CN111725524A - Fuel cell cathode catalyst, preparation method thereof, membrane electrode and fuel cell - Google Patents

Fuel cell cathode catalyst, preparation method thereof, membrane electrode and fuel cell Download PDF

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CN111725524A
CN111725524A CN201910223826.7A CN201910223826A CN111725524A CN 111725524 A CN111725524 A CN 111725524A CN 201910223826 A CN201910223826 A CN 201910223826A CN 111725524 A CN111725524 A CN 111725524A
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platinum alloy
fuel cell
nitrogen
cathode catalyst
platinum
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CN111725524B (en
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王中奇
王恒
卢荻
高正飞
史曦伶
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Qingdao Chuangqixinneng Catalysis Technology Co ltd
Three Gorges Technology Co ltd
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Qingdao Chuangqixinneng Catalysis Technology 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
    • 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
    • H01M4/88—Processes of manufacture
    • 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
    • H01M4/9041—Metals or alloys
    • H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a fuel cell cathode catalyst and a preparation method thereof, a membrane electrode and a fuel cell. The preparation method of the fuel cell cathode catalyst comprises the following steps: providing or preparing a nitrogen-doped carbon carrier deposited with platinum alloy nanoparticles; wherein the platinum alloy nanoparticles comprise platinum and at least one 3d transition metal; and consuming the 3d transition metal on the surface layer of the platinum alloy nano particles through acid treatment, and then carrying out heat treatment for 1-20 h at the temperature of 100-300 ℃ to obtain the fuel cell cathode catalyst. The fuel cell cathode catalyst prepared by the preparation method has good catalytic activity and stability, and is beneficial to industrial application.

Description

Fuel cell cathode catalyst, preparation method thereof, membrane electrode and fuel cell
Technical Field
The invention relates to the technical field of fuel cells, in particular to a fuel cell cathode catalyst and a preparation method thereof, a membrane electrode and a fuel cell.
Background
Proton Exchange Membrane Fuel Cells (PEMFC) are a type of fuel cell that converts chemical energy into electrical energy by cold combustion of hydrogen, with water being the only emission. The PEMFC is the core of hydrogen energy economy, the overpotential of the cathode oxygen reduction reaction is high, and a noble metal platinum catalyst is needed, so that the high-efficiency utilization of hydrogen energy is realized. Reducing the platinum dosage of the cathode catalyst is key to achieving large-scale commercial application of PEMFCs. Alloying of platinum with 3d transition metals has proven to be an effective means of reducing the amount of platinum used. However, the transition metal in the alloy catalyst is easily lost, which not only causes the oxygen reduction activity of the catalyst to be greatly reduced, but also reduces the proton conduction efficiency of the proton exchange membrane due to the lost metal cations. In addition, the support of the cathode catalyst has problems of uneven loading, low loading amount, and the like. At present, the performance of the improvement on the cathode catalyst on one aspect may be improved, but the performance on other aspects may be generally or even reduced, so that it is difficult to obtain a cathode catalyst with good catalytic activity and stability, which is not beneficial to industrial application.
Disclosure of Invention
In view of the above, it is necessary to provide a fuel cell cathode catalyst, a method for preparing the same, a membrane electrode, and a fuel cell, aiming at the problem of how to simultaneously improve the catalytic activity and stability of the cathode catalyst.
A preparation method of a fuel cell cathode catalyst comprises the following steps:
providing or preparing a nitrogen-doped carbon carrier deposited with platinum alloy nanoparticles; wherein the platinum alloy nanoparticles comprise platinum and at least one 3d transition metal; and
and (3) consuming the 3d transition metal on the surface layer of the platinum alloy nano particles through acid treatment, and then carrying out heat treatment for 1-20 h at the temperature of 100-300 ℃ to obtain the fuel cell cathode catalyst.
In one embodiment, the nitrogen-doped carbon carrier deposited with the platinum alloy nanoparticles is obtained by the following method:
activating a carbon carrier by acid treatment, uniformly mixing the carbon carrier with a nitrogen-containing compound, and carrying out heat treatment for 2-10 h at 500-1000 ℃ in an inert gas atmosphere to obtain a nitrogen-doped carbon carrier; and
and depositing platinum alloy nanoparticles on the nitrogen-doped carbon carrier to obtain the nitrogen-doped carbon carrier deposited with the platinum alloy nanoparticles.
In one embodiment, the nitrogen-doped carbon carrier deposited with the platinum alloy nanoparticles is obtained by the following method:
providing or preparing a carbon support having platinum alloy nanoparticles deposited thereon; and
and uniformly mixing the carbon carrier deposited with the platinum alloy nano particles with a nitrogen-containing compound, and then carrying out heat treatment for 2-10 h at 500-1000 ℃ in an inert gas atmosphere to obtain the nitrogen-doped carbon carrier deposited with the platinum alloy nano particles.
