Non-noble metal catalysts, methods of making the same, fuel cells, and automobiles

Abstract

The application relates to a non-noble metal catalyst, a preparation method thereof, a fuel cell and an automobile. The preparation method of the non-noble metal catalyst comprises the following steps: mixing an amino-containing cyclic compound, a non-noble metal salt and an organic solvent, and then performing a complexing reaction at 60 DEG C-80 DEG C to obtain a non-noble metal chelate; and performing calcination treatment on the non-noble metal chelate to obtain the non-noble metal catalyst. The amino on the amino-containing cyclic compound and the non-noble metal ion in the non-noble metal salt are subjected to a complexing reaction to generate the non-noble metal chelate, the non-noble metal chelate has a cyclic structure, so that after the non-noble metal chelate is subjected to the calcination treatment, the non-noble metal catalyst can be effectively prevented from being dissolved by acid, the stability of the non-noble metal catalyst is effectively improved, and the non-noble metal catalyst obtained has higher mass activity and current density.

Description

Technical Field

[0001] This application relates to the field of batteries, particularly non-precious metal catalysts and their preparation methods, fuel cells, and automobiles. Background Technology

[0002] Proton exchange membrane fuel cells (PEMFCs) are a crucial pathway to achieving a "dual-carbon strategy." However, excessively high costs remain a significant factor hindering the further commercialization of fuel cell vehicles. To date, commercially available PEMFCs still heavily rely on Pt-based catalysts, resulting in catalyst costs accounting for over 40% of the fuel cell's total cost. Reducing or eliminating the use of Pt precious metals without compromising performance is essential for the large-scale application of fuel cells.

[0003] Traditional proton exchange membrane fuel cell catalysts include Pt / C catalysts, which are highly dispersed Pt nanoparticles supported by activated carbon. These Pt / C catalysts are not conducive to further reducing the Pt loading. Currently, modification through alloying, such as adding elements like cobalt, nickel, and palladium to prepare alloy catalysts, has been employed to reduce Pt usage and achieve higher catalytic activity. However, alloying elements are prone to acid dissolution and loss, leading to rapid degradation of the alloy catalyst and resulting in poor stability. Summary of the Invention

[0004] Based on this, this application provides a non-precious metal catalyst with high quality activity and good stability, its preparation method, fuel cell and automobile.

[0005] The technical solution to the above-mentioned technical problems in this application is as follows.

[0006] This application provides a method for preparing a non-noble metal catalyst, comprising the following steps:

[0007] A non-precious metal chelate is obtained by mixing an amino-containing cyclic compound, a non-precious metal salt, and an organic solvent and then carrying out a complexation reaction at 60℃~80℃.

[0008] The non-precious metal chelate was calcined to obtain the non-precious metal catalyst.

[0009] In some embodiments, in the preparation method of the non-noble metal catalyst, the cyclic compound includes at least one of an alicyclic compound and an aromatic compound, wherein the cyclic compound is substituted with an amino group.

[0010] In some embodiments, the alicyclic compound in the preparation method of the non-noble metal catalyst includes at least one of cyclohexane and piperazine.

[0011] In some embodiments, the aromatic compound in the preparation method of the non-noble metal catalyst includes at least one of benzene, pyridazine, anthraquinone, and pyrimidine.

[0012] In some embodiments, in the preparation method of the non-noble metal catalyst, the amino group is directly bonded to the ring atoms in the cyclic compound.

[0013] In some embodiments, the preparation method of the non-noble metal catalyst includes at least one of 3-aminophthalic acid hydrazide, 3-amino-6-chloropyridazine, 1-aminocyclohexanecarboxylic acid, 1-aminoanthraquinone, 4-aminocyclohexanecarboxylic acid, 2-aminopyrimidine, and 1-amino-4-methylpiperazine.

[0014] In some embodiments, the non-precious metal in the preparation method of the non-precious metal catalyst includes at least one of copper, iron and cobalt.

[0015] In some embodiments, the non-precious metal catalyst preparation method includes at least one of non-precious metal nitrates, sulfates, metal chloride salts, and acetates.

[0016] In some embodiments, in the preparation method of the non-precious metal catalyst, the molar ratio of the non-precious metal salt to the amino-containing cyclic compound is 1:(3-10).

