for 1min to 20h, and more preferably 15min to 1h. Iron cannot be oxidized in the air at a lower annealing temperature, and other metals can be oxidized at an excessive annealing temperature, so that the catalytic performance is reduced. Meanwhile, the annealing time is not too long, and too long can oxidize platinum and nickel in the system, so that the catalytic performance is reduced.
The invention has the beneficial effects that:
The composite nano catalyst with the surface oxide modified three-metal nano particles loaded on carbon is a double-function catalyst, has high catalytic activity in the double processes of oxygen reduction and oxygen precipitation, and can effectively reduce the overpotential of a secondary zinc-air battery, thereby having high energy efficiency. The catalyst has higher stability, can effectively improve the stability and cycle number of the new air battery, is an effective catalyst which can be applied to the secondary zinc air battery, and plays an important role in future development of the zinc air battery. Taking platinum nickel iron trimetallic as an example, the specific advantages are as follows:
1) The addition of the nickel iron metal reduces the amount of platinum catalyst, thereby reducing the cost of the catalyst.
2) Compared with pure platinum metal, the addition of the ferronickel can effectively balance the oxygen adsorption and desorption capacity, so that the catalytic activity of the oxygen reduction process is improved; meanwhile, the ferronickel metal oxide also has higher oxygen precipitation catalytic activity, so that the ferronickel metal oxide is more suitable for serving as a bifunctional catalyst of a secondary zinc-air battery than a commercial platinum-carbon catalyst.
3) The method for synthesizing the platinum nickel iron nano particles comprises the steps of firstly synthesizing the platinum nickel iron nano particles and then loading the platinum nickel iron nano particles on a carbon material, so that the size of the nano particles can be precisely controlled, a catalyst with uniform size can be formed, and the uniformity degree of the platinum nickel iron nano particles is greatly improved compared with that of commercial platinum carbon catalysts.
4) The nanoparticle catalyst can be uniformly distributed on the carbon material in the process of post-carbon loading, so that more active sites are provided, and agglomeration is not easy in the catalytic process, so that the nanoparticle catalyst has higher catalytic activity and higher stability.
Drawings
Fig. 1 is a schematic structural view of a cathode catalyst for a zinc-air cell according to the present invention, which includes an enlarged view of metal nanoparticles.
Fig. 2 is a schematic diagram showing a process for preparing a cathode catalyst for a zinc-air cell according to the present invention.
FIG. 3 is a graph of a platinum nickel iron/carbon composite catalyst transmission electron microscope and a high power transmission electron microscope.
Fig. 4 is an electrochemical test curve of platinum on carbon, platinum nickel iron on carbon catalyst (prepared in example 1) in a zinc air cell.
Fig. 5 is an electrochemical test curve of a platinum nickel iron/carbon catalyst (prepared in example 2) in a zinc air cell.
Fig. 6 is an electrochemical test curve of a platinum nickel iron/carbon catalyst (prepared in example 3) in a zinc air cell.
Fig. 7 is an electrochemical test curve of palladium nickel iron on carbon catalyst (prepared in example 4) in a zinc air cell.
Fig. 8 is an electrochemical test curve of iridium nickel cobalt/carbon catalyst (prepared in example 5) in a zinc air cell.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples, but is not meant to limit the scope of the invention.
In a secondary zinc-air cell, the cathode reaction undergoes the following process: The process is a reversible reaction, the forward direction is an oxygen reduction process, the reverse reaction is an oxygen precipitation reaction in the discharging process of the battery, and the reverse reaction is an oxygen precipitation reaction in the charging process of the battery. The reaction involves a 4 electron transfer process, which increases the polarization of the reaction, resulting in too high an overpotential. Typically, both processes each require a suitable catalyst to catalyze the reaction process to achieve the desired catalytic effect. The zinc-air cell cathode catalyst requires both good oxygen reduction catalytic capability and good oxygen evolution catalytic capability.