In one embodiment, before the step of uniformly mixing the carbon carrier deposited with the platinum alloy nanoparticles with the nitrogen-containing compound, the method further comprises the step of performing acid treatment on the carbon carrier deposited with the platinum alloy nanoparticles.
In one embodiment, the heat treatment after the carbon support on which the platinum alloy nanoparticles are deposited and the nitrogen-containing compound are uniformly mixed is defined as a first heat treatment, and the heat treatment after the 3d transition metal on the surface layer of the platinum alloy nanoparticles is consumed by acid treatment is defined as a second heat treatment;
the temperature of the first heat treatment is 600-800 ℃, and the time is 2-6 h; the temperature of the second heat treatment is 150-250 ℃, and the time is 1-8 h.
In addition, the fuel cell cathode catalyst comprises a nitrogen-doped carbon carrier and platinum alloy nanoparticles loaded on the surface of the nitrogen-doped carbon carrier.
In one embodiment, the platinum alloy nanoparticles comprise a platinum alloy core and a platinum shell coated on the surface of the platinum alloy core;
preferably, the thickness of the platinum shell is 0.5nm to 1.5 nm;
preferably, the mass fraction of the platinum alloy core in the platinum alloy nanoparticles is 40-75%.
In one embodiment, the mass fraction of nitrogen in the nitrogen-doped carbon support is 1-30%;
preferably, the size of the nitrogen-doped carbon carrier is 100 nm-25 μm, and the specific surface area of the nitrogen-doped carbon carrier is 200m2/g～1500m2/g；
Preferably, the mass fraction of the platinum alloy nanoparticles in the fuel cell cathode catalyst is 30-50%;
preferably, in the platinum alloy nanoparticles, the molar ratio of platinum to the 3d transition metal is 1: 3-5: 1.
Also provided is a membrane electrode comprising the fuel cell cathode catalyst.
Also provided is a fuel cell comprising the membrane electrode described above.
According to the preparation method of the fuel cell cathode catalyst, through the combination and integral design of nitrogen-doped carbon carrier, acid treatment and heat treatment, the electronic characteristics, surface alkalinity and other physical and chemical properties of the carbon material can be greatly improved, the active sites of metal particles adsorbed on the surface of the carbon material are increased, and metal nanoparticles are stabilized, so that the high-dispersity metal-loaded catalyst is obtained, the surface defects of the catalyst can be reduced, the distribution of platinum on the surface layer of the catalyst is increased, the platinum can be more easily combined with the nitrogen-doped carbon carrier, and the platinum alloy nanoparticles loaded on the surface of the nitrogen-doped carbon carrier are stable and regularly arranged, so that the stability is improved. The fuel cell cathode catalyst prepared by the preparation method has good catalytic activity and stability, and is beneficial to industrial application.
Drawings
Fig. 1 is a flow chart of a method of preparing a fuel cell cathode catalyst according to an embodiment of the present invention;
fig. 2(a) is a Scanning Electron Microscope (SEM) image of the fuel cell cathode catalyst prepared in comparative example 1;
fig. 2(b) is a Scanning Electron Microscope (SEM) image of the fuel cell cathode catalyst prepared in example 1;
fig. 3(a) is a Scanning Electron Microscope (SEM) image of the fuel cell cathode catalyst prepared in comparative example 2;
fig. 3(b) is a Scanning Electron Microscope (SEM) image of the fuel cell cathode catalyst prepared in example 2.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The inventor of the invention finds out in the research process that: the performance of fuel cell catalysts is mainly influenced by the surface structure and composition distribution of the catalyst, and the main obstacle to the progress is that the precise regulation of element distribution at the nano-scale level is difficult to realize. For example, the prior art has generally employed high temperature annealing of platinum alloy nanocatalysts to overcome this. However, while the specific activity improves, high temperatures tend to cause particle sintering and loss of electrochemical surface area. In addition, the surface of the nanometer material is rich in corner and edge sites, the coordination coefficient of the nanometer material is small, oxygen-containing functional groups (such as-OH) are easy to adsorb, the activity of Oxygen Reduction Reaction (ORR) on molecular oxygen is lost, and the specific activity of the catalyst is reduced and the service life is reduced along with the migration of low coordination sites.
Referring to fig. 1, a method for preparing a cathode catalyst of a fuel cell according to an embodiment of the present invention includes the following steps:
s10, providing or preparing the nitrogen-doped carbon carrier deposited with the platinum alloy nano particles; wherein the platinum alloy nanoparticles comprise platinum and at least one 3d transition metal.
