A proton exchange membrane fuel cell electrocatalyst and a method for making the same

Abstract

The application provides a proton exchange membrane fuel cell catalyst and a preparation method thereof. The application is characterized in that a F-treated Pt x Co y nanoparticle is uniformly loaded on the surface of a F-treated carbon carrier, and the atoms on the surface of the catalyst are rearranged through heat treatment, so that a proton exchange membrane fuel cell catalyst with a surface rich in Pt is obtained. The catalyst has good dispersity, obvious Pt and Co enrichment characteristics, the surface enrichment of Pt is beneficial to improving the utilization rate of Pt atoms, thereby improving the mass specific activity of the noble metal of the catalyst, the surface enrichment of Co is beneficial to surface modification and improving the electrochemical stability of the nanoparticle, the addition of F significantly improves the dependence of the proton exchange membrane on water, and the catalyst and the carrier have strong hydrophobicity, which can effectively reduce the corrosion of water and acid on the catalyst, has strong acid corrosion resistance, good catalytic activity, good cycle performance and long service life.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of fuel cells, in particular to a proton exchange membrane fuel cell catalyst and a preparation method thereof. BACKGROUND

[0002] Currently, the cathode oxygen reduction (ORR) catalysts applicable to the proton exchange membrane fuel cell (PEMFC) are still Pt-based catalysts, which are the most ideal electrocatalysts in terms of activity and service life. However, the cost of Pt is high, the activity is high, and the stability is low, which cannot meet the needs of large-scale commercial application. Therefore, at present, the researches at home and abroad mainly focus on improving the catalytic activity and stability of platinum-based catalysts, so as to achieve the goal of reducing the use of noble metals and improving the stability of the catalyst. In terms of the structure of Pt-based catalysts, researchers design and synthesize catalysts with special nanostructures, expose more dominant crystal faces, or perform surface modification and improve the adsorption properties of Pt to O, in order to improve the ORR catalytic activity and electrochemical stability of Pt; or prepare alloy catalysts by combining Pt with non-noble metals, which can partially replace Pt and reduce the amount of Pt, and can also adjust the electronic structure of Pt through metal bonds, thereby improving the ORR catalytic activity of Pt; the third aspect is to design a core-shell structure (M@Pt) catalyst with non-noble metal as the core and Pt as the shell, which can replace Pt atoms that do not participate in the catalytic reaction, thereby greatly improving the utilization rate of Pt atoms and reducing the amount of Pt, and through the interaction between the core and the shell, the electronic structure of the surface Pt atoms can be adjusted to obtain high ORR catalytic activity. For platinum-based catalysts with core-shell structure, a common and effective method is to first prepare the core of the first metal in a non-aqueous system, and then use the underpotential deposition technology to make Pt or Pt and the second metal atoms react with the surface first metal atoms to obtain a Pt shell with a thickness of several atoms. A literature (Platinum monolayer electrocatalysts: tunable activity, stability, and self-healing properties [J]. Electrocatalysis 2012; 3: 163-9.) reports a method for preparing M@Pt / C catalyst with Pt monolayer as the shell. First, non-noble metal-noble metal alloy nanoparticles are prepared, then the noble metal is induced to segregate on the surface after high-temperature induction, an underpotential deposition layer of Cu is prepared, and then Pt is used for replacement, thereby obtaining M@Pt / C catalyst. The catalyst prepared by this method greatly improves the utilization rate of Pt atoms, and the mass specific activity of the noble metal can be more than 4 times that of Pt / C catalyst. However, this electrochemical deposition method has strict requirements on the preparation process and is complicated, which is difficult to realize large-scale production. SUMMARY

[0003] The application aims to provide a process simple and controllable for preparing a proton exchange membrane fuel cell electrocatalyst and a preparation method thereof, the platinum-based catalyst prepared by the method has the outstanding advantages of high activity and good stability. In the potential cyclic scanning test simulating the practical conditions of PEMFC, the catalyst spontaneously performs surface reconstruction, the ORR catalytic activity gradually increases, and excellent activity retention ability is exhibited.