In order to improve the performance of the secondary zinc-air battery, the inventors devised an oxide modified trimetallic catalyst (e.g., a platinum iron nickel composite catalyst) that can be used for both the catalysis of the oxygen reduction and oxygen evolution processes. As shown in fig. 1, the catalyst is composed of a carbon support material 1 and metal nanoparticles 2 supported on the carbon support material 1, wherein the metal nanoparticles 2 have a core-shell structure including a core 3 composed of an alloy of three metals (a first metal, a second metal, and a third metal), a shell layer 4 composed of the first metal, and an oxide 5 of the second metal and the third metal coated on the shell layer. In the catalyst of the present invention, the first metal may be one of platinum, palladium, ruthenium, iridium; the second metal and the third metal can be respectively one of nickel, iron, manganese and cobalt.
As shown in fig. 2, the catalyst of the invention adopts a simple preparation process, synthesizes metal nano particles by a one-pot synthesis method, and prepares the nano composite catalyst through the processes of ultrasonic separation, carbon loading, air oxidation to remove a surfactant, acid washing to form a core-shell structure, air oxidation to form surface oxide and the like. The invention uses a highly controllable one-pot synthesis method, can prepare ternary metal alloy nano particles with uniform morphology, has the nano particle size controllable from 2nm to 10nm, can uniformly distribute on a porous carbon material, and has highly controllable oxide and metal proportion on the surface of the catalyst.
The catalyst provided by the invention is applied to a secondary zinc-air battery, wherein the zinc-air battery is composed of zinc metal or an anode containing zinc ions on the premise of using the catalyst, the electrolyte uses a water-based or organic phase solvent, the solute is composed of a common zinc ion compound, and the composite nano material catalyst can be loaded on carbon cloth or carbon paper or other substrates such as nickel screen and the like.
Example 1
Commercial platinum carbon catalysts are commercially available and the catalysts of the present invention are prepared by a one-step process. To 200mL of xylene ether solution was added a platinum nickel iron precursor: 3mmol of platinum acetylacetonate, 7mmol of nickel acetylacetonate, 1mmol of iron acetylacetonate, 5mL of oleylamine and 5mL of oleic acid as surfactants and 50mL of dichlorobenzene as polar solvent additives were added, and 3mmol of tetradecanediol was used as a reducing agent. The solution is heated to 250 ℃ for 30 minutes to prepare the platinum nickel iron nano particles. And mixing the obtained nanoparticle solution with carbon which is ultrasonically dispersed in chloroform solution, centrifugally separating out a nano material after ultrasonic treatment, annealing at 150 ℃ for 1h under air, pickling for 30min by sulfuric acid, further oxidizing in air at 40 ℃ for 5min, and obtaining the prepared oxide-modified platinum-nickel-iron three-metal catalyst loaded on the carbon, wherein the atomic ratio of platinum-iron-nickel to carbon is about 30% to 70%. The atomic ratio of platinum to nickel to iron in the platinum iron nickel nanoparticles is about 25% to 66% to 9% and the nickel iron oxide coverage is about 10%. The distribution of the element on the surface of the nano catalyst is shown in table 1, and is the atomic ratio analysis result of the element in the energy scattering X-ray spectrum (EDS) of the platinum-nickel-iron nano particles, and the atomic ratio analysis result is obtained by an energy dispersive X-ray spectrometer.
TABLE 1
Element(s) Atomic percent (%)
Pt 25.02
Ni 65.81
Fe 9.17
The prepared catalyst nano-particles are about 3-4nm and uniformly distributed on the carbon material, as shown in fig. 3.
The composite nano catalyst is further loaded on carbon cloth or carbon paper, and Nafion solution can be added as an adhesive for the cathode material of the secondary zinc-air battery. The zinc-air cell consists of a zinc metal anode, an alkaline water-based electrolyte (6M KOH solution), a catalyst cathode and an electrode current collector. Prior to testing, air was passed into the cathode for electrochemical testing, the curve being shown in fig. 4. The cell test results were compared with a commercial platinum carbon catalyst and a platinum nickel carbon catalyst by a platinum nickel iron composite nanocatalyst. Commercial platinum carbon catalyst using a field noble (TKK) catalyst, a platinum nickel carbon catalyst was prepared in the same manner as in example 1, without adding ferric acetylacetonate to the precursor solution. The platinum nickel iron carbon catalyst provided by the invention has higher oxygen reduction potential and lower oxygen precipitation potential, and shows excellent catalytic performance for two processes of a zinc air battery. In the stability test, the platinum nickel iron carbon catalyst cycle performance showed higher cycle performance relative to the other two catalysts.