Preferably, the platinum alloy nanoparticles are selected from at least one of platinum cobalt alloy nanoparticles, platinum nickel nanoparticles, and platinum iron nanoparticles.
Preferably, the platinum alloy nanoparticles further comprise one or two of manganese, iridium, rhodium, niobium and zirconium.
Preferably, the platinum alloy nanoparticles have a particle size in the range of 3nm to 6 nm.
Wherein, the 3d transition metal refers to a metal in which the last electron is arranged on the 3d orbital when the electrons of the atom are arranged. For example, cobalt, nickel, iron, and the like.
In one preferred embodiment, the nitrogen-doped carbon carrier deposited with platinum alloy nanoparticles is obtained by the following method:
and S1, activating the carbon carrier by acid treatment, uniformly mixing the activated carbon carrier with the nitrogen-containing compound, and carrying out heat treatment for 2-10 h at 500-1000 ℃ in an inert gas atmosphere to obtain the nitrogen-doped carbon carrier.
Preferably, the size of the carbon support is 100nm to 25 μm.
Wherein, the acid treatment activation refers to increasing the number of functional groups and defects on the surface of the carbon carrier by the acid treatment, thereby increasing the doping amount of nitrogen.
Among them, the nitrogen-containing compound is preferably urea or ammonia gas. These nitrogen-containing compounds are inexpensive, safe and convenient to use.
Preferably, the heat treatment is performed in an oxygen-containing atmosphere. Wherein, the oxygen-containing atmosphere can be pure oxygen or air. Since the 3d transition metal on the surface layer can be oxidized into oxide after heat treatment in an oxygen-containing atmosphere, the 3d transition metal can be more easily consumed when acid treatment is subsequently adopted.
And S2, depositing platinum alloy nano particles on the nitrogen-doped carbon carrier to obtain the nitrogen-doped carbon carrier deposited with the platinum alloy nano particles.
In another preferred embodiment, the nitrogen-doped carbon support on which the platinum alloy nanoparticles are deposited is obtained by:
s3, providing or preparing a carbon support having platinum alloy nanoparticles deposited thereon.
Wherein, the carbon carrier deposited with the platinum alloy nano particles can be prepared by the following steps: and depositing platinum alloy nanoparticles on the carbon carrier to obtain the carbon carrier deposited with the platinum alloy nanoparticles.
The carbon carrier includes, but is not limited to, carbon nanotubes, carbon nanofibers, mesoporous carbon, carbon spheres, or graphene, and other conductive materials.
Preferably, the operation of depositing the platinum alloy nanoparticles on the carbon support is: adding a carbon carrier, a platinum precursor and at least one 3d transition metal precursor into a solvent, uniformly mixing, adding a reducing agent, and fully reacting to obtain the catalyst.
Wherein, the solvent can be glycol, water, methanol or ethanol. Wherein the addition of the reducing agent reduces the metal salt. The reducing agent may be, for example, NaBH4Ascorbic acid or citric acid.
S4, uniformly mixing the carbon carrier deposited with the platinum alloy nano particles with a nitrogen-containing compound, and then carrying out heat treatment for 2-10 h at 500-1000 ℃ in an inert gas atmosphere to obtain the nitrogen-doped carbon carrier deposited with the platinum alloy nano particles.
Step S4 enables simultaneous nitrogen doping and alloying. After heat treatment, nitrogen doping can be realized, and the stability of the platinum alloy nanoparticles is improved.
Both of the above-described preferred embodiments result in a nitrogen-doped carbon support loaded with platinum alloy nanoparticles. In the nitrogen-doped carbon carrier, nitrogen atoms are introduced into an sp2 hybrid structure, so that the electronic characteristics, surface alkalinity and other physical and chemical properties of the carbon material can be greatly improved, the nitrogen-containing groups can increase the active sites of the metal particles adsorbed on the surface of the carbon material, and the metal nanoparticles are stabilized, thereby being beneficial to obtaining the high-dispersity metal-supported catalyst.
Further, before the step of uniformly mixing the carbon carrier on which the platinum alloy nanoparticles are deposited with the nitrogen-containing compound, the method further comprises the step of performing acid treatment on the carbon carrier on which the platinum alloy nanoparticles are deposited. The aim is to activate the carbon support and the platinum alloy particles simultaneously and consume the 3d transition metal.
