A non-noble metal catalyst for oxygen reduction doped with multiple transition metals for fuel cells and a method for preparing the same

Abstract

The application discloses a kind of multiple transition metal doped oxygen reduction non-noble metal catalysts for fuel cell and preparation method thereof.The preparation method uses normal temperature solvent method and high temperature pyrolysis method, with zinc nitrate and dimethyl imidazole as raw material to synthesize ZIF-8, ZIF-8 is added in the synthesis process Two or more transition metal organic compounds are obtained to obtain catalyst precursor wrapped with multiple transition metal organic compounds, and then multiple transition metal doped non-noble metal catalyst is obtained by high temperature pyrolysis and acid treatment.The application will M1, M2, M … The multiple transition metal co-doped non-noble metal catalyst is used as the cathode catalyst of proton exchange membrane fuel cell, and a kind of excellent oxygen reduction non-noble metal catalyst is prepared.The multiple transition metal doped oxygen reduction non-noble metal catalyst for fuel cell prepared by the application has excellent performance in hydrogen / air proton exchange membrane fuel cell, and also has excellent stability.

Description

TECHNICAL FIELD

[0001] The present application relates to a preparation method of a plurality of transition metal doped oxygen reduction non-noble metal catalysts for fuel cells, in particular to a non-noble metal oxygen reduction catalyst with a wide range of raw material sources, low price, simple synthesis process and high performance and stability, which has very important significance for replacing the noble metal catalyst in the cathode of the proton exchange membrane fuel cell, and can effectively promote the commercialization of fuel cells. BACKGROUND

[0002] Energy is the cornerstone of human survival and development, and with the development of society, the demand for energy is increasing, but the traditional fossil energy reserves are limited, and it will also pollute the environment during use. Therefore, it is very important to develop renewable green new energy. Among many renewable new energies, hydrogen energy is known as the "ultimate mode of energy" and has attracted widespread attention. Hydrogen energy has entered a stage of rapid development.

[0003] The most direct way to use hydrogen energy is fuel cells. Fuel cells can directly convert the chemical energy of fuel into electrical energy without combustion, have high energy conversion efficiency, low noise, are environmentally friendly, and can start quickly at low temperatures, and have broad application prospects in the transportation field. However, fuel cells have not yet been commercialized on a large scale, and the high cost limits the commercialization of fuel cells. One reason for the high cost is the need for a large amount of noble metal catalyst (such as platinum-carbon catalyst) on the cathode side. Therefore, in order to reduce the cost of fuel cells and promote their commercialization, it is very important to develop non-noble metal catalysts with high performance and stability.

[0004] Among many non-noble metal catalysts, transition metal doped non-noble metal catalysts have shown very excellent oxygen reduction catalytic performance and have attracted widespread attention. This type of non-noble metal catalyst is widely available, low in price, and has been applied in fuel cells. However, this type of non-noble metal catalyst still has some shortcomings: first, its catalytic activity under hydrogen / air conditions is still inferior to that of commercial platinum-carbon catalyst; second, its stability is very poor and cannot meet the requirements of practical application. Developing two or more transition metal doped non-noble metal catalysts can effectively improve the oxygen reduction capacity of the catalyst and greatly improve its stability, enabling its real application in fuel cells. SUMMARY

[0005] In order to solve the technical problems existing in the non-noble metal oxygen reduction catalyst, the purpose of the present application is to overcome the shortcomings of the prior art, provide a two or more transition metal doped oxygen reduction non-noble metal catalyst, a preparation method and application, the present application uses two or more transition metal doped ZIF-8 as the precursor of the oxygen reduction catalyst, and constructs an oxygen reduction catalyst with high catalytic activity and high stability through high temperature cracking. The raw materials of the two or more transition metal doped oxygen reduction non-noble metal catalyst prepared by the present application are widely available and low in price, the synthesis process of the precursor and the final product is simple, and at the same time, the catalyst exhibits excellent electrochemical performance and stability in the fuel cell.

