CN113540476B - Preparation method and application of non-noble metal cathode catalyst of fuel cell - Google Patents

Preparation method and application of non-noble metal cathode catalyst of fuel cell Download PDF

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CN113540476B
CN113540476B CN202111073557.4A CN202111073557A CN113540476B CN 113540476 B CN113540476 B CN 113540476B CN 202111073557 A CN202111073557 A CN 202111073557A CN 113540476 B CN113540476 B CN 113540476B
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zif
fuel cell
noble metal
cathode catalyst
ball
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CN113540476A (en
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刘建国
吴永康
李佳
张天任
曹寅亮
王胜平
张树国
徐淳川
赵海敏
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Nanjing University
Tianneng Battery Group Co Ltd
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Tianneng Battery Group Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a fuel cell non-noble goldBelongs to a preparation method and application of cathode catalyst material, and the method comprises the following steps: preparing a zeolite imidazolate metal organic framework polymer; preparing a metal organic framework polymer containing transition metal by liquid phase adsorption; ball milling; liquid phase recrystallization; and (4) pyrolyzing at high temperature under inert atmosphere. Also discloses the catalyst prepared by the method in H2‑O2Fuel cells and methanol fuel cells. The material has rich active sites and an excellent hierarchical pore structure; by introducing ball milling and liquid phase recrystallization methods, the M-N-C material obtained by pyrolysis of the metal organic framework adsorbed with the transition metal is rich in a rich mesoporous structure and more transition metal single atoms on the surface, provides more active sites, and shows excellent electrochemical performance when applied to a fuel cell cathode.

Description

Preparation method and application of non-noble metal cathode catalyst of fuel cell
Technical Field
The invention relates to a preparation method and application of an electrode catalyst, in particular to a preparation method and application of a non-noble metal cathode catalyst of a fuel cell.
Background
A fuel cell is a device that converts chemical energy in chemicals into electric energy, and is paid much attention to its advantages of high energy conversion efficiency, small environmental pollution, high controllability, and the like. However, the fuel cell electrocatalyst widely used in commerce still mainly comprises precious metals (platinum, rhodium, palladium, iridium, and the like), which are expensive and scarce in resources, and greatly restricts the commercial development and application of the fuel cell, so that research and development of a catalyst material without the precious metals are of great significance.
Early researchers found that transition metal doped nitrogen carbon materials have excellent catalytic activity and perform particularly well on oxygen reduction. In this regard, researchers have conducted a great deal of research here, the most representative of which is the use of transition metal doped nitrogen carbon materials as oxygen reduction catalyst materials. Although the catalytic activity of the M-N-C catalyst material is greatly improved, the M-N-C catalyst material has a large difference with a noble metal such as a Pt-based catalyst, and the difference is particularly obvious in a fuel cell and is far from the time of the service life of the fuel cell in both power output and working conditions. For this reason, it is very important to further develop a cathode catalyst material with high catalytic activity and realize a fuel cell with high power output. The monatomic transition metal doped M-N-C derived from the MOF has excellent oxygen reduction catalytic activity, but the obtained catalyst active site is mostly monatomic M-Nx based on micropore confinement, so that the accessibility of reactants is greatly limited, and the catalytic activity is greatly reduced, so that the development of the M-N-C catalyst with higher catalytic activity and high utilization rate is the key for realizing a high-power fuel cell.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of a non-noble metal catalyst of a fuel cell, which has high utilization rate of active sites and excellent electrochemical performance;
a second object of the present invention is to provide a use of a non-noble metal catalyst for fuel cells.
