WO2023070877A1 - Preparation method for fuel cell catalyst, fuel cell catalyst and fuel cell - Google Patents

Preparation method for fuel cell catalyst, fuel cell catalyst and fuel cell Download PDF

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WO2023070877A1
WO2023070877A1 PCT/CN2021/138101 CN2021138101W WO2023070877A1 WO 2023070877 A1 WO2023070877 A1 WO 2023070877A1 CN 2021138101 W CN2021138101 W CN 2021138101W WO 2023070877 A1 WO2023070877 A1 WO 2023070877A1
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fuel cell
cell catalyst
sodium
mixture
potassium
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PCT/CN2021/138101
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French (fr)
Chinese (zh)
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唐永炳
苟佳利
郑勇平
季必发
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中国科学院深圳先进技术研究院
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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
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
    • 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

Definitions

  • the present application relates to the field of fuel cells, in particular to a preparation method of a fuel cell catalyst, a fuel cell catalyst and a fuel cell.
  • High-entropy rare-earth single-atom catalysts refer to catalysts with excellent catalytic performance formed by uniformly dispersing rare-earth metals on the carrier in the form of single atoms. At present, there are very few researches and applications on high-entropy rare-earth single-atom catalysts.
  • the inventions similar to high-entropy rare-earth single-atom catalysts include noble metal single-atom catalysts (such as platinum single-atom catalysts, gold single-atom catalysts, palladium single-atom catalysts, etc.) and Transition metal single-atom catalysts (such as iron single-atom catalysts, cobalt single-atom catalysts, nickel single-atom catalysts, etc.).
  • noble metal catalysts are high cost and deactivation by poisoning, while transition metal single-atom catalysts are difficult to exert excellent performance in fuel cells. Therefore, there is an urgent need to find an efficient electrocatalyst with low cost, stable performance and environmental friendliness.
  • the application provides a kind of preparation method of fuel cell catalyst, comprises the following steps:
  • the sintered product is vacuum-dried to obtain the fuel cell catalyst.
  • the step of dissolving the template agent, the initiator and the nitrogen-containing polymer precursor in the aqueous solution to obtain the first mixture specifically:
  • Dissolving the template agent in an aqueous solution adding an initiator after ultrasonic dissolution, adding a nitrogen-containing polymer precursor after stirring and dissolving, and then continuing to stir and age the obtained solution for at least 24 hours to obtain a first mixture; when the template agent or initiator
  • the aqueous solution is added with an acid solution, and the acid solution includes hydrochloric acid or sulfuric acid or nitric acid.
  • the template agent in the step of dissolving the template agent, the initiator and the nitrogen-containing polymer precursor in the aqueous solution to obtain the first mixture, includes cetyltrimethylammonium bromide, Sodium lauryl sulfate, sodium dodecylbenzene sulfonate, octadecyl sulfobetaine, polyacrylamide, polyethylene glycol, polyvinylpyrrolidone, polydextrose, polybenzyl ester, various organic One or more of amines and quaternary ammonium compounds.
  • the initiator is at least one of a peroxide initiator or an azo initiator
  • the peroxide initiator includes an organic peroxide or an inorganic peroxide
  • the Organic peroxides include organic peroxides with a general structural formula of R-O-O-H or R-O-O-R, wherein R is an alkyl group, an acyl group, or a carbonate group
  • the inorganic peroxides include ammonium persulfate, potassium persulfate or sodium persulfate
  • the azo initiator includes azobisisobutyronitrile or azobisisoheptanonitrile or dimethyl azobisisobutyrate.
  • the nitrogen-containing polymer precursor can be one or more of pyrrole, pyridine, pyrazole, imidazole, thiazole, pyrimidine, quinoline, purine, aniline and derivatives of the above compounds .
  • the molar concentration ratio of the template agent, the initiator, and the nitrogen-containing polymer precursor is 1:1 ⁇ 6:4 ⁇ 50.
  • a second mixture in the step of dispersing the first mixture in a solution containing a rare earth metal precursor and an alkali metal salt, stirring and adsorbing to obtain a second mixture, specifically:
  • the first mixture is alternately sucked and washed with water and ethanol to remove the template agent and the low-polymerization degree precursor, then dispersed in a solution containing the rare earth metal precursor and the alkali metal salt, and stirred and adsorbed to obtain the second mixture.
  • the alkali metal salt can be any one or more soluble alkali metal salts, and the soluble alkali metal salt is lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, Lithium sulfate, lithium carbonate, lithium acetate, lithium perchlorate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium iron phosphate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium nitrate, Sodium sulfate, sodium carbonate, sodium acetate, sodium perchlorate, sodium hexafluoroarsenate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium ferric phosphate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium nitrate , Potassium sulfate,
  • the rare earth metal precursor comprises at least Soluble salts of five metals
  • the molar concentration ratio of the rare earth metal precursor and the alkali metal salt in the solution is 1:2-20, the sum of the molar concentrations of the rare earth metal precursor is 1-1000 mmol/L, and each rare earth metal precursor
  • the body content is any ratio other than zero.