[0006] In order to achieve the above-mentioned purpose of the application, the technical scheme adopted by the present application is as follows:

[0007] A preparation method of a plurality of transition metal doped oxygen reduction non-noble metal catalyst for fuel cells, comprising the following steps:

[0008] (1) Synthesizing a zeolitic imidazolate metal organic framework compound wrapped with two or more transition metal organic compounds by using a normal temperature solvent method; wherein one of the two or more transition metals is a pre-transition metal, and the rest are post-transition metals;

[0009] (2) Preparing a plurality of transition metal doped oxygen reduction non-noble metal catalyst by using a high temperature cracking method;

[0010] The synthesis method of step (1) is as follows:

[0011] Dimethyl imidazole and zinc nitrate hexahydrate are respectively dissolved in a methanol solution, and a transparent solution is formed by stirring, and two or more transition metal organic compounds are dissolved in the dimethyl imidazole methanol solution; the methanol solution containing zinc nitrate hexahydrate is slowly added to the methanol solution containing dimethyl imidazole and transition metal organic compounds, and the reaction is carried out by stirring at normal temperature; after continuous reaction, the precursor is collected by centrifugation, and washed several times with methanol, and dried to obtain a ZIF-8 precursor containing a plurality of transition metals;

[0012] The specific method of step (2) is as follows: the ZIF-8 precursor containing a plurality of transition metals is placed in an inert atmosphere, and heated to a set cracking temperature at a certain heating rate, and after high temperature cracking, it is cooled to room temperature to obtain a plurality of transition metal doped non-noble metal catalyst sample after the first cracking; the catalyst sample after the first cracking is subjected to acid treatment, and subjected to a second high temperature cracking in an inert atmosphere to obtain a plurality of transition metal doped oxygen reduction non-noble metal catalyst (M1-M2-M … / N / C, M1, M2, M … , wherein one is a pre-transition metal, and the rest are post-transition metals).

[0013] In the method, the concentration of the dimethyl imidazole methanol solution in step (1) is 10-20 mmol / mL; and the concentration of the zinc nitrate hexahydrate methanol solution is 0.5-2 mmol / L.

[0014] In the method, the front transition metal in step (1) is one of Sc, Ti, V, Cr, Y, Zr, Nb, Mo and Hf.

[0015] The rear transition metal is one or more of Mn, Fe, Co, Ni, Cu and Zn.

[0016] In the method, the molar ratio of the zinc nitrate hexahydrate and the front transition metal organic compound in step (1) is (5-25):1.

[0017] The molar ratio of the zinc nitrate hexahydrate and each rear transition metal organic compound is 5:(1-3).

[0018] In the method, the reaction time in step (1) is 5-12 hours.

[0019] In the method, the heating rate in step (2) is 2-10℃ / min.

[0020] In the method, the first cracking temperature in step (2) is 850-1050℃; and the first high-temperature cracking time is 2-6 hours.

[0021] In the method, the acid used for acid treatment in step (2) is one of sulfuric acid, hydrochloric acid, nitric acid and hydrofluoric acid; the acid concentration is 0.05-1.0 mol / L; and the acid treatment time is 6-12 hours.

[0022] In the method, the second cracking temperature in step (2) is 850-1050℃; and the second high-temperature cracking time is 2-6 hours.

[0023] The application further provides a fuel cell multiple transition metal doped oxygen reduction non-noble metal catalyst, which is prepared by the preparation method of the fuel cell multiple transition metal doped oxygen reduction non-noble metal catalyst.

[0024] The application further provides a fuel cell multiple transition metal doped oxygen reduction non-noble metal catalyst, which is prepared by the preparation method of the fuel cell multiple transition metal doped oxygen reduction non-noble metal catalyst.

[0025] As a preferred technical scheme of the present application, the fuel cell multiple transition metal doped oxygen reduction non-noble metal catalyst has a positive dodecahedron structure and a particle size of 150-250 nm.