Example 2
The catalyst preparation was similar to example 1. To 200mL of the xylene ether solution were added 2mmol of platinum acetylacetonate, 6mmol of nickel acetylacetonate, 2mmol of iron acetylacetonate, 5mL of oleylamine and 5mL of oleic acid as surfactants and 50mL of dichlorobenzene as a polar solvent additive, and 3mmol of tetradecanediol as a reducing agent. The solution is heated to 500 ℃ for 1 hour to prepare the platinum nickel iron nano particles. And mixing the obtained nanoparticle solution with carbon which is ultrasonically dispersed in chloroform solution, performing centrifugal separation to obtain a nanomaterial after ultrasonic treatment, annealing the nanomaterial at 600 ℃ for 10 hours under argon, pickling the nanomaterial by sulfuric acid for 1 hour and further oxidizing the nanomaterial in air at 200 ℃ for 10 hours to obtain the prepared oxide-modified platinum-nickel-iron trimetallic catalyst supported on the carbon, wherein the ratio of platinum-iron-nickel to the carbon is about 40 percent to 60 percent. The atomic ratio of platinum to nickel to iron in the platinum iron nickel nanoparticles is about 25% to 55% to 20% and the nickel iron oxide coverage is about 20%.
The composite nano catalyst is further loaded on carbon cloth or carbon paper, and Nafion solution is added as an adhesive to be used in the cathode of the secondary zinc-air battery. The battery test method and procedure were similar to example 1. Electrochemical test curves as shown in fig. 5, the performance exceeded that of commercial platinum carbon catalysts and platinum nickel carbon catalysts.
Example 3
The catalyst was prepared in a similar manner to example 1, and 3mmol of platinum acetylacetonate, 6mmol of nickel acetate, 1mmol of iron acetate, 5mL of a surfactant such as oleylamine and 5mL of oleic acid, 50mL of dichlorobenzene as a polar solvent additive, and 3mmol of tetradecanediol as a reducing agent were added to 200mL of a xylene ether solution. The solution is heated to 1000 ℃ for 5 hours to prepare the platinum nickel iron nano particles. And mixing the obtained nanoparticle solution with carbon which is ultrasonically dispersed in a chloroform solution, performing centrifugal separation after ultrasonic treatment to obtain a nanomaterial, annealing the nanomaterial at 300 ℃ under argon-hydrogen mixed gas for 1h, further oxidizing the nanomaterial in air after pickling with sulfuric acid for 5h at a temperature of 100 ℃ for 10h, and obtaining the prepared oxide-modified platinum-nickel-iron trimetallic supported on the carbon, wherein the ratio of platinum-iron-nickel to the carbon is about 30 percent to 70 percent. In the platinum iron nickel nanoparticle, the atomic ratio of platinum to nickel to iron is about 30 percent to 60 percent to 10 percent, and the coverage of nickel iron oxide is about 30 percent.
Electrochemical testing of the composite catalyst in a zinc air cell was similar to example 1. The electrochemical test curves are shown in fig. 6.
Example 4
The catalyst preparation was similar to example 1, adding 3mmol of palladium acetylacetonate, 6mmol of nickel acetylacetonate, 1mmol of iron acetylacetonate to 200mL of a xylene ether solution, and adding 5mL of oleylamine and 5mL of oleic acid as surfactants and 50mL of dichlorobenzene as a polar solvent additive, using 3mmol of tetradecanediol as a reducing agent. The solution is heated to 250 ℃ for 30 minutes to prepare the palladium nickel iron nano particles. And mixing the obtained nanoparticle solution with carbon which is ultrasonically dispersed in chloroform solution, centrifugally separating out a nano material after ultrasonic treatment, annealing at 150 ℃ for 1h under air, pickling for 30min by sulfuric acid, further oxidizing in air at 40 ℃ for 5min, and obtaining the prepared oxide-modified palladium-nickel-iron trimetallic catalyst loaded on the carbon, wherein the atomic ratio of the palladium-nickel-iron to the carbon is about 30 percent to 70 percent. In the palladium iron nickel nanoparticle, the atomic ratio of palladium to nickel to iron is about 30 percent to 60 percent to 10 percent, and the coverage of nickel iron oxide is about 10 percent.