[0004] A preparation method of a proton exchange membrane fuel cell catalyst, comprising:

[0005] (1) dissolving Pt and Co precursors in alcohol;

[0006] (2) adding an alcohol solution of sodium hydroxide and introducing high-purity Ar;

[0007] (3) slowly adding an alcohol solution of sodium borohydride under a reducing atmosphere, and after 1-8 h of reaction, obtaining a Pt x Co y nanoparticle solution treated by F;

[0008] (4) dispersing the F-treated carbon carrier in alcohol, adding the Pt x Co y nanoparticle solution treated by F, stirring at room temperature, and uniformly loading the Pt x Co y nanoparticles treated by F on the surface of the F-treated carbon carrier;

[0009] (5) adding an acid solution in step (4) to adjust the pH to 1 and performing sedimentation;

[0010] (6) after obvious sedimentation of the system, performing filtration, washing, and vacuum drying to obtain a Pt x Co y / CF catalyst treated by F;

[0011] (7) heat-treating the Pt x Co y / CF catalyst treated by F in a reducing atmosphere to obtain a Pt x Co y (OF) z / CF catalyst with high activity and high stability.

[0012] Preferably, in steps (3) and (7), the reducing atmosphere is a mixed gas of F2 and an inert gas, wherein the volume ratio of F2 to the inert gas is 1:0.1-0.5:1, and the inert gas is one of high-purity Ar and high-purity He.

[0013] Preferably, the molar ratio of Pt to Co is 0.5:1 to 5:1.

[0014] Preferably, the Pt precursor is one or more of H2PtCl6, PtCl4, K2PtCl6, Na2PtCl6, and K2PtCl4; and the Co precursor is one or more of cobalt nitrate hexahydrate, cobalt chloride, and cobalt sulfate.

[0015] Preferably, the mass content of Pt in the catalyst is 10% to 60%.

[0016] Preferably, the alcohol is one of ethylene glycol, propylene glycol, and glycerol.

[0017] Preferably, the F-treated carbon carrier is heat-treated in a reducing atmosphere, and the reducing atmosphere is a mixed gas of F2 and an inert gas, wherein the volume ratio of F2 to the inert gas is 1:0.1 to 0.5:1, the heat treatment temperature is 30 to 150°C, and the heat treatment time is 2 to 8 hours.

[0018] Specifically, the carbon carrier is any one of Vulcan XC-72, KB300, KB600, BP2000, and the like.

[0019] Preferably, in step (7), the heat treatment temperature is 120 to 300°C, the optimal treatment temperature is 150 to 250°C, the heat treatment time is 0.5 to 5 hours, and the optimal treatment time is 2 to 4 hours.

[0020] Compared with the prior art, the present application has the following advantages:

[0021] (1) The catalyst nanoparticles prepared by the present application have good dispersibility, and have obvious Pt and Co enrichment characteristics. The surface enrichment of Pt is conducive to improving the utilization rate of Pt atoms, thereby improving the mass specific activity of the noble metal of the catalyst, and the surface enrichment of Co is conducive to realizing surface modification and improving the electrochemical stability of the nanoparticles.

[0022] (2) The Pt x Co y (OF) z nanoseed of the present application can maximize the exposure of platinum high-activity crystal faces, thereby improving the mass specific activity of the noble metal of the catalyst and further improving the performance of the catalyst.

[0023] (3) The present application uses a heat treatment process to rearrange the atoms on the surface of the catalyst, and utilizes the high affinity between platinum and F to promote the aggregation of platinum elements to the surface of the catalyst particles.

[0024] (4) The present application uses F-containing gas to treat the carbon carrier, which can effectively remove impurities contained in the carrier itself, and can also maximize the hydrophobicity of the carrier.

[0025] (5) The preparation method of the electrocatalyst is simple and controllable, the low-temperature preparation condition and the lower heat treatment temperature make the method save energy and reduce manufacturing cost, and the method is easy to realize large-scale industrial application.

[0026] (6) The platinum-based catalyst prepared by the method can be directly applied to the cathode of a proton exchange membrane fuel cell, and can also be used as a cathode catalyst of other fuel cells. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 TEM image of the PtCo / XC-72 catalyst prepared by synthesis of Comparative Example 1.

[0028] Figure 2 TEM image of the PtCo 0.2 (OF)3 / CF catalyst prepared by synthesis of Example 3.

[0029] Figure 3 CV cycle voltammetry curve of the catalyst synthesized by Example 1 and Example 3.

[0030] Figure 4 Contact angle test image of the catalyst prepared by synthesis of Example 4 sprayed on carbon paper.

[0031] Figure 5 Contact angle test image of the catalyst prepared by synthesis of Comparative Example 1 sprayed on carbon paper.