[0026] The present application also provides a fuel cell multiple transition metal doped oxygen reduction non-noble metal catalyst and an application thereof. The catalyst is prepared by a method for preparing a fuel cell multiple transition metal doped oxygen reduction non-noble metal catalyst slurry, which is sprayed onto the cathode side of a proton exchange membrane. After drying, an anode Pt / C catalyst slurry is prepared by the method for preparing a fuel cell multiple transition metal doped oxygen reduction non-noble metal catalyst slurry and is sprayed onto the anode side of the proton exchange membrane. The proton exchange membrane fuel cell single cell is composed of the cathode side multiple transition metal doped oxygen reduction non-noble metal catalyst, the anode side Pt / C catalyst, and the cathode and anode gas diffusion layers. The catalyst loading on the cathode side is 0.5-4 mg / cm 2 , and the catalyst loading on the anode side is 0.05-0.2 mg / cm 2 .

[0027] The fuel cell multiple transition metal doped oxygen reduction non-noble metal catalyst is used as a cathode oxygen reduction catalyst material for fuel cells. 2.5-20 mg of the catalyst, 25-200 mg of a 5 wt% Nafion solution, and 2-10 mL of isopropyl alcohol are mixed and ultrasonically treated for at least 30 min to prepare a catalyst slurry.

[0028] Compared with the prior art, the present application has the following obvious and substantial features and advantages.

[0029] 1. The fuel cell multiple transition metal doped oxygen reduction non-noble metal catalyst prepared by the present application has a wide source of raw materials and a low price, and the preparation method is simple.

[0030] 2. The fuel cell multiple transition metal doped oxygen reduction non-noble metal catalyst prepared by the present application uses ZIF-8 as a precursor and dopes one pre-transition metal and one or more post-transition metals.

[0031] 3. In the catalyst prepared by the method of the present application, the post-transition metal mainly provides the first oxygen reduction active site, while the pre-transition metal has the functions of providing the second oxygen reduction active site, eliminating hydrogen peroxide and active oxygen free radicals, effectively enhancing the intrinsic catalytic activity of the catalyst, reducing the attack of hydrogen peroxide and active oxygen free radicals on the catalyst and the proton exchange membrane, and enhancing the binding force of the post-transition metal, effectively inhibiting the dissolution and destruction of the metal active center and improving the stability of the active center.

[0032] 4. The catalyst prepared by the method has excellent performance and stability in an air / hydrogen proton exchange membrane fuel cell single cell, and can be practically applied in a fuel cell.

[0033] 5. The method is simple, low in cost, and suitable for large-scale application and promotion. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 A comparison chart of membrane electrode polarization performance of the various transition metal doped oxygen reduction non-noble metal catalysts for fuel cells prepared in Examples 1-3 of the present application and single transition metal doped oxygen reduction non-noble metal catalysts (comparative examples) under hydrogen / oxygen conditions.

[0035] Figure 2 A comparison chart of membrane electrode stability performance of the various transition metal doped oxygen reduction non-noble metal catalysts for fuel cells prepared in Examples 1-3 of the present application and single transition metal doped oxygen reduction non-noble metal catalysts (comparative examples) under hydrogen / oxygen conditions. DETAILED DESCRIPTION

[0036] The above scheme is further described below in conjunction with specific examples, and preferred embodiments of the present application are described in detail as follows:

[0037] Example 1

[0038] In this example, a method for preparing a cobalt-zirconium co-doped carbon-based catalyst includes the following steps:

[0039] a. Synthesizing an imidazole type metal organic framework compound wrapped with cobalt acetylacetonate and zirconium acetylacetonate by using a room temperature solvent method, and the synthesis method is as follows:

[0040] 2.463 g of dimethyl imidazole and 0.297 g of zinc nitrate hexahydrate were respectively dissolved in 20 mL and 10 mL of methanol solution to form transparent solutions by stirring, and 0.104 g of cobalt acetylacetonate and 0.049 g of zirconium acetylacetonate were dissolved in the dimethyl imidazole methanol solution;