  • the second mixture is first calcined in N2 for 0.2-5h at a temperature of 600°C-1000°C, and then calcined in NH3 for 0.2-5h to obtain a sintered product ,
  • a sintered product Specifically:
  • the second mixture was suction-filtered and vacuum-dried to obtain a solid sample, which was then heated to 600-1000°C under N2 flow and calcined for 0.2-5h; after cooling down to room temperature, the obtained The solid powder is heated to 600-1000°C under NH 3 flow, and calcined for 0.2-5h, and then cooled to room temperature to obtain a sintered product.
  • the step of vacuum drying the sintered product to obtain the fuel cell catalyst specifically includes:
  • the present application also provides a fuel cell catalyst, which is prepared by the preparation method of the fuel cell catalyst.
  • the present application also provides a fuel cell, which is added with the fuel cell catalyst.
  • the template agent, the initiator and the nitrogen-containing polymer precursor are dissolved in the aqueous solution to obtain the first mixture, and the first mixture is dispersed in the mixture containing the rare earth metal precursor and the alkali metal salt.
  • the second mixture is obtained by stirring and adsorbing in the solution, and the second mixture is calcined at 600°C-1000°C for 0.2-5h to obtain a sintered product, and the sintered product is vacuum-dried to obtain the fuel cell catalyst, and the obtained fuel cell Catalyst, the above method, the high-entropy rare earth single-atom catalyst prepared by organic polymerization and high-temperature calcination, the obtained catalyst has the advantages of small diameter, small pore size, high porosity, good fiber uniformity, etc., and has good ORR catalytic performance, It can be widely used in fuel cells and metal-air batteries.
  • the above method has the advantages of simple process, low cost of raw materials, safety, reliability and environmental friendliness.
  • Fig. 1 is the flow chart of the steps of the preparation method of the fuel cell catalyst provided by the present application
  • Fig. 2 is the HE (La/Ce/Pr/Nd/Pm) catalytic material scanning electron microscope picture prepared in the embodiment 1 of the present application;
  • Fig. 3 is the comparison chart of ORR performance of the catalytic material prepared in Examples 1-5 of the present application when the electrode load is 0.22 mg/cm 2 (test conditions: three-electrode system, the working electrode is a catalyst, and the counter electrode is a carbon rod, see The specific electrode is a saturated calomel electrode, and the electrolyte is 0.1mol/L KOH solution);
  • Fig. 4 is a comparison chart of ORR performance of high-entropy rare earth (La/Ce/Pr/Nd/Pm) electrocatalysts in Example 1 of the present application under different addition ratios of rare earth metal precursors (test conditions: three-electrode system, working electrode is catalyst, the counter electrode is a carbon rod, the reference electrode is a saturated calomel electrode, and the electrolyte is 0.1mol/L KOH solution).
  • first and second are used for descriptive purposes only, and cannot be interpreted as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features. Thus, a feature defined as “first” and “second” may explicitly or implicitly include one or more of these features.
  • “plurality” means two or more, unless otherwise specifically defined.
  • Fig. 1 the flow chart of the steps for the preparation method of the fuel cell catalyst provided by the embodiment of the present application, including the following steps:
  • Step S110 dissolving the templating agent, the initiator and the nitrogen-containing polymer precursor in the aqueous solution to obtain a first mixture.
  • the template agent is dissolved in the aqueous solution, the initiator is added after ultrasonic dissolution, the nitrogen-containing polymer precursor is added after stirring and dissolving, and the obtained solution is continuously stirred and aged for at least 24 hours to obtain the first mixture; when When the solubility of the template agent or initiator is limited in the aqueous solution, an acid solution is added to the aqueous solution, and the acid solution includes hydrochloric acid, sulfuric acid or nitric acid.
  • the template can be: cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), octadecyl Hydroxybetaine (DHSB), polyacrylamide (PAM), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polydextrose, polybehenate, various organic amines, quaternary ammonium compounds one or more of.
  • CTAB cetyltrimethylammonium bromide
  • SDS sodium dodecyl sulfate
  • SDBS sodium dodecylbenzenesulfonate
  • DHSB octadecyl Hydroxybetaine
  • PAM polyacrylamide
  • PEG polyethylene glycol
  • PVP polyvinylpyrrolidone
  • polydextrose polybehenate
  • various organic amines quaternary ammonium compounds one or more of.
  • the initiator is at least one of a peroxide initiator or an azo initiator
  • the peroxide initiator includes an organic peroxide or an inorganic peroxide
  • the organic peroxide Including organic peroxides with a general structural formula of R-O-O-H or R-O-O-R, wherein R is an alkyl group, an acyl group, or a carbonate group
  • the inorganic peroxides include ammonium persulfate or potassium persulfate or sodium persulfate
  • the azo Types of initiators include azobisisobutyronitrile or azobisisoheptanonitrile or dimethyl azobisisobutyrate.
  • the organic peroxide may include materials such as benzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl benzoate, tert-butyl peroxy-tert-valerate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and the like.
  • materials such as benzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl benzoate, tert-butyl peroxy-tert-valerate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and the like
  • the nitrogen-containing polymer precursor may be one or more of pyrrole, pyridine, pyrazole, imidazole, thiazole, pyrimidine, quinoline, purine, aniline and derivatives of the above compounds.
