Proton exchange membrane fuel cell catalyst as well as preparation method and application thereof

Abstract

The invention discloses a proton exchange membrane fuel cell catalyst and a preparation method and application thereof.The proton exchange membrane fuel cell catalyst comprises a carrier and an active component which is loaded on the carrier and has a core-shell structure, the core of the core-shell structure is platinum Pt nanoparticles and / or platinum alloy PtM nanoparticles, and M is selected from one or more of Fe, Co, Ni, Ru, Mo, V, Pd and Ga; the shell layer of the core-shell structure is selected from one or more of metal oxide, metal and carbon-nitrogen organic matters. The preparation process is simple to operate and easy to control, and the obtained catalyst can continuously, efficiently and stably maintain the operation of a system under the working condition of the high-temperature proton exchange membrane fuel cell.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of materials, and particularly relates to a proton exchange membrane fuel cell catalyst, a preparation method and use thereof. BACKGROUND

[0002] High temperature proton exchange membrane fuel cell (HT-PEMFC) has become a research hotspot in the field of clean energy due to its excellent performance under the working condition of 120-200 DEG C. Compared with traditional low-temperature PEMFC, its high-temperature operation characteristics not only significantly improve the CO tolerance, but also can realize higher energy conversion efficiency by simplifying the water and heat management system. However, this technical system has long been plagued by the problem of irreversible poisoning of phosphoric acid-based electrolyte to the electrocatalyst, which seriously restricts the output performance and service life of the cell.

[0003] In the prior art, platinum-based catalysts are still the main active materials of HT-PEMFC. However, in HT-PEMFC, a phosphoric acid doped polybenzimidazole (PBI) membrane is often used as a proton exchange membrane, which relies on phosphoric acid to maintain proton conduction. Phosphoric acid may seep from the membrane into the catalyst layer. Phosphoric acid dihydrogen (H2PO4 - ) or phosphoric acid (H3PO4) will be adsorbed on the surface of the platinum-based catalyst, occupying the Pt active sites and hindering the adsorption and reaction of hydrogen or oxygen, thereby causing voltage loss, power drop and cell durability decline. Therefore, it is urgent to develop a phosphoric acid poisoning-resistant catalyst to improve the performance of the cell. SUMMARY

[0004] In order to overcome the defects of the prior art, the present application provides a proton exchange membrane fuel cell catalyst, a preparation method and use thereof.

[0005] The first aspect of the present application provides a proton exchange membrane fuel cell catalyst, which can include a carrier and an active component with a core-shell structure supported on the carrier, wherein, The core of the core-shell structure is a platinum Pt nanoparticle and / or a platinum alloy PtM nanoparticle, and M is selected from one or more of Fe, Co, Ni, Ru, Mo, V, Pd, Ga; The shell layer of the core-shell structure is selected from one or more of a metal oxide, a metal, and a carbon-nitrogen organic matter.

[0006] The second aspect of the present application provides a preparation method of the proton exchange membrane fuel cell catalyst of the first aspect, which can include: (1) providing catalyst substrate powder and shell layer precursor material powder, wherein the catalyst substrate includes a carrier and platinum Pt and / or platinum alloy PtM supported on the surface of the carrier, and M is selected from one or more of Fe, Co, Ni, Ru, Mo, V, Pd, Ga; (2) Place the catalyst matrix powder from step (1) in the second temperature zone of the heating furnace under an inert atmosphere; (3) Place the shell precursor material powder from step (1) in the first temperature zone of the heating furnace under an inert atmosphere; (4) Heat the first temperature zone to the first temperature; (5) Heat the second temperature zone to the second temperature; (6) Using an inert gas carrier gas flow, the shell precursor material powder of the first temperature zone is introduced into the second temperature zone, so that the platinum Pt and / or platinum alloy PtM on the support surface of the catalyst matrix are combined with the shell precursor material. (7) Turn off the inert gas carrier gas flow, introduce the reducing gas flow, and heat the second temperature zone to the third temperature to reduce the shell precursor material combined with the catalyst matrix to form a core-shell structure, thereby obtaining the proton exchange membrane fuel cell catalyst.

