Non-platinum electrocatalytic hydrogen evolution catalyst and preparation method and application thereof
By preparing polyaniline with a fiber tubular hollow structure and increasing its nitrogen content through high-temperature heat treatment and ball milling, the problem of high cost of existing platinum-based catalysts is solved, and an efficient non-platinum electrocatalytic hydrogen evolution catalyst is achieved, which is suitable for large-scale Scale application.
Patent Information
- Application Number
- CN202411567180.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-05
- Publication Date
- 2025-02-14
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Among the existing fuel cell catalysts, platinum-based catalytic materials are expensive and rare, and difficult to apply on a large scale, resulting in low efficiency of oxygen reduction reaction.
By reacting aniline with ammonium persulfate and m-chlorperoxybenzoic acid and other compounds, polyaniline with a fiber tubular hollow structure is prepared, and the nitrogen content and specific surface area are increased through high-temperature heat treatment and ball milling to form Highly efficient non-platinum electrocatalytic hydrogen evolution catalyst.
The catalyst exhibits sufficient redox reaction (ORR) electrocatalytic activity in terms of starting potential and limit current density values, and is low in cost and is suitable for large-scale applications.
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Figure CN119433570A_ABST
Abstract
Description
Technical Field
[0001] The present application belongs to the field of fuel cell technology, and in particular relates to a non-platinum electrocatalytic hydrogen evolution catalyst and a preparation method and application thereof. Background Art
[0002] In the related technologies, facing the energy crisis and environmental problems caused by traditional fossil fuels, sustainable clean energy is urgently needed to improve these situations. Fuel cells and metal-air batteries have attracted much attention due to their high energy conversion efficiency, safety and environmental friendliness. The oxygen reduction reaction (ORR) is a key half-reaction of such energy devices, but its kinetics are very slow. Platinum-based catalytic materials can effectively improve the efficiency of the oxygen reduction reaction, but platinum is expensive and scarce and difficult to apply on a large scale. It can be seen that it is necessary to develop low-cost non-precious metal catalysts.
[0003] Based on this, the present invention aims to provide a non-platinum electrocatalytic hydrogen evolution catalyst and a preparation method and application thereof. Summary of the invention
[0004] The present application aims to solve at least one of the technical problems existing in the prior art. To this end, the present application proposes a non-platinum electrocatalytic hydrogen evolution catalyst and a preparation method and application thereof, which can reduce the cost of fuel cell catalysts.
[0005] According to the preparation method of the non-platinum electrocatalytic hydrogen evolution catalyst of the first aspect embodiment of the present application, S1: add ammonium persulfate solution to aniline solution, let stand at room temperature for 24 to 36 hours, centrifuge, filter, wash and dry to obtain the first powder; S2: add the first powder and dichloromethane to a container, keep warm at 0°C, and stir for 15 to 30 minutes, and drop meta-chloroperbenzoic acid therein, continue to keep warm at 0°C, and stir for 1 to 3 hours to obtain the first liquid; S3: stir the first liquid at room temperature for 18 to 48 hours, filter and obtain the second powder; using aniline as the basic raw material, ammonium sulfate as an initiator, and using dichloromethane and meta-chloroperbenzoic acid for doping treatment, so that aniline grows along the intrinsic structure of the organic acid during the polymerization process, and obtains polyaniline with a fiber tubular hollow structure. At the same time, in the process of benzene ring oxidation reconstruction, a ring-open intermediate is generated with an electron affinity site. The benzene ring substituted with different positions and groups is converted into a pyridine derivative by doping, and the carbon atom is converted into a nitrogen atom to obtain a pyridine-N with high catalytic activity.
[0006] S4: Under a protective atmosphere, the second powder is kept at 600-1100°C for 2-6 hours to obtain a third powder; high-temperature heat treatment not only does not change the hollow tubular structure, but also is conducive to the shedding of some short-chain small molecule polyaniline, exposing more active sites, breaking covalent bonds to form free radicals, causing condensation and polymerization, retaining the carbon skeleton, and increasing graphitized -N, which is also an important factor in enhancing the electrocatalytic activity of N-doped carbon nanomaterials OPP.