  • the molar concentration ratio of the template agent, the initiator, and the nitrogen-containing polymer precursor is 1:1 ⁇ 6:4 ⁇ 50.
  • the coordination environment of the high-entropy rare earth single atom can be adjusted by changing the type and amount of the polymer precursor, the type and content of the rare earth element, and the electronic structure of the active center can be improved, thereby realizing the adjustment of the performance of the rare earth single atom catalyst.
  • Step S120 dispersing the first mixture in a solution containing rare earth metal precursors and alkali metal salts, stirring and adsorbing to obtain a second mixture.
  • the first mixture is alternately suction-filtered and washed with water and ethanol to remove the template agent and the low-polymerization degree precursor, and then dispersed in a solution containing a rare earth metal precursor and an alkali metal salt, Stir and adsorb to obtain the second mixture.
  • the alkali metal salt can be any one or more soluble alkali metal salts, and the soluble alkali metal salt is lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, lithium sulfate, carbonic acid Lithium, lithium acetate, lithium perchlorate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium iron phosphate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium nitrate, sodium sulfate, carbonic acid Sodium, sodium acetate, sodium perchlorate, sodium hexafluoroarsenate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium ferric phosphate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium nitrate, potassium sulfate, One or more of potassium potassium flu
  • the rare earth metal precursor may be: containing scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium At least Soluble salts of 5 metals.
  • the rare earth metal precursor provided by this application includes soluble salts of at least five metals mentioned above, thereby breaking the symmetry of the carbon ring, destroying the large ⁇ bond, enhancing the regulation activity of the carbon substrate, and synergistically increasing the catalytic performance of the multi-element.
  • the molar concentration ratio of the rare earth metal precursor and the alkali metal salt in the solution is 1:2 to 20, the sum of the molar concentrations of the rare earth metal precursor is 1 to 1000 mmol/L, and the content of each rare earth metal precursor is not Any ratio of 0.
  • Step S130 calcining the second mixture at 600°C-1000°C for 0.2-5h to obtain a sintered product.
  • the second mixture is suction-filtered and vacuum-dried to obtain a solid sample, and the solid sample is then heated to 600-1000° C. under N 2 airflow, and calcined for 0.2-5 h; After reaching room temperature, the obtained solid powder is heated to 600-1000° C. under NH 3 flow, and calcined for 0.2-5 h, and then lowered to room temperature to obtain a sintered product.
  • Step S140 vacuum drying the sintered product to obtain the fuel cell catalyst.
  • the sintered product is acid-washed at 40-80°C for 2-8 hours, and after the washing is completed, a solid sample is obtained by suction filtration, and the solid sample is vacuum-dried, and then the obtained product is acid-washed. Washing, vacuum drying again to obtain the fuel cell catalyst.
  • the high-entropy rare earth single-atom catalyst prepared by organic polymerization and high-temperature calcination has the advantages of small diameter, small pore size, high porosity, good fiber uniformity, etc., and has good ORR catalytic performance, can be widely used in fuel cells, metal-air batteries.
  • the prepared fuel cell catalyst modifies the material with a variety of rare earth elements in the form of single atoms to improve the electrocatalytic activity of the material, so that the electrocatalytic activity of the substrate material is greatly improved.
  • a variety of rare earth elements were introduced on the polymer fiber, and after high-temperature pyrolysis and acid treatment, a nano-electrocatalyst with high-entropy rare-earth single-atom modification and rich surface defects was obtained, which showed excellent performance in electrocatalytic ORR performance.
  • a preparation method of a high-entropy rare earth metal single-atom catalyst comprises the following steps:
  • CTAB was used as a template
  • APS was used as an initiator
  • LiNO 3 was used as an alkali metal salt
  • pyrrole was used as a nitrogen-containing polymer precursor
  • EuCl 3 , GdCl 3 , TbCl 3 , DyCl 3 and HoCl 3 at a concentration of 4 mmol/L were used as
  • the KOH concentration in the electrochemical test is 0.1mol/L, and the electrochemical test is performed with reference to Example 1.
  • CTAB was used as template, potassium persulfate was used as initiator, NaNO 3 was used as alkali metal salt, aniline was used as nitrogen-containing polymer precursor, LaNO 3 , CeNO 3 , PrNO 3 , NdNO 3 and PmNO 3 is used as a rare earth metal precursor, and the KOH concentration in the electrochemical test is 0.1 mol/L, and the electrochemical test is performed with reference to Example 1.
  • CTAB was used as a template
  • APS was used as an initiator
  • NaCl was used as an alkali metal salt
  • aniline was used as a nitrogen-containing polymer precursor
  • ScCl 3 , PrCl 3 , EuCl 3 , HoCl 3 and YbCl 3 with a concentration of 4 mmol/L were used as For the rare earth metal precursor, the KOH concentration in the electrochemical test was 1mol/L, and the electrochemical test was performed with reference to Example 1.