[0017] In some embodiments, the organic solvent in the preparation method of the non-precious metal catalyst includes at least one of ethanol, cyclohexane, and acetone.

[0018] In some embodiments, in the preparation method of the non-precious metal catalyst, the calcination treatment is carried out at a temperature of 600℃ to 1000℃ for a time of 1h to 4h.

[0019] In some embodiments, the calcination atmosphere in the preparation method of the non-precious metal catalyst includes at least one of nitrogen, argon and helium.

[0020] In some embodiments, the preparation method of the non-precious metal catalyst further includes a step of removing impurities from the calcined product by using an acid solution after the calcination treatment is completed.

[0021] The second aspect of this application provides a non-precious metal catalyst, which is prepared using the preparation method provided in the first aspect.

[0022] A third aspect of this application provides a fuel cell, including the non-precious metal catalyst provided in the second aspect.

[0023] The fourth aspect of this application provides a vehicle including the fuel cell provided in the third aspect.

[0024] Compared with existing technologies, the preparation method of the non-precious metal catalyst in this application has the following advantages:

[0025] The above-mentioned method for preparing non-precious metal catalysts involves mixing an amino-containing cyclic compound, a non-precious metal salt, and an organic solvent, followed by a complexation reaction at a specific temperature. The amino groups on the cyclic compound and the non-precious metal ions in the non-precious metal salt undergo a complexation reaction to generate a non-precious metal chelate. This chelate has a cyclic structure, allowing for further carbonization and reduction reactions during calcination. Using the amino-containing cyclic compound as the carbon and nitrogen source, the carbon elements form a uniform and stable porous structure. Nitrogen atoms linked to the carbon framework and non-precious metal atoms complexed with nitrogen atoms are uniformly distributed within the carbon's porous structure. The resulting non-precious metal-NC catalyst exhibits strong interactions between the non-precious metal and the carbon framework, effectively preventing acid dissolution and thus significantly improving the catalyst's stability. Furthermore, since no additional carbon or nitrogen source is required, additional degradation due to catalyst size inhomogeneity is avoided. Moreover, the non-precious metal in the non-precious metal-NC catalyst exists in single-atom form, fully exposing the catalytic sites and resulting in a high mass activity and current density for the obtained non-precious metal catalyst.

[0026] The above-mentioned methods for preparing non-precious metal catalysts are simple, low-cost, and have good development prospects. Detailed Implementation

[0027] Reference will now be made to detailed embodiments of the present invention, one or more of which are described below. Each example is provided for explanation and not for limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made to the invention without departing from its scope or spirit. For example, features described or illustrated as part of one embodiment may be used in another embodiment to produce further embodiments.

[0028] Therefore, this invention is intended to cover such modifications and variations falling within the scope of the appended claims and their equivalents. Other objects, features, and aspects of the invention are disclosed in or will be apparent from the following detailed description. It will be understood by those skilled in the art that this discussion is merely a description of exemplary embodiments and is not intended to limit the broader aspects of the invention.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0030] The terms “comprising,” “including,” or any other variations thereof are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element preceded by the phrase “comprising one…” does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element. The indefinite articles “a” and “an” preceding an element or component of the invention are not restrictive in terms of the number of elements or components (i.e., the number of times they appear). Therefore, “an” or “an” should be interpreted as including one or at least one, and singular elements or components also include plural forms, unless the quantity clearly refers only to the singular. “A plurality” means at least two, such as two, three, etc., unless otherwise expressly specified.

[0031] The weights of the relevant components mentioned in the embodiments of this invention can refer not only to the specific content of each component, but also to the proportional relationship between the weights of the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this invention is within the scope disclosed in the embodiments of this invention. Specifically, the weights mentioned in the embodiments of this invention can be well-known units of mass in the chemical industry, such as μg, mg, g, and kg.

[0032] Unless otherwise shown or indicated in the operational embodiments, all figures used to represent the amounts, physicochemical properties, etc., of ingredients in the specification and claims are to be understood to be adjusted by the term "about" in all cases. For example, therefore, unless stated to the contrary, the numerical parameters listed in the foregoing specification and appended claims are approximations, and those skilled in the art can appropriately modify these approximations to obtain the desired characteristics by utilizing the teachings disclosed herein. The use of numerical ranges indicated by endpoints includes all numbers within that range and any range within that range; for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, etc.