And S20, consuming the 3d transition metal on the surface layer of the platinum alloy nano particles through acid treatment, and then carrying out heat treatment for 1-20 h at the temperature of 100-300 ℃ to obtain the fuel cell cathode catalyst. The acid treatment means that the nitrogen-doped carbon carrier deposited with the platinum alloy nanoparticles is soaked in an acid solution and is taken out after being maintained for a period of time. Wherein, the soaking process can be stirred. The stability of the alloy catalyst is improved by the acid treatment.
Wherein the acid used in the acid treatment process is preferably at least one of acetic acid, sulfuric acid, nitric acid and perchloric acid. Preferably, the pH of the acid treatment environment is less than 1, the temperature of the acid treatment is 50-80 ℃, and the time of the acid treatment is 1-12 h.
After the heat treatment in step S20, the surface defects of the catalyst can be reduced, and the distribution of platinum on the surface layer of the catalyst can be increased.
Preferably, the heat treatment in step S20 is performed in an oxygen-containing atmosphere. After the acid treatment, unconsumed 3d transition metal may remain on the surface layer of the product, and after the heat treatment in the oxygen-containing atmosphere, the residual 3d transition metal is continuously oxidized, and after the residual 3d transition metal is reduced in the subsequent use process, the oxidized part is continuously removed, so that the residual 3d transition metal on the surface layer is reduced.
Of course, the atmosphere of the heat treatment in step S20 is not limited, and may be performed in an oxygen-free atmosphere.
Further, the heat treatment after the carbon support on which the platinum alloy nanoparticles are deposited and the nitrogen-containing compound are uniformly mixed is defined as a first heat treatment, and the heat treatment after the 3d transition metal on the surface layer of the platinum alloy nanoparticles is consumed by the acid treatment is defined as a second heat treatment;
the temperature of the first heat treatment is 600-800 ℃, and the time is 2-6 h; the temperature of the second heat treatment is 150-250 ℃ and the time is 1-8 h. Through the combination of the first heat treatment and the second heat treatment in the temperature and time, the finally prepared fuel cell cathode catalyst has good catalytic activity and stability.
According to the preparation method of the fuel cell cathode catalyst, after two times of heat treatment, the platinum alloy nanoparticles loaded on the surface of the nitrogen-doped carbon carrier are stable and regularly arranged. By uniformly mixing the carbon carrier and the nitrogen-containing compound and then carrying out first heat treatment, nitrogen atoms can be introduced into an sp2 hybrid structure, the electronic characteristics, surface alkalinity and other physical and chemical properties of the carbon material can be greatly improved, and the nitrogen-containing groups can increase the active sites of metal particles adsorbed on the surface of the carbon material and stabilize the metal nanoparticles, so that the high-dispersity metal-supported catalyst can be obtained. Through the second heat treatment, the surface defects of the catalyst can be reduced, and the distribution of platinum on the surface layer of the catalyst is increased, so that the platinum can be more easily combined with the nitrogen-doped carbon carrier, and the stability is improved. In particular, by performing the first heat treatment in an oxygen-containing atmosphere, the 3d transition metal of the surface layer can be oxidized to an oxide, and this portion of the 3d transition metal can be more easily consumed in conjunction with the subsequent acid treatment. The fuel cell cathode catalyst prepared by the preparation method has good catalytic activity and stability, and is beneficial to industrial application.
The preparation method of the fuel cell cathode catalyst of the present invention is not limited to the above-described technical solutions, and the following technical solutions may be adopted:
s1, providing a carbon carrier deposited with platinum alloy nano particles; wherein the platinum alloy nanoparticles comprise platinum and at least one 3d transition metal.
And S2, carrying out acid treatment on the carbon carrier deposited with the platinum alloy nano particles to obtain the carbon carrier deposited with the platinum alloy nano particles after the acid treatment.
S3, uniformly mixing the carbon carrier deposited with the platinum alloy nano particles after acid treatment with a nitrogen-containing compound, and then carrying out heat treatment to obtain a fuel cell cathode catalyst; the fuel cell cathode catalyst comprises a nitrogen-doped carbon carrier and platinum alloy nanoparticles loaded on the surface of the nitrogen-doped carbon carrier.
According to the preparation method of the fuel cell cathode catalyst, through the combination and integral design of nitrogen-doped carbon carrier, acid treatment and heat treatment, the electronic characteristics, surface alkalinity and other physical and chemical properties of the carbon material can be greatly improved, the active sites of metal particles adsorbed on the surface of the carbon material are increased, and metal nanoparticles are stabilized, so that the high-dispersity metal-loaded catalyst is obtained, the surface defects of the catalyst can be reduced, the distribution of platinum on the surface layer of the catalyst is increased, the platinum can be more easily combined with the nitrogen-doped carbon carrier, and the platinum alloy nanoparticles loaded on the surface of the nitrogen-doped carbon carrier are stable and regularly arranged, so that the stability is improved. The fuel cell cathode catalyst prepared by the preparation method has good catalytic activity and stability, and is beneficial to industrial application.