  • the present invention assembles the high-entropy rare earth metal single-atom catalyst obtained in the above embodiments into a three-electrode system, with the catalyst as the working electrode, the carbon rod as the counter electrode, and the saturated calomel electrode
  • electrolytic solution is the KOH solution of 0.1mol/L
  • catalyst load is 0.22mg/cm
  • voltage range is 1.0V-0.4V vs.RHE (subsequent embodiments of the present invention all adopt the same The test method to obtain electrochemical performance results).
  • the test results and other parameters are shown in Table 1.
  • Example 1 of the present invention CTAB is used as template agent, APS is used as initiator, and chloride salts of La, Ce, Pr, Nd, and Pm are used as rare earth metal precursors, showing a higher initial potential and a higher High half-wave potential, good ORR performance.
  • embodiment 2-76 The difference between embodiment 2-76 and embodiment 1 is that the type or content of the rare earth metal precursor is different, specifically as shown in table 2, the high entropy rare earth metal single-atom catalyst obtained in embodiment 5-76 is tested for ORR, and its The test results are shown in Table 2:
  • Example 77-103 The only difference between Examples 77-103 and Example 1 is the type of templating agent, which is specifically shown in Table 3.
  • the high-entropy rare earth metal single-atom catalyst obtained in Example 77-103 was tested for ORR, and the test results are shown in the table 3 shows:
  • Example 104-122 The difference between Examples 104-122 and Example 1 is that the types of initiators are different, as shown in Table 4.
  • the high-entropy rare earth metal single-atom catalysts obtained in Examples 104-122 were tested for ORR, and the test results are shown in the table 4 shows:
  • Example 123-152 The only difference between Examples 123-152 and Example 1 is that the type of nitrogen-containing polymer precursor is different, specifically as shown in Table 5, the ORR test was performed on the high-entropy rare earth metal single-atom catalyst obtained in Example 123-, and the test The results are shown in Table 5:
  • Example 153-The only difference from Example 1 is that the type of alkali metal salt is different, as shown in Table 6.
  • the high-entropy rare earth metal single-atom catalyst obtained in Example 153- was subjected to an ORR test, and the test results are shown in Table 6 Shown:
  • the catalyst has better ORR performance when the alkali metal salt is lithium chloride, showing higher onset potential and half-wave potential.
  • the application of the high-entropy rare earth single-atom catalyst involved in the embodiment of the present invention is not limited to the three-electrode system, and is also applied in fuel cells.
  • the important component of the embodiment of the present invention is to synthesize a rare earth single-atom electrocatalyst with high entropy distribution from a variety of rare earth elements, which maintains good ORR performance and has good stability. This is also the first time that rare earth metals have prepared electrocatalysts in the form of high-entropy single atoms, which makes electrocatalysts have a lower cost and opens up another important preparation method and application of single-atom catalysts.

Abstract

In the preparation method for a fuel cell catalyst provided in the present application, a template agent, an initiator and a nitrogen-containing polymer precursor are dissolved in an aqueous solution to obtain a first mixture; the first mixture is dispersed in a solution containing a rare earth metal precursor and an alkali metal salt, and a second mixture is obtained by stirring and adsorbing; the second mixture is calcined at 600℃-1000℃ for 0.2-5 h to obtain a sintered product; vacuum drying is carried out on the sintered product to obtain a fuel cell catalyst, and a fuel cell catalyst is prepared obtained. According to the described method, a high-entropy rare earth monatomic catalyst is prepared and obtained by using organic polymerization and high-temperature calcination. The obtained catalyst has the advantages of a small diameter, small pore size, high porosity, good fiber uniformity, and the like; moreover, the catalyst has good ORR catalytic performance, and may be widely used in fuel cells and metal air batteries. The described method has the advantages of a simple process, low raw material costs, and being safe, reliable, environmentally friendly and the like.

Description

一种燃料电池催化剂的制备方法、燃料电池催化剂及燃料电池Preparation method of fuel cell catalyst, fuel cell catalyst and fuel cell 技术领域technical field
本申请涉及燃料电池领域，特别涉及一种燃料电池催化剂的制备方法、燃料电池催化剂及燃料电池。The present application relates to the field of fuel cells, in particular to a preparation method of a fuel cell catalyst, a fuel cell catalyst and a fuel cell.
背景技术Background technique
高熵稀土单原子催化剂是指稀土金属以单原子的形式均匀分散在载体上形成的具有优异催化性能的催化剂。目前对于高熵稀土单原子催化剂的研究和应用极少，与高熵稀土单原子催化剂相似的发明有贵金属单原子催化剂(如：铂单原子催化剂、金单原子催化剂、钯单原子催化剂等)和过渡金属单原子催化剂(如：铁单原子催化剂、钴单原子催化剂、镍单原子催化剂等)。贵金属催化剂目前主要面临的问题是成本较高且以中毒失活，而过渡金属单原子催化剂又很难在燃料电池中发挥出优异的性能。因此，寻找一种成本低廉、性能稳定且环境友好的高效电催化剂有迫切的应用需求。High-entropy rare-earth single-atom catalysts refer to catalysts with excellent catalytic performance formed by uniformly dispersing rare-earth metals on the carrier in the form of single atoms. At present, there are very few researches and applications on high-entropy rare-earth single-atom catalysts. The inventions similar to high-entropy rare-earth single-atom catalysts include noble metal single-atom catalysts (such as platinum single-atom catalysts, gold single-atom catalysts, palladium single-atom catalysts, etc.) and Transition metal single-atom catalysts (such as iron single-atom catalysts, cobalt single-atom catalysts, nickel single-atom catalysts, etc.). The main problems faced by noble metal catalysts are high cost and deactivation by poisoning, while transition metal single-atom catalysts are difficult to exert excellent performance in fuel cells. Therefore, there is an urgent need to find an efficient electrocatalyst with low cost, stable performance and environmental friendliness.