[0033] One embodiment of this application provides a method for preparing a non-precious metal catalyst, comprising:

[0034] Step S10: The amino-containing cyclic compound, the non-precious metal salt and the organic solvent are mixed and subjected to a complexation reaction at 60℃~80℃ to obtain the non-precious metal chelate.

[0035] It is understood that the temperature for complexation reactions includes, but is not limited to, 60℃, 62℃, 65℃, 68℃, 70℃, 72℃, 75℃, 78℃, and 80℃. In some examples, any two of these point values ​​can be used as endpoints within a range, and the same applies below.

[0036] By controlling the reaction temperature, the amino group in the amino-containing cyclic compound and the non-noble metal ion in the non-noble metal salt undergo a complexation reaction to form a non-noble metal chelate, and the non-noble metal chelate has a cyclic structure.

[0037] In some of these examples, the temperature of the complexation reaction in step S10 is 60°C to 70°C.

[0038] Furthermore, the temperature for the complexation reaction is 60℃~65℃.

[0039] In some of these examples, the complexation reaction in step S10 takes 1 to 4 hours.

[0040] It is understandable that the time for complexation reaction includes, but is not limited to, 1 hour, 2 hours, 3 hours, and 4 hours.

[0041] It can be understood that the amino group in a cyclic compound containing an amino group indicates that the cyclic compound is substituted by at least one amino group. Furthermore, the amino-substituted atom in a cyclic compound can be located on the ring, meaning the amino group is directly connected to a ring atom in the cyclic compound. For example, when an amino group replaces a hydrogen atom on a benzene ring, the amino group is directly connected to a carbon atom on the benzene ring. Alternatively, the amino-substituted atom in a cyclic compound can be not located on the ring, meaning there are other atoms between the amino group and a ring atom in the cyclic compound. For example, when an amino group replaces a methyl hydrogen atom on toluene. Furthermore, cyclic compounds can also contain other substituents, such as carboxyl groups, hydroxyl groups, halogens, etc. Furthermore, cyclic compounds are classified into alicyclic compounds and aromatic compounds, and based on the number of ring atoms, they can be classified into carbocyclic compounds and heterocyclic compounds. They can also be classified based on the number of rings, into monocyclic and polycyclic compounds.

[0042] In some of these examples, in step S10, the cyclic compound includes at least one of an alicyclic compound and an aromatic compound, wherein the cyclic compound is substituted with an amino group.

[0043] It is understandable that alicyclic compounds are a class of carbocyclic compounds with properties similar to aliphatic compounds; aromatic compounds are compounds whose molecules contain benzene rings or fused benzene systems.

[0044] Furthermore, the alicyclic compound includes at least one of cyclohexane and piperazine.

[0045] Furthermore, the aromatic compounds include at least one of benzene, pyridazine, anthraquinone, and pyrimidine.

[0046] In some of these examples, in step S10, the amino group is directly bonded to a ring atom in the cyclic compound.

[0047] In some of these examples, in step S10, the amino-containing cyclic compound includes amino-substituted cyclohexane, amino-substituted pyridazine, amino-substituted anthraquinone, amino-substituted pyrimidine, amino-substituted piperazine, and amino-substituted phthalic acid hydrazide.

[0048] In some of these examples, in step S10, the amino-containing cyclic compound includes at least one of 3-aminophthalic acid hydrazide, 3-amino-6-chloropyridazine, 1-aminocyclohexanecarboxylic acid, 1-aminoanthraquinone, 4-aminocyclohexanecarboxylic acid, 2-aminopyrimidine, and 1-amino-4-methylpiperazine.

[0049] In some of these examples, in step S10, the non-precious metal in the non-precious metal salt includes at least one of copper, iron, and cobalt.

[0050] In some of these examples, in step S10, the non-precious metal in the non-precious metal salt includes copper.

[0051] In some of these examples, in step S10, the non-precious metal salt is a soluble metal salt.

[0052] It is understood that soluble metal salts include, but are not limited to, nitrates, sulfates, halides, acetates, carbonates, acetylacetone compounds, etc.

[0053] In some of these examples, in step S10, the non-precious metal salt includes at least one of non-precious metal nitrates, sulfates, halides, and acetates.