The technical scheme is as follows: the preparation method of the non-noble metal cathode catalyst of the fuel cell comprises the following steps:
(1) respectively dissolving imidazole monomer and metal ligand salt in a solvent to obtain solution A and solution B, mixing the solution A and the solution B, performing hydrothermal reaction, and centrifuging, washing and drying after the reaction is finished to obtain a zeolite imidazole ester metal organic framework material ZIF;
(2) adding ZIF, nitrogenous organic matter and transition metal salt into a solvent, stirring and evaporating to dryness to obtain transition metal doped ZIF, and recording as M-ZIF;
(3) performing Ball milling on the M-ZIF to obtain M-ZIF with a pulverized structure and defects, and marking as M-ZIF-Ball;
(4) dissolving M-ZIF-Ball in a solvent, stirring, standing for recrystallization, centrifuging, washing, and drying to obtain recrystallized M-ZIF-Ball, and marking as M-ZIF-Recry; and then obtaining the metal-nitrogen-carbon catalyst material through pyrolysis, and marking the metal-nitrogen-carbon catalyst material as M-N-C-Recry.
In the step (3), the mass ratio of ball-milling ball materials is 100-10: 1; the ball milling speed is 200-1000 rpm, and the ball milling time is 1-24 h.
In the step (4), the crystallization time of room-temperature recrystallization is 1-48 h; the atmosphere of pyrolysis is N2Or Ar inert atmosphere, the pyrolysis temperature is 800-1100, and the pyrolysis time is 0.5-2 h.
In the step (2), the mass ratio of the transition metal salt to the nitrogen-containing organic compound to the ZIF is 1: 10-50: 20 to 500.
In the step (2), the transition metal salt is one or more of acetate, chloride, nitrate, carbonate, phosphate, sulfate, oxalate, citrate and acetylacetone-based compound of Fe or Co; the nitrogen-containing organic matter is one or more of phenanthroline, acetamide, ethylamine, pyrrole, aniline, ethylenediamine, dopamine, dicyandiamide, urea, butyronitrile and melamine. The N element in the nitrogen-containing organic matter is coordinated with the transition metal to form a transition metal-N bond, so that the transition metal element is ensured to be distributed in a single atom form; on the other hand, the nitrogen-containing complex is used as a pore-forming agent during pyrolysis, thereby being more beneficial to generation of mesopores.
In the step (1), the ZIF is any one of ZIF-8, ZIF-67, ZIF-7, ZIF-9, ZIF-11, ZIF-14, ZIF-68, ZIF-69, ZIF-70 and ZIF-90; the molar ratio of the imidazole monomer to the metal salt ligand is 1-100: 1, and the solvothermal reaction temperature is 100-240 ℃.
The non-noble metal cathode catalyst for the fuel cell comprises a metal-nitrogen-carbon catalyst material, wherein the metal-nitrogen-carbon catalyst material is a nitrogen-doped carbon material with a hierarchical pore structure and single transition metal atoms are distributed on the nitrogen-doped carbon material, and the transition metal atoms are mainly distributed on the surface layer of the metal-nitrogen-carbon catalyst material in a single atom form; wherein the content of the transition metal is 1-4 wt%, and the ratio of micropores to mesopores in the hierarchical pore structure is 4-1: 1.
wherein the transition metal in the metal-nitrogen-carbon support is Fe and/or Co; the metal-nitrogen-carbon catalyst material is a nitrogen-doped carbon material with a hierarchical pore structure, wherein transition metal single atoms are uniformly distributed on the nitrogen-doped carbon material.
The fuel cell non-noble metal cathode catalyst prepared by the preparation method of the fuel cell non-noble metal cathode catalyst is used in H2-O2Fuel cells and methanol fuel cells.
The basic principle is as follows: the ZIF crystal framework is directly pulverized and disordered by the huge energy provided by ball milling, a large number of mesopores, macropores and other defects are generated, and then nucleation and aggregation forming are carried out again during recrystallization, but the nucleation rate of ZIF is faster and stable, so that the metal organic complex is uniformly coordinated around the outer layer of the ZIF crystal framework after nucleation, and the content of transition metal atoms on the surface layer of the M-N-C catalyst obtained by pyrolyzing the recrystallized ZIF precursor is richer. The pyrolysis product M-N-C which is not subjected to ball milling and recrystallization is mainly microporous, but micropores have great limitation on the entrance of reactants, so that the catalytic activity is not high or the utilization rate is low; the recrystallized pyrolysis product M-N-C-Recry has the most mesopores, and the mesopores are beneficial to mass transfer in a fuel cell, so that the catalytic activity is improved.