[0007] A third aspect of this application provides a battery, which is a proton exchange membrane fuel cell, and the proton exchange membrane fuel cell may include a proton exchange membrane fuel cell catalyst as described in the first aspect or a proton exchange membrane fuel cell catalyst prepared according to the method of the second aspect.

[0008] The fourth aspect of this application provides the use of the proton exchange membrane fuel cell catalyst of the first aspect or the proton exchange membrane fuel cell catalyst prepared according to the method of the second aspect in the resistance to phosphoric acid poisoning of proton exchange membrane fuel cells.

[0009] The proton exchange membrane fuel cell catalyst of this application has, but is not limited to, the following beneficial effects: This application provides a high-temperature proton exchange membrane fuel cell catalyst with a core-shell structure. The catalyst is characterized by a core consisting of platinum or platinum alloy nanoparticles supported on a carrier, covered by a metal oxide shell. The preparation method involves loading platinum or platinum alloy nanoparticles onto a carrier and then coating their surface with a metal oxide shell using chemical vapor deposition to obtain the final catalyst. The preparation process of this application is simple and easy to control, and the resulting catalyst can continuously, efficiently, and stably maintain the system's operation under the operating conditions of a high-temperature proton exchange membrane fuel cell. Attached Figure Description

[0010] Figure 1 A TEM image of the catalyst prepared in Example 1 is shown.

[0011] Figure 2 A TEM image of the catalyst prepared in Example 2 is shown.

[0012] Figure 3 The results of the antiphosphoric acid test for Test Example 1 of this application are shown.

[0013] Figure 4 The anti-phosphoric acid test results of the present application test example 2 are shown. DETAILED DESCRIPTION

[0014] The present application is further described in detail by the accompanying drawings and embodiments. Through these descriptions, the features and advantages of the present application will become more apparent.

[0015] The word "exemplary" is used herein to mean "serving as an example, instance, or illustration." Any implementation described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other implementations. Unless specifically indicated otherwise, the drawings are not necessarily to scale.

[0016] In addition, the technical features involved in the different embodiments of the present application described below can be combined with each other as long as there is no conflict.

[0017] The present application provides a proton exchange membrane fuel cell catalyst, which comprises a carrier and an active component with core-shell structure supported on the carrier, wherein, The core of the core-shell structure is platinum Pt nanoparticles and / or platinum alloy PtM nanoparticles, M is selected from one or more of Fe, Co, Ni, Ru, Mo, V, Pd, Ga; The shell layer of the core-shell structure is selected from one or more of metal oxides, metals.

[0018] The proton exchange membrane fuel cell catalyst provided by the present application comprises a carrier and an active component supported on the carrier, and the active component has a core-shell structure, and the core of the core-shell structure is platinum Pt or platinum alloy PtM nanoparticles, and the surface of the core is wrapped by a shell layer. The catalyst of the present application is designed by the core-shell structure, and a shell layer is wrapped on the surface of the platinum Pt or platinum alloy PtM nanoparticles, which is beneficial to weaken the adsorption of dihydrogen phosphate (H2PO4 - ) or phosphoric acid (H3PO4) on the surface of the platinum-based catalyst, promote the adsorption and reaction of hydrogen or oxygen on the Pt active site, and further ensure that the battery continuously, efficiently and stably maintains the operation of the system under the working condition.

[0019] In an embodiment, the shell layer of the core-shell structure can be selected from one or more of CoO, MoO2, RuO2, NiO, preferably MoO2 and / or CoO.

[0020] The present application preferably uses the above-mentioned material as the shell layer material of the active component of the catalyst, which can effectively construct a suitable thickness of anti-phosphoric acid poisoning shell layer.

[0021] In an embodiment, the particle size of the platinum Pt nanoparticles and / or platinum alloy PtM nanoparticles in the core-shell structure can be 2-8 nm, preferably 3-6 nm; and / or The thickness of the shell layer of the core-shell structure can be 0.1-2 nm, preferably 1-1.5 nm.