The fuel cell cathode catalyst of an embodiment comprises a nitrogen-doped carbon carrier and platinum alloy nanoparticles loaded on the surface of the nitrogen-doped carbon carrier.
Preferably, the fuel cell cathode catalyst is prepared by the preparation method of the fuel cell cathode catalyst. The fuel cell cathode catalyst prepared by the preparation method has at least one tightly arranged platinum monoatomic layer on the surface, and has good catalytic activity and stability.
Preferably, the platinum alloy nanoparticles include a platinum alloy core and a platinum shell coated on the surface of the platinum alloy core.
More preferably, the thickness of the platinum shell is 0.5nm to 1.5 nm. Preferably, the mass fraction of the platinum alloy core in the platinum alloy nanoparticles is 40-75%.
Preferably, the mass fraction of nitrogen in the nitrogen-doped carbon carrier is 1-30%.
Preferably, the nitrogen-doped carbon support has a size of 100nm to 25 μm and a specific surface area (BET) of 200m2/g～1500m2(ii) in terms of/g. The stability of the carbon support can be optimized while ensuring the catalyst loading.
Preferably, the mass fraction of the platinum alloy nanoparticles in the fuel cell cathode catalyst is 30% to 50%.
Preferably, in the platinum alloy nanoparticles, the molar ratio of platinum to the 3d transition metal is 1: 3-5: 1. Advantageously providing catalyst stability.
An embodiment membrane electrode includes the fuel cell cathode catalyst described above.
The fuel cell of an embodiment includes the membrane electrode.
The fuel cell cathode catalyst, the method for preparing the same, the membrane electrode, and the fuel cell according to the present invention will be further described with reference to the following embodiments.
Example 1
100mg of XC-72 carbon support (average particle size 2 μm, BET 250 m)2/g) in H2SO4/HNO3(v/v. 3:1) stirring at room temperature for 2H, then with 200mg H2PtCl6、200mg Co(NO3)2Adding the mixture into 50mL of glycol, mixing uniformly, and then adding 50mgNaBH4And after sufficient reaction, obtaining the carbon carrier deposited with the platinum alloy nano particles.
And (3) washing and drying the carbon carrier deposited with the platinum alloy nano particles, and then carrying out primary heat treatment for 4 hours at 700 ℃ in an ammonia atmosphere to obtain a product after the primary heat treatment.
The above product was subjected to acid treatment in nitric acid having a pH of 1.0 for 2 hours, filtered and washed, and then subjected to a second heat treatment in an argon atmosphere at 250 ℃ for 1 hour to obtain a fuel cell cathode catalyst of example 1.
According to the characterization, in the obtained fuel cell cathode catalyst, the mass part of nitrogen in the nitrogen-doped carbon carrier is 3%, and the platinum loading capacity of the platinum-cobalt nanoparticles on the nitrogen-doped carbon carrier is 30%. The particle size of the platinum-cobalt particles is 4nm, the ratio of platinum to cobalt elements is 3:1, the thickness of a shell layer in the platinum-cobalt core-shell structure is about 0.5nm, and the content of cobalt in an inner core is about 45%. After cyclic voltammetry of the platinum-cobalt alloy carbon particle catalyst, the electrochemical surface area of the catalyst obtained in example 1 was 33.1m2/g Pt。
Example 2
100mg of XC-72 carbon support (average particle size 2 μm, BET 250 m)2/g) in H2SO4/HNO3(v/v. 3:1) stirring at room temperature for 2H, then with 200mg H2PtCl6、300mgNiCl2Adding the mixture into 50mL of glycol, mixing uniformly, and then adding 50mgNaBH4Fully reactThe carbon support with the platinum alloy nanoparticles deposited thereon is then obtained.
And (3) washing and drying the carbon carrier deposited with the platinum alloy nano particles, and then carrying out primary heat treatment for 4 hours at 700 ℃ in an ammonia atmosphere to obtain a product after the primary heat treatment.
The above product was subjected to acid treatment in nitric acid having a pH of 1.0 for 2 hours, filtered and washed, and then subjected to a second heat treatment in an argon atmosphere at 250 ℃ for 1 hour to obtain a fuel cell cathode catalyst of example 2.
Example 3
100mg of XC-72 carbon support (average particle size 2 μm, BET 250 m)2/g) in H2SO4/HNO3(v/v. 3:1) stirring at room temperature for 2H, then with 200mg H2PtCl6、200mg Fe(NO3)3Adding the mixture into 50mL of glycol, mixing uniformly, and then adding 50mgNaBH4And after sufficient reaction, obtaining the carbon carrier deposited with the platinum alloy nano particles.