Has the advantages that: compared with the prior art, the invention has the following remarkable effects: 1. the non-noble metal cathode catalyst material is rich in transition metal monoatomic atoms on the surface layer and has an excellent multi-stage pore channel structure, the transition metal monoatomic atoms on the surface layer enable active sites to be more easily contacted with reactants, and the multi-stage pore channel structure is beneficial to mass transfer in a fuel cell, so that the super-high electrocatalytic activity is shown; 2. the ball milling and liquid phase recrystallization method is introduced, so that the prepared M-N-C catalyst material is rich in a mesoporous structure, and the surface layer is more rich in transition metal monoatomic atoms, thereby being beneficial to mass transfer and greatly improving the utilization rate of active sites, and when the catalyst is applied to the cathode of a fuel cell, the catalyst shows excellent electrochemical performance; 3. the preparation method is simple and controllable, has high consistency and is easy to realize batch production; 4. the application shows ultrahigh output power in the fuel cell.
Drawings
FIG. 1 is a XRD diffraction pattern of a ZIF-8 series of non-noble metal catalyst materials according to the present invention;
FIG. 2 is a comparative transmission electron microscope image of a ZIF-8 series of M-N-C, M-N-C-Ball and M-N-C-Recry non-noble metal catalyst materials of the present invention;
FIG. 3 is a graph comparing the isothermal adsorption curves for Fe-N-C, Fe-N-C-Ball and Fe-N-C-Recry in example 1;
FIG. 4 is a graph comparing pore volumes and micropore to mesopore ratios for Fe-N-C, Fe-N-C-Ball and Fe-N-C-Recry in example 1;
FIG. 5 is a comparison graph of inductively coupled plasma spectra of Fe-N-C, Fe-N-C-Ball and Fe-N-C-Recry versus Fe content calibration in example 1;
FIGS. 6a, 6b and 6C are comparative X-ray photoelectron spectroscopy curves of Fe-N-C, Fe-N-C-Ball and Fe-N-C-Recry in example 1, respectively; FIG. 6d is a comparison graph of X-ray photoelectron spectroscopy of Fe-N-C, Fe-N-C-Ball and Fe-N-C-Recry in example 1 with respect to the calibration of the Fe element content on the particle surface;
FIG. 7 is a graph comparing the linear sweep voltammograms of Fe-N-C, Fe-N-C-Ball and Fe-N-C-Recry in example 1;
FIG. 8 shows the results of example 1 in which Fe-N-C, Fe-N-C-Ball and Fe-N-C-recrry are at H2-O2Polarization curve contrast plots in fuel cell applications;
FIG. 9 is a graph comparing the power density curves calculated from FIG. 8;
FIG. 10 shows the results of examples 1, 2 and 5 with Fe-N-C-recrry at H2-O2Polarization curves in fuel cell applicationsComparing the images;
FIG. 11 is a comparison of the linear sweep voltammograms of Fe-N-C-Recry in examples 10 and 11;
FIG. 12 is a graph comparing the linear sweep voltammograms of Fe-N-C-Recry in examples 14 and 15.
Detailed Description
The present invention is described in further detail below.
Example 1
(1) 9.52 g of Zn (NO) was taken3)2·6H2Dissolving O in 240 mL of methanol, fully stirring to obtain a solution A, dissolving 10.512 g of 2-methylimidazole in 120 mL of methanol, and fully stirring to obtain a solution B. And mixing the solution A and the solution B, stirring vigorously for 1h, adding the white emulsion into 50 mL of PTFE reaction kettle liners with each liner being about 30 mL, putting the assembled reaction kettle into a forced air drying oven, and keeping the temperature at 120 ℃ for 4 h. And centrifuging, washing and drying to prepare the ZIF-8.