[0022] The particle size of the platinum Pt nanoparticles and / or platinum alloy PtM nanoparticles in the present application is set in the above range, which can balance the activity, stability and mass transfer performance of the reaction.

[0023] The thickness of the shell layer of the core-shell structure in the present application can be set to 0.1-2 nm, for example, it can be 0.1 nm, 0.2 nm, 0.5 nm, 1 nm, 1.5 nm, 2 nm, or a range composed of any two of the above values. By setting the shell layer thickness in the above range, it is beneficial to reduce the poisoning of dihydrogen phosphate (H2PO4 - ) or phosphoric acid (H3PO4) on the platinum-based catalyst. When the shell layer thickness is too small, the effect of reducing the poisoning of dihydrogen phosphate or phosphoric acid is not obvious; when the shell layer thickness is too large, the shell layer will hinder the adsorption and reaction of hydrogen or oxygen on the Pt active site.

[0024] In an embodiment, the carrier can be selected from one or more of a carbon carrier, an inorganic oxide carrier, an inorganic nitride carrier, and an inorganic carbide carrier. Preferably, the carrier is a carbon carrier.

[0025] In a specific embodiment, the carbon carrier can be selected as a porous carbon, preferably a mesoporous carbon.

[0026] Specifically, the porous carbon refers to a carbon material with a certain pore structure. The porous carbon material can be divided into three categories according to the pore size: the porous carbon material with a pore size less than 2 nm is microporous carbon material, the porous carbon material with a pore size greater than 50 nm is macroporous carbon material, and the porous carbon material with a pore size between 2-50 nm is mesoporous carbon material.

[0027] The present application also provides a preparation method of the proton exchange membrane fuel cell catalyst, comprising: (1) providing catalyst substrate powder and shell precursor material powder, wherein the catalyst substrate comprises a carrier and platinum Pt and / or platinum alloy PtM supported on the surface of the carrier, M is selected from one or more of Fe, Co, Ni, Ru, Mo, V, Pd, Ga; (2) placing the catalyst substrate powder of step (1) in the second temperature zone of the heating furnace under inert atmosphere; (3) placing the shell precursor material powder of step (1) in the first temperature zone of the heating furnace under inert atmosphere; (4) heating the first temperature zone to a first temperature; (5) heating the second temperature zone to a second temperature; (6) introducing the shell precursor material powder in the first temperature zone into the second temperature zone using an inert gas carrier gas stream to bind the platinum Pt and / or platinum alloy PtM on the support surface of the catalyst matrix with the shell precursor material; (7) closing the inert gas carrier gas stream, introducing a reducing gas stream, and heating the second temperature zone to a third temperature to reduce the shell precursor material bound to the catalyst matrix to form a shell of core-shell structure to obtain the proton exchange membrane fuel cell catalyst resistant to phosphoric acid poisoning.

[0028] The preparation method of the present application is to load platinum or platinum alloy nanoparticles on a support, and then coat a shell such as a metal oxide shell on the surface thereof by chemical vapor deposition to obtain the final proton exchange membrane fuel cell catalyst resistant to phosphoric acid poisoning. The preparation process is simple and easy to control, and the obtained catalyst can continuously, efficiently and stably maintain the operation of the system under the working conditions of high temperature proton exchange membrane fuel cell.

[0029] Without wishing to be bound by any theory, it is believed that in the preparation method of the present application, the shell precursor powder in the first temperature zone is introduced into the second temperature zone by an inert gas carrier gas stream to bind the platinum Pt and / or platinum alloy PtM on the support surface of the catalyst matrix. On the one hand, under high temperature and inert gas atmosphere, the residence time of molecules on the support surface decreases exponentially with temperature, so that physical adsorption on the support surface at high temperature can be almost ignored, and the precursor molecules cannot be stably stopped; on the other hand, under such high temperature and dynamic carrier gas reaction conditions, the Pt / PtM surface is a more thermodynamically favorable chemical adsorption site, so that the relatively firm chemical bond between the shell precursor molecules and the Pt / PtM surface atoms is formed through coordination bond or partial charge transfer, and then a shell is formed on the Pt / PtM surface.