[0032] Figure 6 Water adsorption energy diagram of the catalyst prepared by Example 1, Example 2, Example 3 and Example 4. DETAILED DESCRIPTION

[0033] The F-treated Pt x Co y nanoparticles with a core-shell structure are uniformly supported on the surface of the F-treated carbon carrier, and finally the atoms on the surface of the catalyst are rearranged by heat treatment, so that a proton exchange membrane fuel cell catalyst with a surface rich in element Pt is obtained.

[0034] Catalyst electrochemical performance test conditions:

[0035] Working electrode: glassy carbon electrode coated with PtxCoy(OF)z / CFm thin film

[0036] Counter electrode: platinum wire

[0037] Reference electrode: saturated calomel electrode (SCE)

[0038] Electrolyte: freshly prepared 0.5M HClO4 aqueous solution

[0039] CV curve test before electrolyte pass high purity Ar 30 min or more to saturation.

[0040] Scan range: 0~1.2V vs RHE

[0041] Scan rate: 20mV s -1

[0042] Linear scan (ORR) test before electrolyte pass O2, 30 min or more to saturation, potential from 0V scan to 1.0V, scan rate 10mV s -1 , electrode speed 1600rpm.

[0043] Example 1

[0044] 1) Under stirring at room temperature, 160mg H2PtCl6·6H2O (M: 517.9) and 40mg Co(NO3)2·6H2O were uniformly dissolved in 100ml propylene glycol;

[0045] 2) Under stirring at room temperature, 7.5ml sodium hydroxide propylene glycol solution was added to 1), the concentration of the solution was 0.04g / ml, high purity Ar was passed to prevent the generated platinum, cobalt ions from being oxidized, the Ar flow rate was 60ml / min -1 ;

[0046] 3) 31.5mg sodium borohydride was dissolved in 3ml propylene glycol;

[0047] 4) Under room temperature, F2 / Ar=1 / 1 mixed atmosphere, the alcohol solution in 3) was slowly added to 2), the dropwise adding speed was controlled at 0.15ml / s -1 , the reduction reaction started immediately, after 3h reaction, Pt, Co nanoparticles were obtained, which was PtCo nanoparticles solution treated by F, the concentration was 27.5mM; 0.2

[0048] 5) Loading and settlement of platinum-based catalyst nanoparticles

[0049] A 60mg Vulcan XC-72 treated by F at 200℃ for 4h in F2 / Ar=1 / 1 reducing atmosphere was uniformly dispersed in propylene glycol, then the PtCo nanoparticles solution treated by F obtained in step 4) was added, stirring at room temperature for 6h, the PtCo nanoparticles treated by F were uniformly loaded on the surface of Vulcan XC-72 carbon carrier treated by F. 0.2 0.2

[0050] B 2M HNO3 aqueous solution was added to A), the pH was adjusted to 1, and settlement was carried out. ​​​

[0051] C After obvious sedimentation of B) occurs, it is filtered, washed with deionized water, vacuum dried to obtain PtCo treated with F 0.2 / CF catalyst.

[0052] 6) The PtCo treated with F 0.2 / CF catalyst is heat treated at 200°C for 4h in a reducing atmosphere of F2 / Ar=1 / 1 to obtain a PtCo 0.2 (OF) / CF catalyst with high activity and stability.

[0053] The prepared catalyst is subjected to electrochemical activity CV cycle test, and the results are shown in FIG. 1 (dotted line); the catalyst is subjected to water adsorption energy test, and the results are shown in FIG. 2. Figure 3 Figure 6 .

[0054] Example 2

[0055] 1) 160mg H2PtCl6·6H2O (M: 517.9) and 40mg Co(NO3)2·6H2O are uniformly dissolved in 100ml propylene glycol under stirring at room temperature;

[0056] 2) 7.5ml of a potassium hydroxide propylene glycol solution with a concentration of 0.04g / ml is added to 1) under stirring at room temperature, and high-purity Ar is introduced to prevent the generated platinum and cobalt ions from being oxidized, with an Ar flow rate of 60ml / min -1 .

[0057] 3) 31.5mg sodium borohydride is dissolved in 3ml propylene glycol solution;

[0058] 4) The aqueous solution in 3) is slowly added to 2) under stirring at room temperature in an F2 / Ar=3 / 1 atmosphere, and the dropping speed is controlled to be 0.15ml / s -1 , and the reduction reaction starts immediately, and after 3h of reaction, Pt and Co nanoseeds, i.e. PtCo treated with F, are obtained, with a concentration of 27.5mM; 0.2 .