(2) Weighing 25 mg of iron acetate (II), 500 mg of 1, 10-phenanthroline and 2000 mg of ZIF-8 according to the ratio of 1:20:80, and adding the weighed materials into a beaker. 100 mL of methanol and 20 mL of deionized water were added and stirred for 2 h. And putting the powder into a water bath kettle, carrying out rotary evaporation at 85 ℃, putting the powder after evaporation into a forced air drying oven, and standing at 60 ℃ overnight to obtain Fe-ZIF.
(3) Weighing 2 g of Fe-ZIF powder, adding the Fe-ZIF powder into an agate Ball milling tank, then adding 100 g of Ball milling beads, namely, the Ball-to-material ratio is 50:1, setting the Ball milling rotation speed to be 240rpm, and the Ball milling time to be 8 hours, and scraping out the solid after the Ball milling is finished to obtain the Fe-ZIF-Ball.
(4) Weighing 1 g of Fe-ZIF-Ball powder, adding the Fe-ZIF-Ball powder into 100 ml of methanol, fully stirring for 1h, standing for 12 h, and centrifuging, washing and drying after the powder is completely crystallized to obtain Fe-ZIF-Recry.
(5) In order to represent the influence of Ball milling and recrystallization on the performance and the structure of a catalyst material, 600 mg of Fe-ZIF, Fe-ZIF-Ball and Fe-ZIF-Recry are respectively placed in different corundum crucibles, the crucibles are placed in quartz tubes, and then all the materials are pyrolyzed, wherein the pyrolyzing atmosphere is N2The pyrolysis temperature is 1000 ℃, the pyrolysis time is 1h, and the final product is obtained after the pyrolysis is finishedFe-N-C, Fe-N-C-Ball and Fe-N-C-Recry.
As shown in fig. 1, which is an XRD diffraction pattern of the non-noble metal catalyst material ZIF-8 series in this example, it can be seen that the ball-milled material is transformed from a typical ZIF-8 crystal form to an amorphous form, and is transformed again to a ZIF-8 crystal form structure after recrystallization.
FIG. 2 shows a comparative transmission electron microscope image of M-N-C, M-N-C-Ball and M-N-C-Recry of the ZIF-8 series of non-noble metal catalyst materials of the present invention; it can be seen that (a) and (C) in fig. 2 are both regular dodecahedron structures, i.e., M-N-C, M-N-C-recrry is both regular dodecahedron structures, while (b) in fig. 2 represents irregular powder particles, i.e., M-N-C-Ball represents irregular powder particles.
FIG. 3 is a graph showing a comparison of isothermal adsorption curves of Fe-N-C, Fe-N-C-Ball and Fe-N-C-Recry in example 1; it can be seen that the obvious regression line hysteresis of Fe-N-C-Ball shows that the Ball milling causes huge damage to the material structure and a large amount of mesoporous structures appear.
FIG. 4 is a graph showing the pore volume and the micropore to mesopore ratio of Fe-N-C, Fe-N-C-Ball and Fe-N-C-Recry in example 1; the pyrolysis product Fe-N-C-Recry subjected to ball milling and recrystallization has the most micropores, and the pyrolysis product Fe-N-C-recrry subjected to recrystallization has the most mesopores, so that mass transfer in the fuel cell is facilitated.
FIG. 5 is a graph showing the comparison of inductively coupled plasma spectra of Fe-N-C, Fe-N-C-Ball and Fe-N-C-Recry in example 1 with respect to the content of Fe element; it can be seen that there is no significant difference in the Fe content of the three.
FIGS. 6a, 6b and 6C are comparative X-ray photoelectron spectroscopy curves of Fe-N-C, Fe-N-C-Ball and Fe-N-C-Recry in example 1, respectively; it can be seen that the recrystallized pyrolysis product Fe-N-C-Recry contains the most Fe-Nx ligands, i.e. the highest density of surface active sites. FIG. 6d is a graph showing the comparison of X-ray photoelectron spectroscopy of Fe-N-C, Fe-N-C-Ball and Fe-N-C-Recry in example 1 with the calibration of the Fe element content on the particle surface; it can be seen that the Fe content after ball milling and recrystallization is the most enriched on the surface, thus indicating that the ball milling and recrystallization are both beneficial to the enrichment of Fe element on the surface of the catalyst material. The main principle is as follows: because the ZIF-8 crystal framework is directly pulverized and disordered by the huge energy provided during ball milling, and then is nucleated again and aggregated for forming during recrystallization, but because the nucleation rate of the ZIF-8 is faster and stable, the organic complex of iron is uniformly coordinated around the outer layer of the organic complex after nucleation, and the surface transition metal atom content of the M-N-C catalyst obtained by pyrolyzing the recrystallized Fe-ZIF precursor is richer.