[0030] In one embodiment, the catalyst matrix can be platinum on carbon Pt / C and / or platinum alloy on carbon PtM / C; The shell precursor material can be selected from one or more of metal oxides, metal halides, metal polyacid salts, metal carbonyl compounds, urea, oleylamine, cyanamide, amino acids; and / or The inert atmosphere can be argon or nitrogen.

[0031] The metal polyacid salt referred to in the present application refers to a polyacid anion and a metal cation (such as K + , Na +, transition metal ions or rare earth ions) through ionic bonds or coordination bonds, wherein polyoxometalates (POMs) refer to polynuclear cluster anions formed by high oxidation state cations (such as Mo 6+ , W 6+ ) of pre-transition metals (such as Mo, W, V, Nb, Ta, etc.) connected through oxygen bridges.

[0032] In a specific embodiment, the catalyst substrate powder and / or the shell precursor material powder can be ground into a uniform powder.

[0033] In a specific embodiment, the heating furnace can be a tube furnace.

[0034] In an embodiment, the mass ratio of the catalyst substrate powder placed in the second temperature zone of the heating furnace in step (2) to the shell precursor material powder placed in the first temperature zone of the heating furnace in step (3) can be 1: (1.2-2), preferably 1: (1.2-1.5).

[0035] The method of the present application sets the mass ratio of the catalyst substrate powder to the shell precursor material powder in the first temperature zone within the above range, which is beneficial to ensure that there is sufficient shell precursor material powder introduced into the second temperature zone by the inert gas carrier gas stream and combined with the platinum or platinum alloy nanoparticles of the catalyst substrate to form a core-shell structure shell.

[0036] In an embodiment, in step (4), the first temperature can be 200-400°C, preferably 200-350°C; In step (5), the second temperature can be 50-200°C, preferably 150-200°C; and / or In step (7), the third temperature can be 300-600°C, preferably 400-600°C.

[0037] In a specific embodiment, the first temperature zone is maintained within the above temperature range at all times during the first and second time periods to ensure that the system temperature is relatively stable.

[0038] In an embodiment, in step (6), the flow rate of the inert gas carrier gas stream can be 5-30 mL / min, preferably 15-25 mL / min; and / or In step (7), the flow rate of the reducing gas stream can be 5-20 mL / min, preferably 10-15 mL / min.

[0039] In an embodiment, the time of step (6) can be 1-6 hours, preferably 2-5 hours; and / or The time of step (7) can be 2-5 hours, preferably 3-5 hours.

[0040] By controlling the first time within the above range, the present application is advantageous to make the platinum Pt and / or platinum alloy PtM on the carrier surface of the catalyst substrate form the required amount of shell precursor material for the core-shell structure. By controlling the second time within the above range, the present application can regulate the shell thickness of the catalyst active component to be 0.1-2 nm, and the specific time can be adjusted according to the thickness and composition of the shell.

[0041] In one embodiment, the method can further comprise: (8) washing, drying and grinding the proton exchange membrane fuel cell catalyst obtained in step (7).

[0042] In a specific embodiment, the catalyst obtained in step (7) can be washed with deionized water and isopropanol, dried at 80-120℃, and ground to obtain a uniform powder catalyst.

[0043] The present application also provides a battery, which is a proton exchange membrane fuel cell comprising the proton exchange membrane fuel cell catalyst as described above or prepared according to the method described above; Preferably, the battery can be a high-temperature proton exchange membrane fuel cell; More preferably, the working temperature of the battery can be 160-180℃.

[0044] The present application also provides the use of the aforementioned proton exchange membrane fuel cell catalyst or the proton exchange membrane fuel cell catalyst prepared according to the aforementioned method in the resistance to phosphoric acid poisoning of a proton exchange membrane fuel cell.