[0007] S5: The third powder and dichlorodiaminoacetic acid are ball-milled together for 2 to 4 hours to obtain a fourth powder, and then the fourth powder is kept at 800 to 1000 ° C for 1 to 3 hours under a protective atmosphere to obtain a non-platinum electrocatalytic hydrogen evolution catalyst. The polyaniline fiber tube is ball-milled in the presence of dichlorodiaminoacetic acid and heat-treated to further increase the nitrogen content. The smaller particles obtained by ball milling are rougher, and after nitriding ball milling, their defect composition is increased, and the specific surface area is increased. The non-platinum electrocatalytic hydrogen evolution catalyst obtained can show sufficient ORR electrocatalytic activity in terms of starting potential and limiting current density value.
[0008] The non-platinum electrocatalytic hydrogen evolution catalyst according to the embodiment of the present application has at least the following beneficial effects:
[0009] The prepared polyaniline presents a fiber-tube hollow structure with uniform fiber tube size. By oxidative reconstruction of the benzene ring in the polyaniline, the benzene ring substituted with different positions and different groups is converted into the corresponding pyridine derivatives in one step, thereby replacing carbon atoms with nitrogen atoms. This replacement method can control the amount of nitrogen doping, effectively increase the content of nitrogen, and increase graphitized-N and pyridine-N after carbonization. During the carbonization process, polycondensation and polymerization occur, hydrogen and nitrogen atoms escape, and the carbon skeleton is retained. The carbon nanotubes are then ball-milled in the presence of dichlorodiaminoacetic acid and heat-treated to further increase the nitrogen content. The smaller particles obtained by ball milling are coarser, and after nitridation ball milling, their defect composition is increased, and the specific surface area is increased. The obtained non-platinum electrocatalytic hydrogen evolution catalyst can show sufficient ORR electrocatalytic activity in terms of starting potential and limiting current density values.
[0010] According to some embodiments of the present application, in S2, the molar ratio of the first powder, dichloromethane and meta-chloroperbenzoic acid is 5-20:3:15.
[0011] According to some embodiments of the present application, in S3, the second powder is further included being washed with a saturated sodium bicarbonate solution, washed with deionized water, and dried in sequence.
[0012] According to some embodiments of the present application, in S4, the second powder is kept at 850° C. for 2 hours.
[0013] According to some embodiments of the present application, in S5, zirconium dioxide balls are used for ball milling.
[0014] According to some embodiments of the present application, the diameter of the zirconium dioxide ball is 5 mm.
[0015] According to some embodiments of the present application, the protective atmosphere includes at least one component selected from nitrogen, helium, neon, argon or krypton.
[0016] According to some embodiments of the present application, the protective atmosphere is nitrogen.
[0017] According to some embodiments of the present application, a non-platinum electrocatalytic hydrogen evolution catalyst prepared by the above-mentioned method for preparing the non-platinum electrocatalytic hydrogen evolution catalyst is provided.
[0018] According to some embodiments of the present application, a non-platinum electrocatalytic hydrogen evolution catalyst prepared by the above-mentioned method for preparing the non-platinum electrocatalytic hydrogen evolution catalyst is proposed for use as a fuel cell catalyst.
[0019] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become apparent from the description below, or will be learned through the practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] The present application is further described below in conjunction with the accompanying drawings and embodiments, wherein:
[0021] Figure 1 Schematic diagram of a process for preparing a non-platinum electrocatalytic hydrogen evolution catalyst according to an embodiment of the present application;
[0022] Figure 2 This is a transmission electron microscope (TEM) schematic diagram of the non-platinum electrocatalytic hydrogen evolution catalyst of Example 1 of the present application;
[0023] Figure 3 This is a schematic diagram of an emission scanning electron microscope (SEM) of the non-platinum electrocatalytic hydrogen evolution catalyst of Example 1 of the present application;
[0024] Figure 4 This is a cyclic voltammetry (CV) test diagram of the non-platinum electrocatalytic hydrogen evolution catalyst prepared in Example 1 of the present application under acidic conditions;
[0025] Figure 5 This is a cyclic voltammetry (CV) test diagram of the non-platinum electrocatalytic hydrogen evolution catalyst prepared in Example 1 of the present application under alkaline conditions;
[0026] Figure 6 This is a test chart of the cyclic stability of the non-platinum electrocatalytic hydrogen evolution catalyst prepared in Example 1 of the present application under alkaline conditions. DETAILED DESCRIPTION
[0027] The embodiments of the present application are described in detail below, and examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present application, and cannot be understood as limiting the present application.