FIG. 7 is a graph showing a comparison of linear sweep voltammograms of Fe-N-C, Fe-N-C-Ball and Fe-N-C-Recry in example 1; wherein the recrystallized pyrolysis product Fe-N-C-Recry shows the highest half-wave potential, E1/2=0.806V, i.e. the highest catalytic activity.
As shown in FIG. 8, the results of example 1 were obtained when Fe-N-C, Fe-N-C-Ball and Fe-N-C-Recry were in H2-O2Comparing polarization curves in fuel cell applications, it can be seen that the recrystallized pyrolysis product Fe-N-C-Recry exhibits the most excellent polarization curve.
FIG. 9 is a graph comparing the power density curves calculated for FIG. 8; it can be seen that the recrystallized pyrolysis product Fe-N-C-Recry exhibits the highest power density output, typically up to 1.4 w/cm peak power density2。
Example 2
The difference between this example and example 1 is: the mass of 2-methylimidazole added in step 1 was 21.024 g.
Example 3
The difference between this example and example 1 is: the hydrothermal reaction temperature in step 1 was 160 ℃.
Example 4
The difference between this example and example 1 is: the transition metal salt used in step 2 is cobalt acetylacetonate.
Example 5
The difference between this example and example 1 is: the iron acetate (II), the 1, 10-phenanthroline and the ZIF-8 added in the step 2 are respectively as follows by mass: 25 mg, 500 mg and 4000 mg, i.e. in a ratio of 1:20: 160.
Example 6
The difference between this example and example 1 is: in the step 3, the rotation speed of the ball mill is 200 rpm, and the ball milling time is 24 hours.
Example 7
The difference between this example and example 1 is: in the step 3, the rotation speed of the ball mill is 1000rpm, and the ball milling time is 1 h.
Example 8
The difference between this example and example 1 is: the mass of the Fe-ZIF and the ball-milling beads added in the step 3 is respectively 2 g and 200 g, namely the mass ratio of the ball material is 100: 1.
example 9
The difference between this example and example 1 is: the crystallization time in the step 4 is 24 h.
Example 10
The difference between this example and example 1 is: in the step 5, the pyrolysis temperature is 1100 ℃, and the pyrolysis time is 0.5 h.
Example 11
The difference between this example and example 1 is: in the step 5, the pyrolysis temperature is 800 ℃, and the pyrolysis time is 2 hours.
Example 12
The difference between this example and example 1 is: the crystallization time in the step 4 is 1 h.
Example 13
The difference between this example and example 1 is: the mass of the Fe-ZIF and the ball-milling beads added in the step 3 is respectively 20 g and 200 g, namely the mass ratio of the ball material is 10: 1.
example 14
The difference between this example and example 1 is: the iron acetate (II), the 1, 10-phenanthroline and the ZIF-8 added in the step 2 are respectively as follows by mass: 25 mg, 250 mg and 500 mg, i.e. the addition ratio is 1:10: 20.
Example 15
The difference between this example and example 1 is: the iron acetate (II), the 1, 10-phenanthroline and the ZIF-8 added in the step 2 are respectively as follows by mass: 10 mg, 500 mg and 5000 mg, i.e. the addition ratio is 1:50: 500.
Example 16
The difference between this example and example 1 is: the nitrogen-containing organic matter added in the step 2 is dopamine.
Example 17
The difference between this example and example 1 is: the metal salt added in the step 1 is Co (NO)3)2·6H2O, preparation of ZIF-67.