[0041] The methanol solution containing zinc nitrate hexahydrate was slowly added to the methanol solution containing dimethyl imidazole and cobalt acetylacetonate and zirconium acetylacetonate, and the reaction was carried out by stirring at room temperature; after 12 h of continuous reaction, the precursor was collected by centrifugation and washed with methanol 4 times, and then dried to obtain a ZIF-8 precursor containing a front transition metal zirconium and a rear transition metal cobalt;

[0042] b. A cobalt-zirconium co-doped oxygen reduction carbon-based catalyst (Co-Zr / N / C) was prepared by using a high-temperature pyrolysis method:

[0043] The ZIF-8 precursor containing the front transition metal zirconium and the rear transition metal cobalt is placed in a nitrogen atmosphere, and heated to 900℃ at a heating rate of 5℃ / min, and then cooled to room temperature after high-temperature pyrolysis for 3h to obtain a non-noble metal carbon-based catalyst sample of the front transition metal zirconium and the rear transition metal cobalt after the first pyrolysis;

[0044] The catalyst sample after the first pyrolysis is subjected to acid treatment in a 0.5M HF solution for 8h, and subjected to a second high-temperature pyrolysis at 900℃ under a nitrogen atmosphere for 2h to obtain a final catalyst sample (Co-Zr / N / C), and the XRD result of the catalyst is shown in Figure 1 , and the structure of the catalyst is shown in Figure 2 ,

[0045] The Co-Zr / N / C catalyst is prepared into a fuel cell membrane electrode as a cathode catalyst, and the loading of the Co-Zr / N / C catalyst is 2.0 cm -2 , and the loading of Nafion in the cathode catalyst layer is 1.0 mg cm -2 ; and the anode side is a 60% Pt / C catalyst, in which the loading of Pt is 0.1 mg cm -2 , and the loading of Nafion is 0.04 mg / cm2, and the membrane electrode is prepared by spraying the anode and cathode catalyst slurries to both sides of the proton exchange membrane through an air spraying method, and pressing the anode and cathode gas diffusion layers into the anode and cathode catalyst layers through hot pressing.

[0046] The membrane electrode is assembled into a fuel cell single cell, and the membrane electrode is subjected to polarization test under a hydrogen-oxygen condition, and the cell polarization curve is shown in Figure 1 , and the current density can reach 900 mA cm -2 at a voltage of 0.65 V, and the maximum power density is 848 mW cm -2 . Meanwhile, the performance attenuation is 25.6% after 10h constant current discharge. Compared with the comparative example, the current density of the membrane electrode of the Co-Zr / N / C catalyst as the cathode catalyst is improved at 0.65 V, and the stability is also enhanced.

[0047] Example 2

[0048] In this example, a preparation method of a cobalt-yttrium co-doped carbon-based catalyst includes the following steps:

[0049] a. An imidazole type metal organic framework compound wrapped with cobalt acetylacetonate and yttrium acetylacetonate is synthesized by a normal temperature solvent method, and the synthesis method is as follows:

[0050] 2.463 g of dimethylimidazole, 0.297 g of zinc nitrate hexahydrate were dissolved in 20 mL and 10 mL of methanol solution respectively, and transparent solutions were formed by stirring, while 0.104 g of cobalt acetylacetonate and 0.044 g of yttrium acetylacetonate were dissolved into the dimethylimidazole methanol solution;

[0051] The methanol solution containing zinc nitrate hexahydrate was slowly added to the methanol solution containing dimethylimidazole and cobalt acetylacetonate and yttrium acetylacetonate, and the reaction was carried out by stirring at room temperature; after 12 h of continuous reaction, the precursor was collected by centrifugation and washed with methanol 4 times, and the ZIF-8 precursor containing the front transition metal yttrium and the rear transition metal cobalt was obtained after drying;