[0054] Furthermore, the non-precious metal salt includes at least one of copper nitrate, copper sulfate, copper chloride, copper acetate, ferric nitrate, ferric sulfate, ferric chloride, and ferric acetate.

[0055] In some of these examples, in step S10, the non-precious metal salt includes at least one of copper nitrate, copper sulfate, copper chloride, and copper acetate.

[0056] In some of these examples, in step S10, the molar ratio of the non-precious metal salt to the amino-containing cyclic compound is 1:(3-10).

[0057] It is understood that the molar ratio of non-precious metal salts to amino-containing cyclic compounds includes, but is not limited to, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, and 1:10.

[0058] Optionally, the molar ratio of the non-precious metal salt to the amino-containing cyclic compound is 1:(3-7).

[0059] In some of these examples, in step S10, the organic solvent includes at least one of ethanol, cyclohexane, and acetone.

[0060] Alternatively, the organic solvent may include ethanol.

[0061] In some of these examples, in step S10, the total mass of the amino-containing cyclic compound and the non-precious metal salt is in a volume ratio of (20–40) g / L to the organic solvent.

[0062] It is understood that the total mass ratio of amino-containing cyclic compounds and non-precious metal salts to the volume ratio of organic solvents includes, but is not limited to, 20 g / L, 22 g / L, 25 g / L, 28 g / L, 30 g / L, 32 g / L, 35 g / L, 38 g / L, and 40 g / L.

[0063] In some examples, step S10, after the complexation reaction is completed, also includes a step of removing the solvent from the reaction solution after the complexation reaction.

[0064] It is understandable that "removing the solvent" means removing the solvent from the reaction solution. After removing the solvent, a black powder is obtained, which is a non-precious metal chelate.

[0065] In some of these examples, step S10, the solvent removal step, includes drying the reaction solution after the complexation reaction at 30°C to 50°C for 8 to 16 hours.

[0066] It is understood that in the solvent removal step, the drying temperature includes, but is not limited to, 30℃, 35℃, 40℃, 42℃, 46℃, and 50℃, and the time includes, but is not limited to, 8h, 10h, 12h, 15h, and 16h.

[0067] Step S20: Calcine the non-precious metal chelate to obtain a non-precious metal catalyst.

[0068] The above-mentioned method for preparing non-precious metal catalysts involves mixing an amino-containing cyclic compound, a non-precious metal salt, and an organic solvent, followed by a complexation reaction at a specific temperature. The amino groups on the cyclic compound and the non-precious metal ions in the non-precious metal salt undergo a complexation reaction to generate a non-precious metal chelate. This chelate has a cyclic structure, allowing for further carbonization and reduction reactions during calcination. Using the amino-containing cyclic compound as the carbon and nitrogen source, the carbon elements form a uniform and stable porous structure. Nitrogen atoms linked to the carbon framework and non-precious metal atoms complexed with nitrogen atoms are uniformly distributed within the carbon's porous structure. The resulting non-precious metal-NC catalyst exhibits strong interactions between the non-precious metal and the carbon framework, effectively preventing acid dissolution and thus significantly improving the catalyst's stability. Furthermore, since no additional carbon or nitrogen source is required, additional degradation due to catalyst size inhomogeneity is avoided. Moreover, the non-precious metal in the non-precious metal-NC catalyst exists in single-atom form, fully exposing the catalytic sites and resulting in a high mass activity and current density for the obtained non-precious metal catalyst.

[0069] In some of these examples, in step S20, the calcination temperature is 600℃~1000℃ and the time is 1h~4h.

[0070] It is understood that the calcination temperature includes, but is not limited to, 600℃, 650℃, 700℃, 750℃, 800℃, 820℃, 850℃, 900℃, 950℃, and 1000℃, and the time includes, but is not limited to, 1h, 2h, 3h, 3.5h, and 4h.

[0071] Optionally, the calcination temperature is 600℃~900℃.

[0072] Furthermore, the calcination temperature is 800℃~900℃.

[0073] In some of these examples, in step S20, the atmosphere for the calcination treatment includes at least one of nitrogen and an inert gas.

[0074] In some of these examples, in step S20, the atmosphere for the calcination treatment includes at least one of nitrogen, argon, and helium.

[0075] Optionally, the calcination atmosphere is nitrogen.

[0076] In some of these examples, in step S20, calcination is performed in a quartz tube furnace.