[0028] In the description of this application, "several" means more than one, "more" means more than two, "greater than", "less than", "exceed", etc. are understood to exclude the number itself, and "above", "below", "within", etc. are understood to include the number itself. If there is a description of "first" or "second", it is only used for the purpose of distinguishing technical features, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features or implicitly indicating the order of the indicated technical features.
[0029] In the description of the present application, the description with reference to the terms "one embodiment", "some embodiments", "illustrative embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials, or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.
[0030] The following is a further description of the present invention, rather than a limitation of the present invention.
[0031] Example 1
[0032] like Figure 1 As shown, this embodiment prepares a non-platinum electrocatalytic hydrogen evolution catalyst, and the specific process is:
[0033] (1) 3.423 g of ammonium persulfate as an initiator and 1.02 g of aniline monomer were dissolved in 60 ml of deionized water. The initiator solution was quickly poured into the monomer solution and allowed to stand at room temperature for 24 hours. After centrifugation, filtration, washing and drying, a precipitate was obtained, i.e., the first powder.
[0034] (2) 1 mol of the first powder and 0.3 mol of dichloromethane were added to a 4 ml screw cap bottle, a magnetic stirring bar was added, and then stirred at 0° C. for 15 minutes. Then, 1.5 mol of m-chloroperbenzoic acid was slowly added dropwise, and stirred at 0° C. for 1 hour. The resulting mixture was the first liquid.
[0035] (3) Then, stirring is continued at room temperature for 18 to 48 hours, and a precipitate is obtained by filtration, i.e., a second powder. The precipitate is washed with a saturated sodium bicarbonate solution, and then with deionized water, and the obtained powder is dried.
[0036] (4) 1.0 mg of the second powder was placed in an alumina crucible and carbonized in a horizontal furnace under a pure nitrogen atmosphere according to the following temperature increase program. The sample was first heated to 400°C at a heating rate of 1°C / min and maintained at this temperature for 2 hours, and then heated to a final temperature of 600°C at a heating rate of 0.5°C / min and maintained at the final temperature for 2 hours. The obtained product is the third powder;
[0037] (5) 50 mg of the third powder and 1 g of dichlorodiaminoacetic acid were ball-milled in a ball mill using 5 mm zirconium dioxide balls for 2 hours. The obtained powder, i.e., the fourth powder, was then pyrolyzed in a preheated furnace at 800° C. in a nitrogen atmosphere for 1 hour to obtain a non-platinum electrocatalytic hydrogen evolution catalyst.
[0038] Example 2
[0039] This embodiment prepares a non-platinum electrocatalytic hydrogen evolution catalyst, and the specific process is as follows:
[0040] (1) 3.423 g of ammonium persulfate as an initiator and 1.02 g of aniline monomer were dissolved in 60 ml of deionized water. The initiator solution was quickly poured into the monomer solution and allowed to stand at room temperature for 24 hours. After centrifugation, filtration, washing and drying, a precipitate was obtained, i.e., the first powder.
[0041] (2) 1 mol of the first powder and 0.3 mol of dichloromethane were added to a 4 ml screw cap bottle, a magnetic stirring bar was added, and then stirred at 0° C. for 15 minutes. Then, 1.5 mol of m-chloroperbenzoic acid was slowly added dropwise, and stirred at 0° C. for 1 hour, and the resulting mixture was the first liquid.
[0042] (3) Then, stirring is continued at room temperature for 18 to 48 hours, and a precipitate is obtained by filtration, i.e., a second powder. The precipitate is washed with a saturated sodium bicarbonate solution, and then with deionized water, and the obtained powder is dried.
[0043] (4) 1.0 mg of the second powder was placed in an alumina crucible and carbonized in a horizontal furnace under a pure helium atmosphere according to the following temperature increase program. The sample was first heated to 400°C at a heating rate of 1°C / min and maintained at this temperature for 2 hours, and then heated to a final temperature of 700°C at a heating rate of 0.5°C / min and maintained at the final temperature for 2 hours. The obtained product is the third powder;
[0044] (5) 50 mg of the third powder and 1 gram of dichlorodiaminoacetic acid were ball-milled in a ball mill using 5 mm zirconium dioxide balls for 2 hours. The obtained powder, i.e., the fourth powder, was then pyrolyzed in a preheating furnace at 800° C. in a helium atmosphere for 1 hour to obtain a non-platinum electrocatalytic hydrogen evolution catalyst.