发明内容Contents of the invention
鉴于此，有必要针对现有技术中存在的ORR催化性能不佳的缺陷，提供一种具有良好的ORR催化性能的燃料电池催化剂的制备方法。In view of this, it is necessary to provide a method for preparing a fuel cell catalyst with good ORR catalytic performance for the defect of poor ORR catalytic performance in the prior art.
为解决上述问题，本申请采用下述技术方案：In order to solve the above problems, the application adopts the following technical solutions:
一方面，本申请提供了一种燃料电池催化剂的制备方法，包括下述步骤：On the one hand, the application provides a kind of preparation method of fuel cell catalyst, comprises the following steps:
将模板剂、引发剂及含氮聚合物前驱体溶解于水溶液中得到第一混合物；Dissolving the templating agent, the initiator and the nitrogen-containing polymer precursor in the aqueous solution to obtain the first mixture;
将所述第一混合物分散于含有稀土金属前驱体和碱金属盐的溶液中搅拌吸 附得到第二混合物；Dispersing the first mixture in a solution containing a rare earth metal precursor and an alkali metal salt, stirring and adsorbing to obtain a second mixture;
将所述第二混合物于600℃-1000℃煅烧0.2-5h，得到烧结产物；及calcining the second mixture at 600°C-1000°C for 0.2-5h to obtain a sintered product; and
将所述烧结产物真空干燥得到所述燃料电池催化剂。The sintered product is vacuum-dried to obtain the fuel cell catalyst.
在其中一些实施例中，在将模板剂、引发剂及含氮聚合物前驱体溶解于水溶液中得到第一混合物的步骤中，具体为：In some of these embodiments, in the step of dissolving the template agent, the initiator and the nitrogen-containing polymer precursor in the aqueous solution to obtain the first mixture, specifically:
将模板剂溶解于水溶液中，超声溶解后加入引发剂，搅拌溶解后加入含氮聚合物前驱体，再将所得的溶续搅拌老化至少24h以上得到第一混合物；当所述模板剂或引发剂在水溶液溶解受限时，所述水溶液添加有酸溶液，所述酸溶液包括盐酸或硫酸或硝酸。Dissolving the template agent in an aqueous solution, adding an initiator after ultrasonic dissolution, adding a nitrogen-containing polymer precursor after stirring and dissolving, and then continuing to stir and age the obtained solution for at least 24 hours to obtain a first mixture; when the template agent or initiator When the aqueous solution is limited in solubility, the aqueous solution is added with an acid solution, and the acid solution includes hydrochloric acid or sulfuric acid or nitric acid.
在其中一些实施例中，在将模板剂、引发剂及含氮聚合物前驱体溶解于水溶液中得到第一混合物的步骤中，所述的模板剂包括十六烷基三甲基溴化铵、十二烷基硫酸钠、十二烷基苯磺酸钠、十八烷基羟磺甜菜碱、聚丙烯酞胺、聚乙二醇、聚乙烯吡咯烷酮、聚葡萄糖、聚山黎酯、各种有机胺、季铵盐类化合物中的一种或多种。In some of these embodiments, in the step of dissolving the template agent, the initiator and the nitrogen-containing polymer precursor in the aqueous solution to obtain the first mixture, the template agent includes cetyltrimethylammonium bromide, Sodium lauryl sulfate, sodium dodecylbenzene sulfonate, octadecyl sulfobetaine, polyacrylamide, polyethylene glycol, polyvinylpyrrolidone, polydextrose, polybenzyl ester, various organic One or more of amines and quaternary ammonium compounds.
在其中一些实施例中，所述的引发剂为过氧化物引发剂或偶氮类引发剂中的至少一种，所述过氧化物引发剂包括有机过氧化物或无机过氧化物，所述有机过氧化物包括结构通式为R-O-O-H或R-O-O-R的有机过氧化物，其中，R为烷基、酰基、碳酸酯基；所述无机过氧化物包括过硫酸铵或过硫酸钾或过硫酸钠；所述偶氮类引发剂包括偶氮二异丁腈或偶氮二异庚腈或偶氮二异丁酸二甲酯。In some of these embodiments, the initiator is at least one of a peroxide initiator or an azo initiator, and the peroxide initiator includes an organic peroxide or an inorganic peroxide, and the Organic peroxides include organic peroxides with a general structural formula of R-O-O-H or R-O-O-R, wherein R is an alkyl group, an acyl group, or a carbonate group; the inorganic peroxides include ammonium persulfate, potassium persulfate or sodium persulfate; The azo initiator includes azobisisobutyronitrile or azobisisoheptanonitrile or dimethyl azobisisobutyrate.