[0077] In some examples, step S20, after the calcination treatment step is completed, also includes a step of removing impurities from the calcined product using an acid solution.

[0078] Using acid to remove impurities from the calcined product can remove non-precious metal oxides and incompletely pyrolyzed non-precious metal chelates produced by the oxidation of uncomplexed metal ions during calcination.

[0079] In some of these examples, the acid solution used in the impurity removal step includes at least one of sulfuric acid and hydrochloric acid.

[0080] In some of these examples, the concentration of the acid solution in the impurity removal step is 0.05 mol / L to 0.15 mol / L.

[0081] It is understood that the concentration of the acid solution includes, but is not limited to, 0.05 mol / L, 0.08 mol / L, 0.1 mol / L, 0.12 mol / L, 0.14 mol / L, and 0.15 mol / L.

[0082] In some of these examples, the impurity removal step includes immersing the calcined product in an acid solution.

[0083] In some of these examples, the acid treatment time in the impurity removal step is 16h to 24h.

[0084] It is understood that the acid treatment time includes, but is not limited to, 16h, 18h, 20h, 22h, and 24h.

[0085] The above-mentioned methods for preparing non-precious metal catalysts are simple, low-cost, and have good development prospects.

[0086] One embodiment of this application provides a non-precious metal catalyst, which is prepared using the above-described preparation method.

[0087] The non-precious metal catalyst provided in this application has the general formula Me-NC, where Me is a non-precious metal element.

[0088] One embodiment of this application provides the application of the above-described non-precious metal catalyst in the preparation of fuel cells.

[0089] Another embodiment of this application provides a fuel cell including the above-described non-precious metal catalyst.

[0090] The aforementioned non-precious metal catalysts can endow fuel cells with a large electrochemical active surface area (ECSA), high mass activity and current density, as well as good stability.

[0091] It is understood that a fuel cell includes a membrane electrode assembly (MEA) and bipolar plates disposed on both sides of the MEA. The MEA includes a proton exchange membrane, a catalyst layer, and a gas diffusion layer. The catalyst layer is located on both sides of the proton exchange membrane, and the gas diffusion layer is located on the side of the catalyst layer away from the proton exchange membrane. The catalyst layer includes the aforementioned non-precious metal catalyst.

[0092] One embodiment of this application provides an electrical device, including the aforementioned fuel cell.

[0093] It is understood that electrical devices include, but are not limited to, automobiles, airplanes, medical equipment, and household appliances.

[0094] One embodiment of this application provides a vehicle including the aforementioned fuel cell.

[0095] The present application will be described in further detail below with reference to specific embodiments, but the embodiments of the present application are not limited thereto.

[0096] Example 1

[0097] 1) Add 2.0 g of copper chloride and 8.0 g of 3-amino-6-chloropyridazine to 200 mL of ethanol, disperse evenly by ultrasonication, and react at 60 °C for 5 hours. Then place the reaction solution in a drying oven and dry at 40 °C for 10 hours to remove the solvent, and obtain a black powder, which is a non-precious metal chelate; wherein, the molar ratio of copper chloride to 3-amino-6-chloropyridazine is 1:4.2.

[0098] 2) The black powder was transferred to a quartz tube furnace and pyrolyzed at 800°C for 2 hours under nitrogen protection. After cooling to room temperature, the sample was soaked in 0.1 mol / L dilute sulfuric acid for 16 hours, then filtered and the filter residue was washed three times with deionized water. The sample was then dried at 60°C for 12 hours to obtain a non-precious metal catalyst.

[0099] Example 2

[0100] 1) Add 2.4g of copper sulfate and 8.4g of 4-aminocyclohexanecarboxylic acid to 200mL of ethanol, disperse evenly by ultrasonication, and react at 70℃ for 4 hours. Then place the reaction solution in a drying oven and dry at 40℃ for 12 hours to remove the solvent, and obtain a black powder, which is a non-precious metal chelate.

[0101] 2) The black powder was transferred to a quartz tube furnace and pyrolyzed at 700°C for 2 hours under nitrogen protection. After cooling the sample to room temperature, it was soaked in 0.1 mol / L dilute sulfuric acid for 24 hours, then filtered and the filter residue was washed three times with deionized water. The sample was then dried at 50°C for 16 hours to obtain a non-precious metal catalyst.