[0052] b. Cobalt-yttrium co-doped oxygen reduction carbon-based catalyst (Co-Y / N / C) was prepared by high-temperature pyrolysis:

[0053] The ZIF-8 precursor containing the front transition metal yttrium and the rear transition metal cobalt was placed in a nitrogen atmosphere, and the temperature was raised to 900℃ at a rate of 5℃ / min, and the sample of the non-noble metal carbon-based catalyst of the front transition metal yttrium and the rear transition metal cobalt was obtained after high-temperature pyrolysis for 3 h and cooling to room temperature;

[0054] The catalyst sample after the first pyrolysis was subjected to acid treatment in a 0.5 M HF solution for 8 hours, and the final catalyst sample (Co-Y / N / C) was obtained after the second high-temperature pyrolysis at 900℃ under a nitrogen atmosphere for 2 hours.

[0055] The Co-Y / N / C catalyst was prepared into a fuel cell membrane electrode as a cathode catalyst, wherein the loading of the Co-Y / N / C catalyst was 2.0 cm -2 , and the loading of Nafion in the cathode catalyst layer was 1.0 mg cm -2 ; and the anode side was a 60% Pt / C catalyst, wherein the loading of Pt was 0.1 mg cm -2 , and the loading of Nafion was 0.04 mg / cm2, the anode and cathode catalyst slurries were sprayed onto both sides of the proton exchange membrane by air spraying, and the anode and cathode gas diffusion layers were pressed into the anode and cathode catalyst layers to prepare the membrane electrode.

[0056] The membrane electrode was assembled into a fuel cell single cell, and the membrane electrode was subjected to polarization test under hydrogen-oxygen condition, and the cell polarization curve is shown in Figure 1 , and the current density can reach 750 mA cm -2 at a voltage of 0.65 V, and the maximum power density is 734 mW cm -2Meanwhile, after 10 hours of constant current discharge, the performance decay is 39.2%. Compared with the comparative example, the current density of the membrane electrode at 0.65 V is also improved when the Co-Y / N / C catalyst is used as the cathode catalyst, and the stability is also enhanced.

[0057] Example 3

[0058] In this embodiment, a preparation method of a cobalt-nickel-zirconium co-doped carbon-based catalyst includes the following steps:

[0059] a. An imidazole type metal organic framework compound wrapped with cobalt acetylacetonate, nickel acetylacetonate and zirconium acetylacetonate is synthesized by using a normal temperature solvent method, and the synthesis method is as follows:

[0060] 2.463 g of dimethyl imidazole and 0.297 g of zinc nitrate hexahydrate are respectively dissolved in 20 mL and 10 mL of a methanol solution to form transparent solutions by stirring, and 0.104 g of cobalt acetylacetonate, 0.103 g of nickel acetylacetonate and 0.049 g of zirconium acetylacetonate are dissolved in the dimethyl imidazole methanol solution;

[0061] The methanol solution containing zinc nitrate hexahydrate is slowly added to the methanol solution containing dimethyl imidazole and cobalt acetylacetonate, nickel acetylacetonate and zirconium acetylacetonate, and the reaction is carried out by stirring at room temperature; after 12 h of continuous reaction, the precursor is collected by centrifugation and washed with methanol for 4 times, and the ZIF-8 precursor containing the front transition metal zirconium and the rear transition metals cobalt and nickel is obtained after drying;

[0062] b. A cobalt-zirconium co-doped oxygen reduction carbon-based catalyst (Co-Ni-Zr / N / C) is prepared by using a high-temperature pyrolysis method:

[0063] The ZIF-8 precursor containing the front transition metal zirconium and the rear transition metals cobalt and nickel is placed in a nitrogen atmosphere, and the temperature is increased to 900℃ at a heating rate of 5℃ / min, and the high-temperature pyrolysis is carried out for 3 h, and then the temperature is cooled to room temperature, and the non-noble metal carbon-based catalyst sample of the front transition metal zirconium and the rear transition metals cobalt and nickel after the first pyrolysis is obtained;

[0064] The catalyst sample after the first pyrolysis is subjected to acid treatment in a 0.5M HF solution for 8 hours, and the second high-temperature pyrolysis is carried out at 900℃ under a nitrogen atmosphere for 2 hours to obtain the final catalyst sample (Co-Zr / N / C).