[0059] 5) Loading and sedimentation of platinum-based catalyst nanoparticles

[0060] A 60mg Vulcan XC-72 is uniformly dispersed in propylene glycol and then the PtCo treated with F nanoparticle solution obtained in step 4) is added, and the mixture is stirred at room temperature for 6h, and the PtCo treated with F is uniformly loaded on the surface of the Vulcan XC-72 carbon carrier treated with F. 0.2 . 0.2 ​​

[0061] B To A) add 2M HNO3 aqueous solution, adjust pH to 1, and settle.

[0062] C After B) is settled obviously, filter, deionized water wash, vacuum dry to obtain PtCo 0.2 / CF catalyst treated by F.

[0063] 6) Heat treat PtCo 0.2 / CF catalyst treated by F in F2 / Ar = 3 / 1 reducing atmosphere at 200°C for 4h to obtain PtCo 0.2 (OF)2 / CF catalyst with high activity and high stability.

[0064] Water adsorption capacity test is performed on the catalyst, and the results are as follows Figure 6 .

[0065] Example 3

[0066] 1) Under stirring at room temperature, dissolve 160mg H2PtCl6·6H2O (M: 517.9) and 40mg Co(NO3)2·6H2O uniformly in 100ml propylene glycol;

[0067] 2) Under stirring at room temperature, add 7.5ml potassium hydroxide propylene glycol solution with a concentration of 0.04g / ml to 1), and pass high-purity Ar to prevent the generated platinum and cobalt ions from being oxidized, with an Ar flow rate of 60ml / min -1 ;

[0068] 3) Dissolve 31.5mg sodium borohydride in 3ml propylene glycol solution;

[0069] 4) Under room temperature and F2 / Ar = 9 / 2 atmosphere, slowly drop the aqueous solution in 3) into 2) at a dropping speed of 0.15ml / s -1 , and the reduction reaction starts immediately. After 3h of reaction, Pt and Co nanoseeds, i.e. PtCo 0.2 nanoparticle solution treated by F with a concentration of 27.5mM are obtained;

[0070] 5) Loading and settling of platinum-based catalyst nanoparticles

[0071] A Disperse 60mg Vulcan XC-72 treated by F at 200°C for 4h in F2 / Ar = 9 / 2 reducing atmosphere uniformly in propylene glycol, and then add the PtCo 0.2 nanoparticle solution treated by F obtained in step 4), stir at room temperature for 6h, and obtain PtCo 0.2The nanoparticles are uniformly supported on the F-treated Vulcan XC-72 carbon carrier surface.

[0072] B) Add 2M HNO3 aqueous solution to A), adjust pH to 1, and settle.

[0073] C) After B) is settled, filter, wash with deionized water, and vacuum dry to obtain F-treated PtCo 0.2 / CF catalyst.

[0074] 6) Heat-treat the F-treated PtCo 0.2 / CF catalyst in a reducing atmosphere of F2 / Ar = 9 / 2 at 200°C for 4h to obtain a PtCo 0.2 (OF)3 / CF catalyst with high activity and stability.

[0075] TEM test the synthesized catalyst, and the results are as shown in Figure 2 ; perform electrochemical activity CV cycle test on the prepared catalyst, and the results are as shown in Figure 3 (solid line); and perform water adsorption energy test on the catalyst, and the results are as shown in Figure 6 .

[0076] Example 4

[0077] 1) Under stirring at room temperature, uniformly dissolve 160mg H2PtCl6·6H2O (M: 517.9) and 40mg Co(NO3)2·6H2O in 100ml propylene glycol;

[0078] 2) Under stirring at room temperature, add 7.5ml potassium hydroxide propylene glycol solution with a concentration of 0.04g / ml to 1), and pass high-purity Ar to prevent the generated platinum and cobalt ions from being oxidized, with an Ar flow rate of 60ml min -1 ;

[0079] 3) Dissolve 31.5mg sodium borohydride in 3ml propylene glycol solution;

[0080] 4) Under room temperature and F2 / Ar = 7 / 1 atmosphere, slowly drop the aqueous solution in 3) into 2) at a dropping speed of 0.15ml s -1 , and the reduction reaction starts immediately. After 3h of reaction, stable Pt, Co nanoparticle seeds, i.e., F-treated PtCo 0.2 nanoparticle solution with a concentration of 27.5mM is obtained;

[0081] 5) Support and settlement of platinum-based catalyst nanoparticles

[0082] A 60 mg Vulcan XC-72 heat-treated at 200 °C for 4 h in a reducing atmosphere of F2 / Ar = 7 / 1 was uniformly dispersed in propylene glycol, and then the F-treated PtCo obtained in step 4) was added 0.2 The nanoparticle solution was stirred at room temperature for 6 h, and the F-treated PtCo 0.2 The nanoparticles were uniformly supported on the surface of the F-treated Vulcan XC-72 carbon carrier.