[0045] Example 3
[0046] This embodiment prepares a non-platinum electrocatalytic hydrogen evolution catalyst, and the specific process is as follows:
[0047] (1) 3.423 g of ammonium persulfate as an initiator and 1.02 g of aniline monomer were dissolved in 60 ml of deionized water. The initiator solution was quickly poured into the monomer solution and allowed to stand at room temperature for 24 hours. After centrifugation, filtration, washing and drying, a precipitate was obtained, i.e., the first powder.
[0048] (2) 1 mol of the first powder and 0.3 mol of dichloromethane were added to a 4 ml screw cap bottle, a magnetic stirring bar was added, and then stirred at 0° C. for 15 minutes. Then, 1.5 mol of m-chloroperbenzoic acid was slowly added dropwise, and stirred at 0° C. for 1 hour, and the resulting mixture was the first liquid.
[0049] (3) Then, stirring is continued at room temperature for 18 to 48 hours, and a precipitate is obtained by filtration, i.e., a second powder. The precipitate is washed with a saturated sodium bicarbonate solution, and then with deionized water, and the obtained powder is dried.
[0050] (4) 1.0 mg of the second powder was placed in an alumina crucible and carbonized in a horizontal furnace under a pure neon atmosphere according to the following temperature increase program. The sample was first heated to 400°C at a heating rate of 1°C / min and maintained at this temperature for 2 hours, and then heated to a final temperature of 850°C at a heating rate of 0.5°C / min and maintained at the final temperature for 2 hours. The obtained product is the third powder;
[0051] (5) 50 mg of the third powder and 1 gram of dichlorodiaminoacetic acid were ball-milled in a ball mill using 5 mm zirconium dioxide balls for 2 hours. The obtained powder, i.e., the fourth powder, was then pyrolyzed in a preheated furnace at 800° C. in a neon atmosphere for 1 hour to obtain a non-platinum electrocatalytic hydrogen evolution catalyst.
[0052] Example 4
[0053] This embodiment prepares a non-platinum electrocatalytic hydrogen evolution catalyst, and the specific process is as follows:
[0054] (1) 3.423 g of ammonium persulfate as an initiator and 1.02 g of aniline monomer were dissolved in 60 ml of deionized water. The initiator solution was quickly poured into the monomer solution and allowed to stand at room temperature for 24 hours. After centrifugation, filtration, washing and drying, a precipitate was obtained, i.e., the first powder.
[0055] (2) 0.5 mol of the first powder and 0.3 mol of dichloromethane were added to a 4 ml screw cap bottle, a magnetic stirring bar was added, and then stirred at 0° C. for 15 minutes. Then, 1.5 mol of m-chloroperbenzoic acid was slowly added dropwise, and stirred at 0° C. for 1 hour, and the obtained mixture was the first liquid.
[0056] (3) Then, stirring is continued at room temperature for 18 to 48 hours, and a precipitate is obtained by filtration, i.e., a second powder. The precipitate is washed with a saturated sodium bicarbonate solution, and then with deionized water, and the obtained powder is dried.
[0057] (4) 1.0 mg of the second powder was placed in an alumina crucible and carbonized in a horizontal furnace under a pure argon atmosphere according to the following temperature increase program. The sample was first heated to 400°C at a heating rate of 1°C / min and maintained at this temperature for 2 hours, and then heated to a final temperature of 1000°C at a heating rate of 0.5°C / min and maintained at the final temperature for 2 hours. The obtained product is the third powder;
[0058] (5) 50 mg of the third powder and 1 g of dichlorodiaminoacetic acid were ball-milled in a ball mill using 5 mm zirconium dioxide balls for 2 hours. The obtained powder, i.e., the fourth powder, was then pyrolyzed in a preheated furnace at 800° C. in an argon atmosphere for 1 hour to obtain a non-platinum electrocatalytic hydrogen evolution catalyst.