[0045] The catalyst of the present application can be used in a proton exchange membrane fuel cell, in particular a high-temperature proton exchange membrane fuel cell, which is advantageous to improve the poisoning of the platinum-based catalyst by dihydrogen phosphate or phosphoric acid, so that the catalyst can continuously, efficiently and stably maintain the operation of the system under working conditions.

[0046] The present application does not have special restrictions on the source of all raw materials, and except for special instructions, it is a conventional product that can be obtained by market purchase.

[0047] The carbon-supported platinum catalyst used in the following examples and test examples was purchased from Suzhou Shengernuo Energy Co., Ltd., and the loading was 40%.

[0048] Example 1 This example is used to illustrate the preparation method of the high-temperature proton exchange membrane fuel cell platinum-cobalt catalyst with core-shell structure of the present application, which comprises the following steps: (1) 1.5 g of carbon-supported platinum catalyst was weighed and ground into a uniform powder in a mortar.

[0049] (2) The carbon-supported platinum catalyst powder was spread in a first porcelain boat and placed in the second temperature zone of the tube furnace under argon protection.

[0050] (3) 17.8 g of Co(acac)2(acetylacetonatocobalt) was weighed and ground into a uniform powder in a mortar, and then spread in a second porcelain boat and placed in the first temperature zone of the tube furnace under argon protection.

[0051] (4) The first temperature zone of the tube furnace was heated to 220°C.

[0052] (5) The second temperature zone of the tube furnace was heated to 150°C.

[0053] (6) 15 mL / min of argon carrier gas flow was introduced, Co(acac)2was introduced into the second temperature zone, and the platinum nanoparticles supported on carbon were allowed to fully combine with Co(acac)2for 3 h.

[0054] (7) The constant flow of argon carrier gas was turned off, 10 mL / min of hydrogen gas flow was introduced, the temperature of the first temperature zone was kept unchanged, the second temperature zone was heated to 400°C, and kept for 2 h. Then the obtained solid was washed with deionized water and isopropanol in turn and dried at 80°C to obtain the platinum-cobalt catalyst nanoparticles supported on porous carbon with a core-shell structure, which were protected from phosphoric acid poisoning by a cobalt oxide shell.

[0055] Figure 1 The TEM image of the catalyst prepared in this example is shown. As can be seen from the figure, the carbon support surface of the carbon-supported platinum catalyst forms an active component with a core-shell structure, and the red dashed line part of the figure shows the cobalt oxide shell structure of the active component. As can be seen, a layer of cobalt oxide shell is formed on the surface of the platinum nanoparticles by the method of the present application. In this core-shell structure, the thickness of the cobalt oxide shell is about 0.5 nm, and the particle size of the Pt nanoparticles is about 3 nm.

[0056] Example 2 The difference between this example and Example 1 is that the shell structure component is molybdenum oxide.

[0057] (1) 1.5 g of carbon-supported platinum catalyst was weighed and ground into a uniform powder in a mortar.

[0058] (2) The carbon-supported platinum catalyst powder was spread in a first porcelain boat and placed in the second temperature zone of the tube furnace under argon protection.

[0059] (3) 19.6 g of ammonium molybdate heptahydrate was weighed as a shell metal precursor, ground into a uniform powder in a mortar, and then laid flat in a second porcelain boat, which was placed in the first temperature zone of the tube furnace under argon protection.

[0060] (4) The first temperature zone of the tube furnace was heated to 220°C.

[0061] (5) The second temperature zone of the tube furnace was heated to 150°C.

[0062] (6) 15 mL / min of argon carrier gas flow was introduced, and ammonium molybdate heptahydrate was introduced into the second temperature zone, and maintained for 2 h, so that the platinum nanoparticles supported on carbon and the ammonium molybdate heptahydrate were fully combined.