[0065] The Co-Ni-Zr / N / C catalyst is used as the cathode catalyst to prepare a fuel cell membrane electrode, and the loading of the Co-Ni-Zr / N / C catalyst is 2.0 cm -2 , and the loading of Nafion in the cathode catalytic layer is 1.0 mg cm -2; and 60% Pt / C catalyst with 0.1 mg cm -2 -2 The anode and cathode catalyst slurries were sprayed on both sides of the proton exchange membrane by air spraying method, and the anode and cathode gas diffusion layers were pressed into the anode and cathode catalyst layers by hot pressing to prepare the membrane electrode.

[0066] The membrane electrode was assembled into a fuel cell single cell, and the polarization test of the membrane electrode was carried out under hydrogen-oxygen condition. The cell polarization curve is shown in Figure 1 -2 , and the maximum power density was 950 mW cm -2 . At the same time, after 10 hours of constant current discharge, the performance decay was only 16.8%. Compared with Example 1, Example 2 and the comparative example, the current density of the membrane electrode at 0.65V was greatly improved when the Co-Ni-Zr / N / C catalyst was used as the cathode catalyst, and the stability was also greatly improved.

[0067] Comparative Example 1

[0068] In this comparative example, a method for preparing a cobalt-doped carbon-based catalyst includes the following steps:

[0069] a. Synthesizing an imidazole type metal organic framework compound wrapped with cobalt acetylacetone by room temperature solvent method, and the synthesis method is as follows:

[0070] 2.463 g of dimethyl imidazole and 0.297 g of zinc nitrate hexahydrate were respectively dissolved in 20 mL and 10 mL of methanol solution to form transparent solutions by stirring, and 0.104 g of cobalt acetylacetone was dissolved in the dimethyl imidazole methanol solution;

[0071] The methanol solution containing zinc nitrate hexahydrate was slowly added to the methanol solution containing dimethyl imidazole and cobalt acetylacetone, and the reaction was carried out by stirring at room temperature; after 12 h of continuous reaction, the precursor was collected by centrifugation and washed with methanol for 4 times, and dried to obtain a ZIF-8 precursor containing cobalt;

[0072] b. A cobalt-doped oxygen reduction carbon-based catalyst (Co / N / C) was prepared by high temperature pyrolysis method:

[0073] The ZIF-8 precursor containing cobalt was placed in a nitrogen atmosphere, and the temperature was increased to 900℃ at a rate of 5℃ / min, and after pyrolysis at high temperature for 3 h, it was cooled to room temperature to obtain a once-pyrolyzed cobalt-doped non-noble metal carbon-based catalyst sample;

[0074] The first cracked catalyst sample was acid treated in 0.5 M HF solution for 8 hours and second high temperature cracking was carried out at 900 °C under nitrogen atmosphere for 2 hours to obtain the final catalyst sample (Co / N / C).

[0075] The Co / N / C catalyst was prepared as cathode catalyst for fuel cell membrane electrode, where the loading of Co / N / C catalyst was 2.0 cm -2 , and the loading of Nafion in cathode catalyst layer was 1.0 mg cm -2 ; while the anode side was 60% Pt / C catalyst, where the loading of Pt was 0.1 mg cm -2 , and the loading of Nafion was 0.04 mg / cm2. The membrane electrode was prepared by spraying the anode and cathode catalyst slurry to both sides of the proton exchange membrane by air spraying method, and pressing the anode and cathode gas diffusion layers into the anode and cathode catalyst layers by hot pressing.