[0102] Example 3

[0103] 1) Add 3.0g of copper nitrate and 12.0g of 1-aminoanthraquinone to 300mL of ethanol, disperse evenly by ultrasonication, and react at 80℃ for 5 hours. Then place the reaction solution in a drying oven and dry at 50℃ for 14 hours to remove the solvent, and obtain a black powder, which is a non-precious metal chelate.

[0104] 2) The black powder was transferred to a quartz tube furnace and pyrolyzed at 900°C for 1 hour under nitrogen protection. The sample was then cooled to room temperature, soaked in 0.1 mol / L dilute sulfuric acid for 24 hours, filtered, and the filter residue was washed three times with deionized water. The sample was then dried at 50°C for 14 hours to obtain a non-precious metal catalyst.

[0105] Example 4

[0106] 1) Add 2.0g of copper acetate and 8.4g of 1-aminocyclohexanecarboxylic acid to 250mL of ethanol, disperse evenly by ultrasonication, and react at 80℃ for 5 hours. Then place the reaction solution in a drying oven and dry at 40℃ for 12 hours to remove the solvent, and obtain a black powder, which is a non-precious metal chelate.

[0107] 2) The black powder was transferred to a quartz tube furnace and pyrolyzed at 600°C for 4 hours under nitrogen protection. After cooling the sample to room temperature, it was soaked in 0.1 mol / L dilute sulfuric acid for 24 hours, then filtered and the filter residue was washed three times with deionized water. The sample was then dried at 50°C for 16 hours to obtain a non-precious metal catalyst.

[0108] Example 5

[0109] The process is basically the same as in Example 1, except that in step 2) of Example 5, the black powder is transferred to a quartz tube furnace and the sample is pyrolyzed at 700°C for 4 hours under nitrogen protection.

[0110] Example 6

[0111] It is basically the same as Example 1, except that in step 1) of Example 6, the temperature of the complexation reaction is 70°C.

[0112] Example 7

[0113] The example is basically the same as Example 1, except that in step 1) of Example 7, the molar ratio of the non-precious metal salt to the amino-containing cyclic compound is 1:7.

[0114] Example 8

[0115] The example is basically the same as Example 1, except that in step 1) of Example 8, the molar ratio of the non-precious metal salt to the amino-containing cyclic compound is 1:10.

[0116] Comparative Example 1

[0117] The comparison is basically the same as that in Example 1, except that in Comparative Example 1, 3-amino-6-chloropyridazine in step 1) of Example 1 is replaced with an equimolar amount of thiourea.

[0118] Comparative Example 2

[0119] The comparison example is basically the same as Example 1, except that in Comparative Example 1, 3-amino-6-chloropyridazine in step 1) of Example 1 is replaced with an equimolar amount of 2,2-bipyridine.

[0120] Comparative Example 3

[0121] The comparison example is basically the same as Example 1, except that in Comparative Example 1, 3-amino-6-chloropyridazine in step 1) of Example 1 is replaced with an equimolar amount of 4-(methylamino)benzoic acid.

[0122] Comparative Example 4

[0123] The results are basically the same as in Example 1, except that in step 1) of Comparative Example 4, the temperature of the complexation reaction is 30°C.

[0124] Comparative Example 5

[0125] 1) Add 2.0g of copper chloride and 8.0g of 3-amino-6-chloropyridazine to 200mL of ethanol, disperse evenly by ultrasonication, and react at 60℃ for 5h. Then add 60g of activated carbon and stir for 24h. Place the reaction solution in a drying oven and dry at 40℃ for 10h to remove the solvent, and obtain a black powder, which is a non-precious metal chelate. The molar ratio of copper chloride to 3-amino-6-chloropyridazine is 1:4.2.

[0126] 2) The black powder was transferred to a quartz tube furnace and pyrolyzed at 800°C for 2 hours under nitrogen protection. After cooling to room temperature, the sample was soaked in 0.1 mol / L dilute sulfuric acid for 16 hours, then filtered and the filter residue was washed three times with deionized water. The sample was then dried at 60°C for 12 hours to obtain a non-precious metal catalyst.

[0127] The main parameters of each embodiment and comparative example are shown in Table 1.