在其中一些实施例中，所述的含氮聚合物前驱体可以是吡咯、吡啶、吡唑、咪唑、噻唑、嘧啶、喹啉、嘌呤、苯胺及以上化合物的衍生物中的一种或多种。In some of these embodiments, the nitrogen-containing polymer precursor can be one or more of pyrrole, pyridine, pyrazole, imidazole, thiazole, pyrimidine, quinoline, purine, aniline and derivatives of the above compounds .
在其中一些实施例中，所述模板剂、引发剂、含氮聚合物前驱体的摩尔浓度比为1:1～6:4～50。In some of the embodiments, the molar concentration ratio of the template agent, the initiator, and the nitrogen-containing polymer precursor is 1:1˜6:4˜50.
在其中一些实施例中，在将所述第一混合物分散于含有稀土金属前驱体和碱金属盐的溶液中搅拌吸附得到第二混合物的步骤中，具体为：In some of these embodiments, in the step of dispersing the first mixture in a solution containing a rare earth metal precursor and an alkali metal salt, stirring and adsorbing to obtain a second mixture, specifically:
将所述第一混合物用水和乙醇交替抽滤洗涤，以去除所述模板剂以及低聚合度前驱体后，分散于含有稀土金属前驱体和碱金属盐的溶液中，搅拌吸附得到第二混合物。The first mixture is alternately sucked and washed with water and ethanol to remove the template agent and the low-polymerization degree precursor, then dispersed in a solution containing the rare earth metal precursor and the alkali metal salt, and stirred and adsorbed to obtain the second mixture.
在其中一些实施例中，所述的碱金属盐可以为任一种或多种可溶性碱金属盐，所述可溶性碱金属盐为氟化锂、氯化锂、溴化锂、碘化锂、硝酸锂、硫酸锂、碳酸锂、醋酸锂、高氯酸锂、六氟砷酸锂、六氟磷酸锂、四氟硼酸锂、磷酸铁锂、氟化钠、氯化钠、溴化钠、碘化钠、硝酸钠、硫酸钠、碳酸钠、醋酸钠、高氯酸钠、六氟砷酸钠、六氟磷酸钠、四氟硼酸钠、磷酸铁钠、氟化钾、氯化钾、溴化钾、碘化钾、硝酸钾、硫酸钾、碳酸钾、醋酸钾、高氯酸钾、六氟砷酸钾、六氟磷酸钾、四氟硼酸钾、磷酸铁钾中的一种或多种。In some of these embodiments, the alkali metal salt can be any one or more soluble alkali metal salts, and the soluble alkali metal salt is lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, Lithium sulfate, lithium carbonate, lithium acetate, lithium perchlorate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium iron phosphate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium nitrate, Sodium sulfate, sodium carbonate, sodium acetate, sodium perchlorate, sodium hexafluoroarsenate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium ferric phosphate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium nitrate , Potassium sulfate, potassium carbonate, potassium acetate, potassium perchlorate, potassium hexafluoroarsenate, potassium hexafluorophosphate, potassium tetrafluoroborate, and potassium iron phosphate.
在其中一些实施例中，所述的稀土金属前驱体包含钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥中至少5种金属的可溶性盐，所述可溶性盐为MClx、MI x、MBr x、MF x、M(NO 3) x、M x(SO 4) y、M(Ac) x、Mx(PO 4) y、M x(C 2O 4) y中的至少一种，其中M＝Sc,Y,La,Ce,Pr,Nd,Pm Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu；x＝2,3,4；y＝2,3,4或以上稀土金属盐的水合物。 In some of these embodiments, the rare earth metal precursor comprises at least Soluble salts of five metals, the soluble salts are MClx, MI x , MBr x , MF x , M(NO 3 ) x , M x (SO 4 ) y , M(Ac) x , Mx(PO 4 ) y , at least one of M x (C 2 O 4 ) y , where M=Sc, Y, La, Ce, Pr, Nd, Pm Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; x=2,3,4; y=2,3,4 or more hydrates of rare earth metal salts.
在其中一些实施例中，所述溶液中稀土金属前驱体和碱金属盐的摩尔浓度比为1:2～20，稀土金属前驱体摩尔浓度之和为1～1000mmol/L，且各稀土金属前驱体含量为不为0的任意比例。In some of these embodiments, the molar concentration ratio of the rare earth metal precursor and the alkali metal salt in the solution is 1:2-20, the sum of the molar concentrations of the rare earth metal precursor is 1-1000 mmol/L, and each rare earth metal precursor The body content is any ratio other than zero.
在其中一些实施例中，在将所述第二混合物于600℃-1000℃温度下，先在N 2中煅烧0.2-5h，再在NH 3中煅烧0.2-5h，，得到烧结产物的步骤中，具体为： In some of these embodiments, the second mixture is first calcined in N2 for 0.2-5h at a temperature of 600°C-1000°C, and then calcined in NH3 for 0.2-5h to obtain a sintered product ,Specifically:
将所述第二混合物抽滤并真空干燥后研磨均匀得到固体样品，将所述固体样品后在N 2气流下加热到600-1000℃，并煅烧0.2-5h；降到室温后，将得到的固体粉末放到NH 3气流下加热到600-1000℃，并煅烧0.2-5h，降到室温下得到烧结产物。 The second mixture was suction-filtered and vacuum-dried to obtain a solid sample, which was then heated to 600-1000°C under N2 flow and calcined for 0.2-5h; after cooling down to room temperature, the obtained The solid powder is heated to 600-1000°C under NH 3 flow, and calcined for 0.2-5h, and then cooled to room temperature to obtain a sintered product.