[0059] Example 5
[0060] This embodiment prepares a non-platinum electrocatalytic hydrogen evolution catalyst, and the specific process is as follows:
[0061] (1) 3.423 g of ammonium persulfate as an initiator and 1.02 g of aniline monomer were dissolved in 60 ml of deionized water. The initiator solution was quickly poured into the monomer solution and allowed to stand at room temperature for 24 hours. After centrifugation, filtration, washing and drying, a precipitate was obtained, i.e., the first powder.
[0062] (2) 2 mol of the first powder and 0.3 mol of dichloromethane were added to a 4 ml screw cap bottle, a magnetic stirring bar was added, and then stirred at 0° C. for 15 minutes. Then, 1.5 mol of m-chloroperbenzoic acid was slowly added dropwise, and stirred at 0° C. for 1 hour, and the obtained mixture was the first liquid.
[0063] (3) Then, stirring is continued at room temperature for 18 to 48 hours, and a precipitate is obtained by filtration, i.e., a second powder. The precipitate is washed with a saturated sodium bicarbonate solution, and then with deionized water, and the obtained powder is dried.
[0064] (4) 1.0 mg of the second powder was placed in an alumina crucible and carbonized in a horizontal furnace under a pure krypton atmosphere according to the following temperature increase program. The sample was first heated to 400°C at a heating rate of 1°C / min and maintained at this temperature for 2 hours, and then heated to a final temperature of 1100°C at a heating rate of 0.5°C / min and maintained at the final temperature for 2 hours. The obtained product is the third powder;
[0065] (5) 50 mg of the third powder and 1 g of dichlorodiaminoacetic acid were ball-milled in a ball mill using 5 mm zirconium dioxide balls for 2 hours. The obtained powder, i.e., the fourth powder, was then pyrolyzed in a preheating furnace at 800° C. in a krypton atmosphere for 1 hour to obtain a non-platinum electrocatalytic hydrogen evolution catalyst.
[0066] Working principle:
[0067] The prepared polyaniline presents a fiber-tube hollow structure with uniform fiber tube size. Through the oxidative reconstruction of the benzene ring in polyaniline, an open-ring intermediate with electron affinity sites is generated, which is ready for ring closure and carbon-based leaving groups. An intermediate with two carbonyl groups is generated in situ, activated to form a carboxylate leaving group, and the activation promotes the condensation of ammonia to finally obtain the product. The benzene rings substituted with different positions and groups are converted into corresponding pyridine derivatives in one step, thereby replacing carbon atoms with nitrogen atoms. This replacement method can control the amount of nitrogen doping and can effectively increase the content of nitrogen. Increasing graphitized-N and pyridine-N is an important factor in enhancing the ORR electrocatalytic activity of N-doped carbon nanomaterials. In addition, the temperature resistance of the polyaniline carbon fiber tube is enhanced by the doping treatment of dichloromethane and benzoic acid. The hollow tubular structure remains basically unchanged after high-temperature heat treatment. As the carbonization temperature increases, some short-chain small molecule polyaniline falls off, more active functional groups are exposed, and some functional groups and small molecules are destroyed at high temperatures, mainly reflected in the breakage of the -NH- bond and the breakage of the -C=N- double bond connected to the quinone structure. Therefore, there may be a breakage of covalent bonds to form free radicals. During the high-temperature treatment process, polycondensation and polymerization occur, hydrogen and nitrogen atoms escape, and the carbon skeleton is retained. After that, the polyaniline fiber tube is ball-milled in the presence of dichlorodiaminoacetic acid and heat-treated to further increase the nitrogen content. The smaller particles obtained by ball milling are rougher. After nitridation ball milling, their defect composition is increased, the specific surface area is increased, and the ORR electrocatalytic activity can be exhibited in terms of starting potential and limiting current density values.
[0068] The non-platinum electrocatalytic hydrogen evolution catalyst was tested and the results were as follows Figures 2 to 6 shown.
[0069] The test was conducted on a rotating disk electrode and an electrochemical workstation. The working electrode was a glassy carbon electrode, the reference electrode was a Hg / HgSO4 electrode, and the counter electrode was a platinum wire. The electrolyte solution under acidic conditions was 0.1M perchloric acid (under oxygen saturation conditions), and the electrolyte solution under alkaline conditions was 0.1M potassium hydroxide (under oxygen saturation conditions). The test method was linear sweep voltammetry, and the test process was completed at room temperature and pressure.