[0063] (7) The constant flow of argon carrier gas was turned off, and 10 mL / min of hydrogen gas flow was introduced. The second temperature zone was heated to 400°C and maintained for 2 h, and then the resulting solid was washed with deionized water and isopropanol in turn and dried at 80°C to obtain a platinum-molybdenum catalyst nanoparticle with a core-shell structure, in which the porous carbon-supported molybdenum oxide shell layer protects against phosphoric acid poisoning.

[0064] Figure 2 A TEM image of the catalyst prepared in this example is shown, and from the image it can be seen that a molybdenum oxide shell layer (red dotted line portion) is formed on the surface of the platinum nanoparticles by the method of the present application. In this core-shell structure, the thickness of the molybdenum oxide shell layer is about 0.5 nm, and the particle size of the Pt nanoparticles is about 3 nm.

[0065] Test Example 1 The platinum-cobalt catalyst with a core-shell structure prepared in Example 1 of the present application and the carbon-supported platinum catalyst used in step (1) of Example 1 were subjected to phosphoric acid resistance testing. The catalysts were placed in a perchloric acid electrolyte solution and a perchloric acid electrolyte solution containing 1 mM phosphoric acid to detect the oxygen reduction reaction polarization curve, and the specific testing method was as follows: The catalysts were tested using an electrochemical workstation in a three-electrode system; first, cyclic voltammetry (CV) was used to scan 20 times in the range of 0.03-1.2 V vs. RHE in a 0.1 M perchloric acid solution with sufficient deoxygenation, and the scan rate was 0.05 V s -1 , to fully activate the catalyst; then linear sweep voltammetry (LSV) was used to scan the oxygen reduction reaction polarization curve in the range of 0.2-1.1 V in a 0.1 M perchloric acid solution saturated with oxygen and a perchloric acid solution containing 1 mM phosphoric acid, and the scan rate was 0.01 V s -1 , and the electrode rotation speed was 1600 rpm, and the test results are shown in Figure 3 .

[0066] from Figure 3 As can be seen, the cobalt oxide-shell-modified platinum catalyst (sample 1) prepared in Example 1 exhibits a half-wave potential drop of 12 mV in a 1 M perchloric acid solution containing 0.1 mM phosphoric acid, while the carbon-supported platinum catalyst shows a half-wave potential drop of 26 mV. This indicates that the cobalt oxide-shell-modified platinum catalyst prepared in Example 1 exhibits less activity decay and significantly improved resistance to phosphoric acid poisoning. Example 1 of this application, by setting a cobalt oxide shell to protect platinum nanoparticles, can effectively improve the poisoning of platinum-based catalysts by phosphoric acid.

[0067] Experimental Example 2 The catalyst prepared in Example 2 of this application was subjected to phosphoric acid resistance testing according to the method of Test Example 1. The test results are as follows: Figure 4 As shown.

[0068] from Figure 4 As can be seen, the molybdenum oxide-shell-modified platinum catalyst (sample 2) prepared in Example 2 exhibits a half-wave potential drop of 13 mV in a 1 M perchloric acid solution containing 0.1 mM phosphoric acid, while the carbon-supported platinum catalyst shows a half-wave potential drop of 26 mV. This indicates that the molybdenum oxide-shell-modified platinum catalyst prepared in Example 2 exhibits less activity decay and significantly improved resistance to phosphoric acid poisoning. Example 2 of this application, by setting a molybdenum oxide shell to protect platinum nanoparticles, can effectively improve the poisoning of platinum-based catalysts by phosphoric acid.

[0069] The present application has been described above with reference to preferred embodiments; however, these embodiments are merely exemplary and illustrative. Various substitutions and modifications can be made to the present application based on these embodiments, all of which fall within the protection scope of the present application.

Claims

1. A proton exchange membrane fuel cell catalyst characterized by, The catalyst comprises a carrier and an active component with core-shell structure supported on the carrier, wherein, The core of the core-shell structure is platinum Pt nanoparticles and / or platinum alloy PtM nanoparticles, M is selected from one or more of Fe, Co, Ni, Ru, Mo, V, Pd, Ga; The shell layer of the core-shell structure is selected from one or more of metal oxides, metals, carbon-nitrogen organic matter.