[0083] B 2M aqueous HNO3 solution was added to A), the pH was adjusted to 1, and sedimentation was performed.

[0084] C After B) was obviously settled, it was filtered, washed with deionized water, and vacuum dried to obtain the F-treated PtCo 0.2 / CF catalyst.

[0085] 6) The F-treated PtCo 0.2 / CF catalyst was heat-treated at 200 °C for 4 h in a reducing atmosphere of F2 / Ar = 7 / 1 to obtain a PtCo 0.2 (OF)5 / CF catalyst with high activity and high stability.

[0086] The synthesized catalyst was sprayed on carbon paper for contact angle testing, and the results are shown in Figure 4 ; the catalyst was subjected to water adsorption energy testing, and the results are shown in Figure 6 .

[0087] Comparative Example 1

[0088] 125 mg of dried Pt / C precursor and 30 mg of cobalt nitrate hexahydrate were dispersed in 20 mL of water and ultrasonicated for 1 hour.

[0089] A 20 mg / mL aqueous NaBH4 solution was prepared, 4 mL of the aqueous NaBH4 solution was taken, and added dropwise to the dispersion. After complete addition of the NaBH4, the mixture was stirred for 12 h, and then the mixture was suction filtered using a sand funnel, using 300 mL of water each time, for three times, and then the Co-containing Pt / C sample was dried.

[0090] The dried Co-containing Pt / C sample was placed in a tube furnace, under argon, at a heating rate of 5 °C / min, heated to 400 °C for 2 h, and then naturally cooled to room temperature to obtain a PtCo / C alloy catalyst containing cobalt particles.

[0091] 100 mg of PtCo / C alloy catalyst containing cobalt particles were treated with 2 mL and 3 mL of concentrated nitric acid respectively to prepare 10 mL solutions, after stirring for 12 h, the dispersions were filtered by using a sand core funnel, 300 mL of water was used each time, three times of washing were performed to obtain the final PtCo / C catalyst, which were named as 2 mL HNO3-PtCo / C and 3 mL HNO3-PtCo / C catalysts respectively according to the amount of concentrated nitric acid treatment.

[0092] The synthesis of the Pt / C precursor specifically comprises the following operations:

[0093] The BP2000 superconducting conductive activated carbon was dispersed in ethylene glycol, and after ultrasonic treatment, a BP2000 / ethylene glycol dispersion was obtained.

[0094] Benzaldehyde was added to the BP2000 / ethylene glycol dispersion, and after ultrasonic treatment, a BP2000 / ethylene glycol-benzaldehyde dispersion was obtained; wherein the volume ratio of the ethylene glycol to the benzaldehyde is 8:1 to 12:1.

[0095] An aqueous solution of chloroplatinic acid hexahydrate with a concentration of 100 mg / mL was added to the BP2000 / ethylene glycol-benzaldehyde dispersion, and after ultrasonic treatment, a uniformly dispersed BP2000 / ethylene glycol-benzaldehyde dispersion was obtained.

[0096] The uniformly dispersed BP2000 / ethylene glycol-benzaldehyde dispersion was placed in a microwave reactor for reaction and then cooled to room temperature to obtain a dispersion containing a Pt / C precursor. The microwave reactor was operated at a power of 600-1000 W for 1-5 minutes.

[0097] After the dispersion containing the Pt / C precursor was filtered, washed and dried, a Pt / C precursor was obtained.

[0098] The synthesized catalyst was subjected to TEM testing, and the results are shown in Figure 1 ; the synthesized catalyst was sprayed on carbon paper for contact angle testing, and the results are shown in Figure 4 .

[0099] Comparative Example 2

[0100] 1) Under room temperature stirring conditions, 200 mg of H2PtCl6·6H2O (M: 517.9) and 90 mg of CoSO4 were uniformly dissolved in 130 ml of glycerol;

[0101] 2) Under room temperature stirring conditions, 7.5 ml of a calcium hydroxide propylene glycol solution with a concentration of 0.04 g / ml was added to 1);

[0102] 3) High-purity Ar was introduced into 2, and the Ar flow rate was 60 ml / min -1 ;

[0103] 4) 31.5 mg of sodium borohydride was dissolved in 3 ml of deionized water;

[0104] 5) The aqueous solution in 4) was slowly added to 3) at room temperature under high argon atmosphere, and the dropping speed was controlled at 0.15 ml / s. -1 The reduction reaction started immediately, and after 3 h of reaction, stable Pt, Co nano-seeds were obtained, with a concentration of 31 mM.