[0076] The membrane electrode was assembled into a fuel cell single cell, and the polarization test of the membrane electrode was carried out under hydrogen-oxygen condition. The cell polarization curve is shown in Figure 1 , where the current density reached 400 mA cm -2 at a voltage of 0.65 V, and the maximum power density was 502 mW cm -2 . At the same time, the performance decay was 60.6% after 10 hours of constant current discharge.

[0077] The above specific description further details the purpose, technical solutions and beneficial effects of the application. It should be understood that the above description is only a specific embodiment of the application and is not intended to limit the protection scope of the application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the application shall be included in the protection scope of the application.

Claims

1. A multiple transition metal doped oxygen reduction non-precious metal catalyst for fuel cells, characterized by: The catalyst is a positive dodecahedron structure, the particle size is 150-250 nm, and the transition metals are uniformly dispersed in the catalyst framework in the form of atoms; the transition metals are a combination of Co and Zr, a combination of Co and Y, a combination of Co and Ni, and Zr; The preparation method comprises the following steps: (1) synthesizing a zeolitic imidazolate metal organic framework compound wrapped with two or more transition metal organic compounds by using a normal temperature solvent method; one of the two or more transition metals is a pre-transition metal, and the rest are post-transition metals; (2) preparing a plurality of transition metal-doped oxygen reduction non-noble metal catalysts by using a high-temperature pyrolysis method; The synthesis method of step (1) is as follows: Dimethyl imidazole and zinc nitrate hexahydrate are respectively dissolved in a methanol solution to form a transparent solution by stirring, and two or more transition metal organic compounds are dissolved in the dimethyl imidazole methanol solution; the methanol solution containing zinc nitrate hexahydrate is slowly added to the methanol solution containing dimethyl imidazole and transition metal organic compounds, and the reaction is carried out by stirring at normal temperature; after continuous reaction, the precursor is collected by centrifugation, washed several times with methanol, and dried to obtain a ZIF-8 precursor containing a plurality of transition metals; The specific method of step (2) is as follows: the ZIF-8 precursor containing a plurality of transition metals is placed in an inert atmosphere, heated at a certain heating rate to a set pyrolysis temperature, cooled to room temperature after high-temperature pyrolysis, and a plurality of transition metal-doped non-noble metal catalyst samples after the first pyrolysis are obtained; The catalyst sample after the first pyrolysis is subjected to acid treatment and second high-temperature pyrolysis in an inert atmosphere to obtain a plurality of transition metal-doped oxygen reduction non-noble metal catalysts; In step (1), the pre-transition metal is one of Y and Zr; and the post-transition metal is one or more of Co and Ni; In step (1), the molar ratio of the zinc nitrate hexahydrate and the pre-transition metal organic compound is (5-25):1; and the molar ratio of the zinc nitrate hexahydrate and each post-transition metal organic compound is 5:(1-3); In step (2), the heating rate is 2-10℃ / min; the first pyrolysis temperature is 850-1050℃; the first high-temperature pyrolysis time is 2-6 hours; the second pyrolysis temperature is 850-1050℃; and the second high-temperature pyrolysis time is 2-6 hours.

2. The transition metal doped oxygen reduction non-precious metal catalyst according to claim 1, wherein: In step (1), the concentration of the dimethyl imidazole methanol solution is 10-20 mmol / mL; and the concentration of the zinc nitrate hexahydrate methanol solution is 0.5-2 mmol / L.

3. The transition metal doped oxygen reduction non-precious metal catalyst according to claim 1, wherein: In step (1), the reaction time is 5-12 hours.

4. The transition metal doped oxygen reduction non-precious metal catalyst according to claim 1, wherein: In step (2), the acid used for acid treatment is one of sulfuric acid, hydrochloric acid, nitric acid, and hydrofluoric acid; the acid concentration is 0.05-1.0 mol / L; and the acid treatment time is 6-12 hours.

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