[0070] like Figure 4 As shown, under acidic conditions, the electrode made of the ZIF-derived non-precious metal electrocatalyst of Example 1 has a starting potential of 0.97 V (vs. RHE) and a half-wave potential of 0.82 V (vs. RHE), reaching the average activity level of currently reported non-precious metal catalysts for fuel cells under acidic test conditions. Figure 5 The CV graph of the electrode made of the ZIF-derived non-precious metal electrocatalyst of Example 1 under alkaline conditions has an initial potential of 1.09 V (vs. RHE) and a half-wave potential of 0.93 V (vs. RHE), indicating that the ZIF-derived non-precious metal electrocatalyst prepared in Example 1 has excellent redox performance, and the limiting current density is close to 6 mA / cm 2 ,like Figure 6 As shown, after 10,000 cycles, the catalytic performance remained almost consistent, with the loss of half-slope potential less than 5 mV, demonstrating excellent stability.
[0071] The embodiments of the present application are described in detail above in conjunction with the accompanying drawings, but the present application is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in the relevant technical field without departing from the purpose of the present application. In addition, the embodiments of the present application and the features in the embodiments can be combined with each other without conflict.
[0072] It should also be noted that the terms "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, commodity or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, commodity or device. In the absence of more restrictions, the elements defined by the sentence "comprises a ..." do not exclude the existence of other identical elements in the process, method, commodity or device including the elements.
[0073] Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.
Claims
1. A method for preparing a non-platinum electrocatalytic hydrogen evolution catalyst, characterized in that: include: S1: adding the ammonium persulfate solution to the aniline solution, leaving it to stand at room temperature for 24 to 36 hours, centrifuging, filtering, washing and drying to obtain a first powder; S2: adding the first powder and dichloromethane into a container, keeping warm at -5°C to 5°C, stirring for 15 to 30 minutes, and dropping m-chloroperbenzoic acid therein, continuing to keep warm at -5°C to 5°C, and stirring for 1 to 3 hours to obtain a first liquid; S3: stirring the first liquid at room temperature for 18 to 48 hours, and filtering to obtain a second powder; S4: In a protective atmosphere, keeping the second powder at 600-1100° C. for 2-6 hours to obtain a third powder; S5: ball-milling the third powder and dichlorodiaminoacetic acid for 2 to 4 hours to obtain a fourth powder, and then keeping the fourth powder at 800 to 1000° C. for 1 to 3 hours under a protective atmosphere to obtain the non-platinum electrocatalytic hydrogen evolution catalyst.
2. The method for preparing a non-platinum electrocatalytic hydrogen evolution catalyst according to claim 1, characterized in that: In S2, the molar ratio of the first powder, the dichloromethane and the meta-chloroperbenzoic acid is 5-20:3:
15.
3. The method for preparing a non-platinum electrocatalytic hydrogen evolution catalyst according to claim 1, characterized in that: In the step S3, the second powder is also washed with a saturated sodium bicarbonate solution, washed with deionized water and dried in sequence.
4. The method for preparing a non-platinum electrocatalytic hydrogen evolution catalyst according to claim 1, characterized in that: In the S4, the second powder is kept at 850°C for 2 hours.
5. The method for preparing a non-platinum electrocatalytic hydrogen evolution catalyst according to claim 1, characterized in that: In the step S5, the ball mill uses zirconium dioxide balls.
6. The method for preparing a non-platinum electrocatalytic hydrogen evolution catalyst according to claim 5, characterized in that: The diameter of the zirconium dioxide ball is 5 mm.
7. The method for preparing a non-platinum electrocatalytic hydrogen evolution catalyst according to claim 1, characterized in that: The protective atmosphere includes at least one component selected from nitrogen, helium, neon, argon or krypton.
8. The method for preparing a non-platinum electrocatalytic hydrogen evolution catalyst according to claim 7, characterized in that: The protective atmosphere is nitrogen.
9. A non-platinum electrocatalytic hydrogen evolution catalyst prepared according to the preparation method according to any one of claims 1 to 8.
10. Use of the non-platinum electrocatalytic hydrogen evolution catalyst according to claim 9 as a fuel cell catalyst.