[0128] Table 1

[0129]

[0130]

[0131] Here, "m1:m2" refers to the molar ratio of a non-precious metal salt to an amino-containing cyclic compound.

[0132] The catalyst slurry was prepared and integrated into a membrane electrode assemblies according to the following steps for performance testing. The membrane electrodes were identical in all aspects except for the type of catalyst used:

[0133] The non-precious metal catalysts obtained in each example and comparative example, as well as the commercially available Pt / C catalyst (purchased from TKK), were mixed with deionized water, and then isopropanol and Nafion D520 solution were added, with an I / C ratio of 0.8. The mixture was ultrasonically sonicated until the catalyst slurry was homogeneous. A CCM was prepared by ultrasonic spraying, and a MEA was prepared by combining it with a gas diffusion layer and a proton exchange membrane. These were then assembled into single cells to test the electrochemical active area (ECSA), mass activity, polarization curves of the single cells, and performance degradation rate after 1000 cycles of accelerated stress testing (AST). The single-cell test conditions were: effective area of ​​5 × 5 cm². 2 The temperature was 80℃, and the test results are shown in Table 2.

[0134] Table 2

[0135]

[0136]

[0137] As shown in Table 2, compared with the comparative examples, the electrochemical active areas of the non-noble metal catalysts prepared in each embodiment of this application are all higher than 90 nm. 2 / g Pt The mass activity of all samples exceeded 0.175 A / g, significantly higher than that of commercial Pt / C catalysts. After fabricating membrane electrodes using the non-noble metal catalysts prepared in each example and comparative example, along with commercial Pt / C, and assembling them into single cells for testing, it was shown that the current density of each example at 0.65 V exceeded 800 mA / cm². 2 The current density at 0.6V is higher than 940 mA / cm². 2 The performance of each embodiment at both 0.6V and 0.65V was also superior to that of the comparative example and commercial Pt / C. Furthermore, compared to the comparative example and commercial Pt / C, the stability of the non-precious metal catalysts prepared in each embodiment was significantly improved. After 1000 cycles of accelerated durability testing, the performance degradation was less than 4.6%, while the degradation of each comparative example was greater than 6%. Comparative example 5, with the addition of a carbon source, even achieved a degradation rate of 9.15%. This demonstrates that the non-precious metal catalyst prepared in this study using the complexation and pyrolysis of metal ions and amino cyclic compounds exhibits high mass activity and current density, as well as good stability.

[0138] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0139] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A method for preparing a non-precious metal catalyst, characterized in that, Includes the following steps: An amino-containing cyclic compound, a non-precious metal salt, and an organic solvent are mixed and subjected to a complexation reaction at 60°C to 80°C to obtain a non-precious metal chelate. The amino-containing cyclic compound includes at least one selected from 3-aminophthalohydrazide, 3-amino-6-chloropyridazine, 1-aminocyclohexanecarboxylic acid, 1-aminoanthraquinone, 4-aminocyclohexanecarboxylic acid, 2-aminopyrimidine, and 1-amino-4-methylpiperazine. The molar ratio of the non-precious metal salt to the amino-containing cyclic compound is 1:3 to 1:

10. The organic solvent includes at least one selected from ethanol, cyclohexane, and acetone. The non-precious metal chelate was calcined to obtain the non-precious metal catalyst.

2. The preparation method according to claim 1, characterized in that, The non-precious metals in the non-precious metal salt include at least one of copper, iron, and cobalt.

3. The preparation method according to claim 1, characterized in that, The non-precious metal salts include at least one of non-precious metal nitrates, sulfates, chlorides, and acetates.

4. The preparation method according to any one of claims 1 to 3, characterized in that, The calcination treatment is carried out at a temperature of 600℃ to 1000℃ for a time of 1 h to 4 h.

5. The preparation method according to any one of claims 1 to 3, characterized in that, The atmosphere for the calcination treatment includes at least one of nitrogen, argon, and helium.

6. The preparation method according to any one of claims 1 to 3, characterized in that, After the calcination treatment is completed, the process also includes a step of removing impurities from the calcined product using an acid solution.

7. A non-precious metal catalyst, characterized in that, It is prepared by the preparation method described in any one of claims 1 to 6.

8. A fuel cell, characterized in that, Including the non-precious metal catalyst as described in claim 7.

9. A car, characterized in that, Including the fuel cell as described in claim 8.

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