[0105] 6) Loading and settling of platinum-based catalyst nanoparticles

[0106] A 80 mg of Vulcan XC-72 treated at 200°C for 4 h in a reducing atmosphere of F2 was uniformly dispersed in glycerol, and then PtCo 0.6 nano-seeds obtained in step 5) was added, and stirred at room temperature for 6 h. 0.6 The PtCo 0.6 nanoparticles were uniformly loaded on the surface of the carbon carrier.

[0107] B 2M aqueous solution of citric acid was added to A), and the PH was adjusted to 1, and the settling of the carbon-loaded PtCo 0.6 catalyst was carried out.

[0108] C After obvious settling of B), it was filtered, washed with deionized water, and vacuum dried to obtain PtCo 0.6 / CF catalyst.

[0109] The CV cyclic voltammetry test was carried out on example 4, comparative example 1 (30% as an example) by the above method, the electrochemical active area was calculated, and the catalyst was sprayed on carbon paper for contact angle test, and the experimental data are shown in Table 1.

[0110] Table 1:

[0111] Electrochemically active area (m 2 / g) Contact angle (°) Example 4 104.85 120 Comparative Example 1 68.55 75 .

Claims

1. A method for preparing a catalyst for a proton exchange membrane fuel cell, characterized by, The method comprises the following steps: (1) dissolving Pt and Co precursors in alcohol; (2) adding an alcohol solution of sodium hydroxide and passing high-purity Ar; (3) under a reducing atmosphere, slowly adding an alcohol solution of sodium borohydride, and after 1-8 h of reaction, obtaining Pt treated with F x Co y nanoparticle solution, wherein the reducing atmosphere is a mixed gas of F2 and an inert gas; (4) The F-treated carbon support is dispersed in alcohol, and F-treated Pt x Co y nanoparticle solution, stirring at room temperature, and F-treated Pt x Co y nanoparticles are uniformly supported on the surface of the F-treated carbon support; (5) adding an acid solution in step (4) to adjust the pH to 1 and performing sedimentation; (6) After obvious sedimentation of the system, it is filtered, washed, vacuum dried to obtain Pt treated by F x Co y / CF catalyst (7) Pt treated with F x Co y The CF catalyst is heat treated in a reducing atmosphere, which is a mixture of F2 and an inert gas, to obtain a catalyst with high activity and stability.

2. The method of claim 1, wherein, In steps (3) and (7), the volume ratio of F2 to inert gas is 1:0.1-0.5:1, and the inert gas is one of high-purity Ar and high-purity He.

3. The method of claim 1, wherein, The Pt and Co precursors are dissolved in alcohol, and the molar ratio of Pt to Co is 0.5:1-5:

1.

4. The method of claim 1, wherein, The Pt precursor is one or more of H2PtCl6, PtCl4, K2PtCl6, Na2PtCl6, and K2PtCl4, and the Co precursor is one or more of cobalt nitrate hexahydrate, cobalt chloride, and cobalt sulfate.

5. The method of claim 1, wherein, The mass content of Pt in the catalyst is 10-60%.

6. The method of claim 1, wherein, The alcohol is one of ethylene glycol, propylene glycol, and glycerol.

7. The method of claim 1, wherein, The F-treated carbon carrier is heat-treated in a reducing atmosphere, and the reducing atmosphere is a mixed gas of F2 and inert gas, wherein the volume ratio of F2 to inert gas is 1:0.1-0.5:1, the heat treatment temperature is 30-150°C, and the heat treatment time is 2-8h.

8. The method according to claim 1 or 7, characterized in that The carbon carrier is any one of Vulcan XC-72, KB300, KB600, and BP2000 activated carbon.

9. The method of claim 1, wherein, In step (7), the heat treatment temperature is 120-300°C, and the heat treatment time is 0.5-5h.

10. The method of claim 1, wherein, In step (7), the heat treatment temperature is 150-250°C, and the heat treatment time is 2-4h.

11. A proton exchange membrane fuel cell catalyst prepared by the method according to any one of claims 1-10.

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