2. The catalyst according to claim 1, characterized in that, The shell layer of the core-shell structure is selected from one or more of CoO, MoO2, RuO2, NiO x , preferably CoO and / or MoO2.

3. The catalyst according to claim 1, characterized in that, In the core-shell structure, the particle size of the platinum Pt nanoparticles and / or platinum alloy PtM nanoparticles is 2-8 nm, preferably 3-6 nm; and / or The thickness of the shell layer of the core-shell structure is 0.1-2 nm, preferably 0.5-1 nm.

4. The catalyst of claim 1, wherein The carrier is selected from one or more of carbon carriers, inorganic oxide carriers, inorganic nitride carriers, and inorganic carbide carriers; Preferably, the carrier is a carbon carrier, more preferably a porous carbon, and further preferably a mesoporous carbon.

5. A method for preparing the proton exchange membrane fuel cell catalyst according to any one of claims 1 to 4, comprising: (1) providing catalyst substrate powder and shell precursor material powder, wherein the catalyst substrate comprises a carrier and platinum Pt and / or platinum alloy PtM supported on the surface of the carrier, M is selected from one or more of Fe, Co, Ni, Ru, Mo, V, Pd, Ga; (2) placing the catalyst substrate powder of step (1) in the second temperature zone of a heating furnace under an inert atmosphere; (3) placing the shell precursor material powder of step (1) in the first temperature zone of a heating furnace under an inert atmosphere; (4) heating the first temperature zone to a first temperature; (5) heating the second temperature zone to a second temperature; (6) introducing the shell precursor material powder in the first temperature zone into the second temperature zone using an inert gas carrier gas stream, so that the platinum Pt and / or platinum alloy PtM on the surface of the carrier of the catalyst substrate combines with the shell precursor material; (7) closing the inert gas carrier gas stream, introducing a reducing gas stream, and heating the second temperature zone to a third temperature, so that the shell precursor material combined with the catalyst substrate is reduced to form a shell layer of the core-shell structure, thereby obtaining the proton exchange membrane fuel cell catalyst.

6. The method of claim 5, wherein, The catalyst substrate is platinum Pt / C and / or platinum alloy PtM / C supported on carbon; The shell precursor material is selected from one or more of metal oxides, metal halides, metal polyacid salts, metal carbonyl compounds, urea, oleylamine, cyanamide, and amino acids; and / or The inert atmosphere is argon or nitrogen.

7. The method of claim 5, wherein, The molar ratio of the catalyst substrate powder placed in the second temperature zone of the heating furnace in step (2) to the shell precursor material powder placed in the first temperature zone of the heating furnace in step (3) is 1:(1.2-2), preferably 1:(1.2-1.5).

8. The method of claim 5, wherein, In step (4), the first temperature is 200-400°C, preferably 200-350°C; In step (5), the second temperature is 50-200°C, preferably 150-200°C; and / or In step (7), the third temperature is 300-600°C, preferably 400-600°C.

9. The method of claim 5, wherein, In step (6), the flow rate of the inert gas carrier gas stream is 5-30 mL / min, preferably 15-25 mL / min; and / or The flow rate of the reducing gas in step (7) is 5-20 mL / min, preferably 10-15 mL / min.

10. The method of claim 5, wherein, The time of step (6) is 1-6 hours, preferably 2-5 hours; and / or The time of step (7) is 2-5 hours, preferably 3-5 hours.

11. The method of claim 5, wherein, The method further comprises: (8) washing, drying and grinding the proton exchange membrane fuel cell catalyst obtained in step (7).

12. A battery, characterized by The cell is a proton exchange membrane fuel cell comprising the proton exchange membrane fuel cell catalyst of any one of claims 1 to 4 or prepared according to the method of any one of claims 5 to 11.

13. Use of the proton exchange membrane fuel cell catalyst of any one of claims 1 to 4 or prepared according to the method of any one of claims 5 to 11 in the resistance of a proton exchange membrane fuel cell to phosphoric acid poisoning.

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