在其中一些实施例中，在将所述烧结产物真空干燥得到所述燃料电池催化剂的步骤中，具体包括：In some of these embodiments, the step of vacuum drying the sintered product to obtain the fuel cell catalyst specifically includes:
将所述烧结产物在40-80℃下酸洗2-8h，洗涤完成后抽滤得到固体样品，将所述固体样品进行真空烘干，再将得到的产物进行酸洗，再次真空烘干得到所述燃料电池催化剂。Pickling the sintered product at 40-80°C for 2-8 hours, suction filtering to obtain a solid sample after washing, vacuum-drying the solid sample, then acid-washing the obtained product, and vacuum-drying again to obtain The fuel cell catalyst.
另一方面，本申请还提供了一种燃料电池催化剂，由所述的燃料电池催化剂的制备方法制备得到。On the other hand, the present application also provides a fuel cell catalyst, which is prepared by the preparation method of the fuel cell catalyst.
再一方面，本申请还提供了一种燃料电池，添加有所述的燃料电池催化剂。In another aspect, the present application also provides a fuel cell, which is added with the fuel cell catalyst.
本申请提供的燃料电池催化剂的制备方法，将模板剂、引发剂及含氮聚合物前驱体溶解于水溶液中得到第一混合物，将所述第一混合物分散于含有稀土金属前驱体和碱金属盐的溶液中搅拌吸附得到第二混合物，将所述第二混合物于600℃-1000℃煅烧0.2-5h，得到烧结产物，将所述烧结产物真空干燥得到所述燃料电池催化剂，制备得到的燃料电池催化剂，上述方法，利用有机聚合和高温煅烧制备得到的高熵稀土单原子催化剂，得到的催化剂具有直径小、孔径小、孔隙率高，纤维均一性好等优点，且具有良好的ORR催化性能，可广泛应用于燃料电池、金属空气电池。上述方法工艺简单，原料成本低廉、安全可靠且环境友好等优点。In the preparation method of the fuel cell catalyst provided by the application, the template agent, the initiator and the nitrogen-containing polymer precursor are dissolved in the aqueous solution to obtain the first mixture, and the first mixture is dispersed in the mixture containing the rare earth metal precursor and the alkali metal salt. The second mixture is obtained by stirring and adsorbing in the solution, and the second mixture is calcined at 600°C-1000°C for 0.2-5h to obtain a sintered product, and the sintered product is vacuum-dried to obtain the fuel cell catalyst, and the obtained fuel cell Catalyst, the above method, the high-entropy rare earth single-atom catalyst prepared by organic polymerization and high-temperature calcination, the obtained catalyst has the advantages of small diameter, small pore size, high porosity, good fiber uniformity, etc., and has good ORR catalytic performance, It can be widely used in fuel cells and metal-air batteries. The above method has the advantages of simple process, low cost of raw materials, safety, reliability and environmental friendliness.
附图说明Description of drawings
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面所描述的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the accompanying drawings that need to be used in the embodiments of the present application or in the description of the prior art. Obviously, the accompanying drawings described below are only of the present application For some embodiments, those of ordinary skill in the art can also obtain other drawings based on these drawings without any creative effort.
图1为本申请提供的燃料电池催化剂的制备方法的步骤流程图；Fig. 1 is the flow chart of the steps of the preparation method of the fuel cell catalyst provided by the present application;
图2为本申请实施例1中制备的HE(La/Ce/Pr/Nd/Pm)催化材料扫描电镜图片；Fig. 2 is the HE (La/Ce/Pr/Nd/Pm) catalytic material scanning electron microscope picture prepared in the embodiment 1 of the present application;
图3为本申请实施例1-5中制备催化材料在电极负载量为0.22mg/cm 2时的ORR性能对比图(测试条件：三电极体系，工作电极为催化剂，对电极为碳棒， 参比电极为饱和甘汞电极，电解液为0.1mol/L的KOH溶液)； Fig. 3 is the comparison chart of ORR performance of the catalytic material prepared in Examples 1-5 of the present application when the electrode load is 0.22 mg/cm 2 (test conditions: three-electrode system, the working electrode is a catalyst, and the counter electrode is a carbon rod, see The specific electrode is a saturated calomel electrode, and the electrolyte is 0.1mol/L KOH solution);
图4为本申请实施例1在不同的稀土金属前驱体添加比例下高熵稀土(La/Ce/Pr/Nd/Pm)电催化剂的ORR性能对比图(测试条件：三电极体系，工作电极为催化剂，对电极为碳棒，参比电极为饱和甘汞电极，电解液为0.1mol/L的KOH溶液)。Fig. 4 is a comparison chart of ORR performance of high-entropy rare earth (La/Ce/Pr/Nd/Pm) electrocatalysts in Example 1 of the present application under different addition ratios of rare earth metal precursors (test conditions: three-electrode system, working electrode is catalyst, the counter electrode is a carbon rod, the reference electrode is a saturated calomel electrode, and the electrolyte is 0.1mol/L KOH solution).