Example 18
The difference between this example and example 1 is: and (3) preparing ZIF-7 by using the imidazole monomer added in the step (1) as benzimidazole.
Example 19
The difference between this example and example 1 is: the crystallization time in step 4 was 48 h.
As can be seen from fig. 10, 11, and 12, example 1 is superior in performance to examples 2, 5, 10, 11, 14, and 15. This is because the active site density is highest under the conditions of example 1, and the ratio of mesopores in the material structure is largest.

Claims (9)

1. A preparation method of a non-noble metal cathode catalyst of a fuel cell is characterized by comprising the following steps:
(1) respectively dissolving imidazole monomer and metal ligand salt in a solvent to obtain solution A and solution B, mixing the solution A and the solution B, performing hydrothermal reaction, and centrifuging, washing and drying after the reaction is finished to obtain a zeolite imidazole ester metal organic framework material ZIF;
(2) adding ZIF, nitrogenous organic matter and transition metal salt into a solvent, stirring and evaporating to dryness to obtain transition metal doped ZIF, and recording as M-ZIF; the transition metal salt is a divalent salt of Fe or Co; the transition metal salt is one or more of Fe or Co acetate, chloride, nitrate, carbonate, phosphate, sulfate, oxalate, citrate and acetylacetone-based compound;
(3) performing Ball milling on the M-ZIF to obtain M-ZIF with a pulverized structure and defects, and marking as M-ZIF-Ball;
(4) dissolving M-ZIF-Ball in a solvent, stirring, standing for recrystallization, centrifuging, washing, and drying to obtain recrystallized M-ZIF-Ball, and marking as M-ZIF-Recry; and then obtaining the metal-nitrogen-carbon catalyst material through pyrolysis, and marking the metal-nitrogen-carbon catalyst material as M-N-C-Recry.
2. The preparation method of the non-noble metal cathode catalyst for the fuel cell according to claim 1, wherein in the step (3), the mass ratio of ball materials subjected to ball milling is 100-10: 1.
3. the preparation method of the non-noble metal cathode catalyst for the fuel cell according to claim 1, wherein in the step (3), the rotation speed of the ball milling is 200-1000 rpm, and the ball milling time is 1-24 h.
4. The method for preparing the non-noble metal cathode catalyst for the fuel cell as recited in claim 1, wherein in the step (4), the crystallization time of recrystallization is 1-48 h.
5. The method for preparing the non-noble metal cathode catalyst for the fuel cell according to claim 1, wherein in the step (2), the mass ratio of the transition metal salt to the nitrogen-containing organic compound to the ZIF is 1: 10-50: 20 to 500.
6. The method for preparing a non-noble metal cathode catalyst for a fuel cell according to claim 1, wherein in the step (1), the ZIF is any one of ZIF-8, ZIF-67, ZIF-7, ZIF-9, ZIF-11, ZIF-14, ZIF-68, ZIF-69, ZIF-70 and ZIF-90.
7. The method for preparing the non-noble metal cathode catalyst of the fuel cell according to claim 1, wherein the metal-nitrogen-carbon catalyst material is a nitrogen-doped carbon material with a hierarchical pore structure, and single atoms of transition metals are distributed on the nitrogen-doped carbon material, and the transition metals are mainly distributed on the surface layer of the metal-nitrogen-carbon catalyst material in a single atom form; wherein the content of the transition metal is 1-4 wt%, and the ratio of micropores to mesopores in the hierarchical pore structure is 4-1: 1.
8. the method for preparing the non-noble metal cathode catalyst of the fuel cell according to claim 1, wherein the nitrogen-containing organic substance is one or more of phenanthroline, acetamide, ethylamine, pyrrole, aniline, ethylenediamine, dopamine, dicyandiamide, urea, butyronitrile and melamine.
9. The fuel cell non-noble metal cathode catalyst prepared by the method for preparing the fuel cell non-noble metal cathode catalyst according to claim 1 in H2-O2Fuel cells and methanol fuel cells.
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