And (3) washing and drying the carbon carrier deposited with the platinum alloy nano particles, and then carrying out primary heat treatment for 4 hours at 700 ℃ in an ammonia atmosphere to obtain a product after the primary heat treatment.
The above product was subjected to acid treatment in nitric acid having a pH of 1.0 for 2 hours, filtered and washed, and then subjected to a second heat treatment in an argon atmosphere at 250 ℃ for 1 hour to obtain a fuel cell cathode catalyst of example 3.
Example 4
100mg of XC-72 carbon support (average particle size 2 μm, BET 250 m)2/g) in H2SO4/HNO3(v/v ═ 3:1) was stirred at room temperature for 2 hours, washed and dried, and then subjected to a first heat treatment under an argon atmosphere at 700 ℃ for 4 hours to obtain a nitrogen-doped carbon support.
Mixing nitrogen-doped carbon carrier with 200mg of H2PtCl6、200mg Co(NO3)2Adding the mixture into 50mL of glycol, mixing uniformly, and then adding 50mgNaBH4And after full reaction, obtaining the nitrogen-doped carbon carrier deposited with the platinum alloy nano particles.
The nitrogen-doped carbon support on which the platinum alloy nanoparticles were deposited was subjected to acid treatment in nitric acid having a pH of 1.0 for 2 hours, filtered and washed, and then subjected to a second heat treatment in an argon atmosphere at 250 ℃ for 1 hour, to obtain a fuel cell cathode catalyst of example 4.
According to the characterization, the thickness of the shell layer in the platinum-cobalt core-shell structure in the obtained fuel cell cathode catalyst is about 1 nm.
Example 5
The difference between this example and example 1 is that the carbon carrier deposited with platinum cobalt nanoparticles is washed and dried, and then mixed with 50mg urea uniformly and heat-treated in argon atmosphere at 700 ℃ for 2 hours to obtain the product after the first heat treatment.
Example 6
The difference between this example and example 1 is that the carbon carrier deposited with platinum cobalt nanoparticles is washed and dried, and then mixed with 50mg urea and heat-treated in air atmosphere at 700 ℃ for 2 hours to obtain the product after the first heat treatment.
According to the characterization, the thickness of the shell layer in the platinum-cobalt core-shell structure in the obtained fuel cell cathode catalyst is about 1 nm.
Example 7
This example is different from example 1 in that the second heat treatment was performed in an air atmosphere and the temperature of the second heat treatment was 150 ℃.
Example 8
100mg of XC-72 carbon support (average particle size 2 μm, BET 250 m)2/g) in H2SO4/HNO3(v/v. 3:1) stirring at room temperature for 2H, then with 200mg H2PtCl6、200mg Co(NO3)2Adding the mixture into 50mL of glycol, mixing uniformly, and then adding 50mgNaBH4And after sufficient reaction, obtaining the carbon carrier deposited with the platinum alloy nano particles.
Washing and drying the carbon carrier deposited with the platinum alloy nanoparticles, then placing the product in nitric acid with the pH value of 1.0 for acid treatment for 2 hours, filtering and washing the product, then uniformly mixing the product with urea, and carrying out heat treatment for 4 hours at the temperature of 700 ℃ in an argon atmosphere to obtain the fuel cell cathode catalyst of the embodiment 8.
Example 9: membrane Electrode (MEA)
Preparation of cathode ink: 400mg of the fuel cell cathode catalyst prepared in example 1 was charged in a glass bottle, and mixed well with 10g of deionized water (Milli-Q), 15mg of isopropyl alcohol (IPA), 4.5ml of 5 wt% Nafion solution (D520) to obtain a cathode ink.
Preparing an anode ink: a homogeneous suspension was prepared using a HiSPEC4000 catalyst from Johnson Matthey by a method similar to that described above.
MEA preparation (CCM mode): the cathode ink and the anode ink were coated on both sides of a proton exchange membrane (Nafion 212) respectively by using an ultrasonic spray apparatus (model Prism 4000, manufactured by USI, USA), and the area of the catalyst layer was 5cm2The Pt loading capacity is quantitatively controlled to be 0.1mg/cm of the anode respectively2Cathode 0.4mg/cm2。
Example 10: fuel cell
Selecting 5cm2Example 9 the resulting two-layer MEA, attached 2.5cm2*2.5cm2The gas diffusion layer GDL (SGL 28BC, thickness 235 μm) of (1), a gasket having a thickness of 180 μm was further interposed between the two layers, and the resultant was packed with a cell holder and assembled with 4.2N-m to complete a cell.