Electrochemical testing of the composite catalyst in a zinc air cell was similar to example 1. The electrochemical test curves are shown in fig. 7.
Example 5
The catalyst preparation was similar to example 1, adding 3mmol of iridium acetylacetonate, 6mmol of nickel acetylacetonate, 1mmol of cobalt acetylacetonate to 200mL of a xylene ether solution, and adding 5mL of oleylamine and 5mL of oleic acid as surfactants and 50mL of dichlorobenzene as a polar solvent additive, using 3mmol of tetradecanediol as a reducing agent. Heating the solution to 300 ℃ for 1h to prepare the iridium nickel cobalt nano particles. And mixing the obtained nanoparticle solution with carbon ultrasonically dispersed in chloroform solution, centrifugally separating the nano material after ultrasonic treatment, annealing at 150 ℃ for 1h under air, further oxidizing in air after pickling for 30min by sulfuric acid at 40 ℃ for 5min to obtain the prepared iridium nickel cobalt trimetallic catalyst modified by the oxide loaded on the carbon, wherein the atomic ratio of iridium nickel cobalt to carbon is about 30% to 70%. The atomic ratio of iridium to nickel to cobalt in the iridium nickel cobalt nanoparticles is about 30% to 60% to 10%, and the coverage of nickel cobalt oxide is about 10%.
Electrochemical testing of the composite catalyst in a zinc air cell was similar to example 1. The electrochemical test curves are shown in fig. 8.
The foregoing description of the preferred embodiments of the invention is merely illustrative of the invention and is not intended to be limiting. It should be noted that, for those skilled in the art, other equivalent modifications can be made in light of the technical teaching provided by the present invention, and the present invention can be implemented as the scope of protection.

Claims (8)

1. A zinc-air battery cathode catalyst, which is characterized by comprising 1-30% of metal nano particles and 70-99% of carbon carrier material by weight percentage, wherein the metal nano particles have a core-shell structure and comprise a core formed by an alloy of three metals, a shell formed by a first metal and oxides of a second metal and a third metal covered on the shell; the surface area coverage of the oxide on the shell layer is 0.1-90%; the first metal is one of platinum, palladium, ruthenium and iridium; the second metal and the third metal are respectively one of nickel, iron, manganese and cobalt; the preparation method of the catalyst comprises the following steps:
(1) Mixing precursors corresponding to three metals with an organic solvent, a reducing agent and a surfactant, heating to 200-1000 ℃ under the protection of inert gas to prepare ternary alloy nano particles, centrifugally cleaning, and loading the ternary alloy nano particles on a carbon carrier;
(2) Surfactant removal by high temperature annealing: annealing at 150-600 deg.c for 5min-20 hr under the protection of air, inert atmosphere or reducing atmosphere;
(3) Forming a core-shell structure by acid washing: pickling with 0.1-1M sulfuric acid, nitric acid or perchloric acid for 1min-20 hr;
(4) Oxide is formed on the shell surface by thermal oxidation in air: heating in air at 40-300 deg.C for 1min-20h.
2. The zinc-air cell cathode catalyst according to claim 1, characterized in that the content of the metal nanoparticles is 10% to 30%.
3. The zinc-air cell cathode catalyst according to claim 1 or 2, wherein in the core-shell structure, the thickness of the shell layer is 1 to 4 atomic layers.
4. The zinc-air cell cathode catalyst of claim 1 or 2, wherein the first metal is platinum, the second metal is nickel, and the third metal is iron.
5. The zinc-air cell cathode catalyst according to claim 4, wherein the nickel content is 30 to 50 atomic percent among the three metals; iron content of 1-10% by atom; in the core composed of platinum nickel iron alloy, the atomic ratio between platinum and nickel is 1:1.
6. The zinc-air cell cathode catalyst according to claim 1, characterized in that in said step (2), annealing is carried out in air at 170-250 ℃ for 5min-20h; or annealing for 5min-20H at 350-600 ℃ under the protection of H 2/Ar mixed atmosphere.
7. The zinc-air cell cathode catalyst according to claim 1, wherein in the step (3), the pickling time is 1h.
8. The zinc-air cell cathode catalyst according to claim 1, wherein in the step (4), heating is performed at 150 to 200 ℃ for 1min to 20h.
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