Comparative example 1
100mg of XC-72 carbon support (average particle size 2 μm, BET 250 m)2/g) in H2SO4/HNO3(v/v. 3:1) stirring at room temperature for 2H, then with 200mg H2PtCl6、200mg Co(NO3)2Adding the mixture into 50mL of glycol, mixing uniformly, and then adding 50mgNaBH4And after sufficient reaction, obtaining the carbon carrier deposited with the platinum alloy nano particles.
The above product was subjected to acid treatment in nitric acid having a pH of 1.0 for 2 hours, filtered and washed, and then subjected to a second heat treatment in an argon atmosphere at 250 ℃ for 1 hour to obtain a fuel cell cathode catalyst of comparative example 1.
Scanning electron microscope characterization of the cathode catalysts of the fuel cells prepared in comparative example 1 and example 1 was performed to obtain fig. 2(a) and fig. 2(b), respectively. As can be seen from a comparison of fig. 2(a) and 2(b), in the fuel cell cathode catalyst prepared in example 1,the loading uniformity of the platinum-cobalt nanoparticles on the nitrogen-doped carbon carrier is good, which shows that the preparation method improves the loading uniformity of the platinum alloy nanoparticles on the nitrogen-doped carbon carrier. After cyclic voltammetry test was performed on the platinum-cobalt alloy carbon particle catalyst, the electrochemical surface area of the catalyst obtained in comparative example 1 was 49.1m2/g Pt。
Comparative example 2
100mg of XC-72 carbon support (average particle size 2 μm, BET 250 m)2/g) in H2SO4/HNO3(v/v. 3:1) stirring at room temperature for 2H, then with 200mg H2PtCl6、300mgNiCl2Adding the mixture into 50mL of glycol, mixing uniformly, and then adding 50mgNaBH4And after sufficient reaction, obtaining the carbon carrier deposited with the platinum alloy nano particles.
The above product was subjected to acid treatment in nitric acid having a pH of 1.0 for 2 hours, filtered and washed, and then subjected to a second heat treatment in an argon atmosphere at 250 ℃ for 1 hour to obtain a fuel cell cathode catalyst of comparative example 2.
Scanning electron microscope characterization of the cathode catalysts of the fuel cells prepared in comparative example 2 and example 2 was performed to obtain fig. 3(a) and fig. 3(b), respectively. As can be seen from comparison between fig. 3(a) and fig. 3(b), in the fuel cell cathode catalyst prepared in example 2, the loading amount of the platinum nickel nanoparticles on the nitrogen-doped carbon support is higher, indicating that the loading amount of the platinum alloy nanoparticles on the nitrogen-doped carbon support is increased by the preparation method of the present application.
Comparative example 3
100mg of XC-72 carbon support (average particle size 2 μm, BET 250 m)2/g) in H2SO4/HNO3(v/v. 3:1) stirring at room temperature for 2H, then with 200mg H2PtCl6、200mg Fe(NO3)3Adding into 50mL of glycol, mixing uniformly, and then adding 50mgNaBH4And after sufficient reaction, obtaining the carbon carrier deposited with the platinum alloy nano particles.
The above product was subjected to acid treatment in nitric acid having a pH of 1.0 for 2 hours, filtered and washed, and then subjected to a second heat treatment in an argon atmosphere at 250 ℃ for 1 hour to obtain a fuel cell cathode catalyst of comparative example 3.
Comparative example 4
100mg of XC-72 carbon support (average particle size 2 μm, BET 250 m)2/g) in H2SO4/HNO3(v/v. 3:1) stirring at room temperature for 2H, then with 200mg H2PtCl6、200mg Co(NO3)2Adding into 50mL of glycol, mixing uniformly, and then adding 50mgNaBH4And after sufficient reaction, obtaining the carbon carrier deposited with the platinum alloy nano particles.
The carbon carrier on which the platinum alloy nanoparticles were deposited was washed and dried, and then heat-treated at 700 deg.c in an ammonia atmosphere for 4 hours to obtain the fuel cell cathode catalyst of comparative example 4.
X-ray photoelectron spectroscopy (XPS) and stability tests were performed on the fuel cell cathode catalysts of examples 1 to 8 and comparative examples 1 to 4, respectively, wherein the stability test procedure was as follows:
the test was performed by assembling a Rotating Disk Electrode (RDE) with an electrolyte of 0.1M HClO saturated with N24The test condition of the aqueous solution is 0.6V-1.0V, and the scanning speed is 200 mV/s. The testing instrument was an electrochemical analyzer model CHI730D (CHI Instruments inc., u.s.) fitted with a rotating disk electrode system (Pine Instruments, u.s.).
The test results are shown in table 1:
TABLE 1 test data for fuel cell cathode catalysts of examples 1-8 and comparative examples 1-4
Figure BDA0002004442510000121
Figure BDA0002004442510000131
As can be seen from table 1, compared with the fuel cell cathode catalysts of comparative examples 1 to 4, the specific activity and the retention rate after 2 ten thousand cycles of the fuel cell cathode catalysts of examples 1 to 8 are higher, which indicates that after the fuel cell cathode catalysts of examples 1 to 8 are subjected to two heat treatments, the platinum alloy nanoparticles loaded on the surface of the nitrogen-doped carbon carrier are more stable and arranged more regularly, so that the catalytic activity and the stability are both good.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A preparation method of a fuel cell cathode catalyst is characterized by comprising the following steps:
providing or preparing a nitrogen-doped carbon carrier deposited with platinum alloy nanoparticles; wherein the platinum alloy nanoparticles comprise platinum and at least one 3d transition metal; and
and (3) consuming the 3d transition metal on the surface layer of the platinum alloy nano particles through acid treatment, and then carrying out heat treatment for 1-20 h at the temperature of 100-300 ℃ to obtain the fuel cell cathode catalyst.
2. The method for preparing a fuel cell cathode catalyst according to claim 1, wherein the nitrogen-doped carbon support on which the platinum alloy nanoparticles are deposited is obtained by:
activating a carbon carrier by acid treatment, uniformly mixing the carbon carrier with a nitrogen-containing compound, and carrying out heat treatment for 2-10 h at 500-1000 ℃ in an inert gas atmosphere to obtain a nitrogen-doped carbon carrier; and
and depositing platinum alloy nanoparticles on the nitrogen-doped carbon carrier to obtain the nitrogen-doped carbon carrier deposited with the platinum alloy nanoparticles.
3. The method for preparing a fuel cell cathode catalyst according to claim 1, wherein the nitrogen-doped carbon support on which the platinum alloy nanoparticles are deposited is obtained by:
providing or preparing a carbon support having platinum alloy nanoparticles deposited thereon; and
and uniformly mixing the carbon carrier deposited with the platinum alloy nano particles with a nitrogen-containing compound, and then carrying out heat treatment for 2-10 h at 500-1000 ℃ in an inert gas atmosphere to obtain the nitrogen-doped carbon carrier deposited with the platinum alloy nano particles.
4. The method for preparing a fuel cell cathode catalyst according to claim 3, further comprising a step of acid-treating the carbon support on which the platinum alloy nanoparticles are deposited, before the step of uniformly mixing the carbon support on which the platinum alloy nanoparticles are deposited with the nitrogen-containing compound.
5. The method for preparing a fuel cell cathode catalyst according to claim 3 or 4, characterized in that the heat treatment after uniformly mixing the carbon support on which the platinum alloy nanoparticles are deposited with the nitrogen-containing compound is defined as a first heat treatment, and the heat treatment after consuming the 3d transition metal on the surface layer of the platinum alloy nanoparticles by acid treatment is defined as a second heat treatment;
the temperature of the first heat treatment is 600-800 ℃, and the time is 2-6 h; the temperature of the second heat treatment is 150-250 ℃, and the time is 1-8 h.
6. The fuel cell cathode catalyst is characterized by comprising a nitrogen-doped carbon carrier and platinum alloy nanoparticles loaded on the surface of the nitrogen-doped carbon carrier.
7. The fuel cell cathode catalyst according to claim 6, wherein the platinum alloy nanoparticles comprise a platinum alloy core and a platinum shell coated on a surface of the platinum alloy core;
preferably, the thickness of the platinum shell is 0.5nm to 1.5 nm;
preferably, the mass fraction of the platinum alloy core in the platinum alloy nanoparticles is 40-75%.
8. The fuel cell cathode catalyst according to claim 6, wherein the mass fraction of nitrogen in the nitrogen-doped carbon support is 1% to 30%;
preferably, the size of the nitrogen-doped carbon carrier is 100 nm-25 μm, and the specific surface area of the nitrogen-doped carbon carrier is 200m2/g～1500m2/g；
Preferably, the mass fraction of the platinum alloy nanoparticles in the fuel cell cathode catalyst is 30-50%;
preferably, in the platinum alloy nanoparticles, the molar ratio of platinum to the 3d transition metal is 1: 3-5: 1.
9. A membrane electrode comprising the fuel cell cathode catalyst according to any one of claims 6 to 8.
10. A fuel cell comprising the membrane electrode of claim 9.
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