具体实施方式Detailed ways
下面详细描述本申请的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本申请，而不能理解为对本申请的限制。Embodiments of the present application are described in detail below, examples of which are shown in the drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the figures are exemplary, and are intended to explain the present application, and should not be construed as limiting the present application.
在本申请的描述中，需要理解的是，术语“上”、“下”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本申请和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本申请的限制。In the description of the present application, it should be understood that the orientation or positional relationship indicated by the terms "upper", "lower", "horizontal", "inner", "outer", etc. is based on the orientation or positional relationship shown in the drawings , is only for the convenience of describing the present application and simplifying the description, but does not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present application.
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本申请的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。In addition, the terms "first" and "second" are used for descriptive purposes only, and cannot be interpreted as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features. Thus, a feature defined as "first" and "second" may explicitly or implicitly include one or more of these features. In the description of the present application, "plurality" means two or more, unless otherwise specifically defined.
为了使本申请的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本申请进行进一步详细说明。In order to make the purpose, technical solution and advantages of the present application clearer, the present application will be further described in detail below in conjunction with the accompanying drawings and embodiments.
请参阅图1，为本申请实施例提供的燃料电池催化剂的制备方法的步骤流程图，包括下述步骤：Please refer to Fig. 1, the flow chart of the steps for the preparation method of the fuel cell catalyst provided by the embodiment of the present application, including the following steps:
步骤S110：将模板剂、引发剂及含氮聚合物前驱体溶解于水溶液中得到第一混合物。Step S110: dissolving the templating agent, the initiator and the nitrogen-containing polymer precursor in the aqueous solution to obtain a first mixture.
在其中一些实施例中，将模板剂溶解于水溶液中，超声溶解后加入引发剂，搅拌溶解后加入含氮聚合物前驱体，再将所得的溶续搅拌老化至少24h以上得到第一混合物；当所述模板剂或引发剂在水溶液溶解受限时，所述水溶液添加有酸溶液，所述酸溶液包括盐酸或硫酸或硝酸。In some of these embodiments, the template agent is dissolved in the aqueous solution, the initiator is added after ultrasonic dissolution, the nitrogen-containing polymer precursor is added after stirring and dissolving, and the obtained solution is continuously stirred and aged for at least 24 hours to obtain the first mixture; when When the solubility of the template agent or initiator is limited in the aqueous solution, an acid solution is added to the aqueous solution, and the acid solution includes hydrochloric acid, sulfuric acid or nitric acid.
进一步地，所述的模板剂可以是：十六烷基三甲基溴化铵(CTAB)、十二烷基硫酸钠(SDS)、十二烷基苯磺酸钠(SDBS)、十八烷基羟磺甜菜碱(DHSB)、聚丙烯酞胺(PAM)、聚乙二醇(PEG)、聚乙烯吡咯烷酮(PVP)、聚葡萄糖、聚山黎酯、各种有机胺、季铵盐类化合物中的一种或多种。Further, the template can be: cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), octadecyl Hydroxybetaine (DHSB), polyacrylamide (PAM), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polydextrose, polybehenate, various organic amines, quaternary ammonium compounds one or more of.
进一步地，所述的引发剂为过氧化物引发剂或偶氮类引发剂中的至少一种，所述过氧化物引发剂包括有机过氧化物或无机过氧化物，所述有机过氧化物包括结构通式为R-O-O-H或R-O-O-R的有机过氧化物，其中，R为烷基、酰基、碳酸酯基；所述无机过氧化物包括过硫酸铵或过硫酸钾或过硫酸钠；所述偶氮类引发剂包括偶氮二异丁腈或偶氮二异庚腈或偶氮二异丁酸二甲酯。Further, the initiator is at least one of a peroxide initiator or an azo initiator, and the peroxide initiator includes an organic peroxide or an inorganic peroxide, and the organic peroxide Including organic peroxides with a general structural formula of R-O-O-H or R-O-O-R, wherein R is an alkyl group, an acyl group, or a carbonate group; the inorganic peroxides include ammonium persulfate or potassium persulfate or sodium persulfate; the azo Types of initiators include azobisisobutyronitrile or azobisisoheptanonitrile or dimethyl azobisisobutyrate.
例如，所述有机过氧化物可以包括下述物质：如过氧化苯甲酰、异丙苯过氧化氢、过氧化二叔丁基、过氧化二异丙苯、过氧化苯甲酸叔丁酯、过氧化叔戊酸叔丁基酯、过氧化甲乙酮、过氧化环己酮、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯等。For example, the organic peroxide may include materials such as benzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl benzoate, tert-butyl peroxy-tert-valerate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and the like.
进一步地，所述的含氮聚合物前驱体可以是吡咯、吡啶、吡唑、咪唑、噻唑、嘧啶、喹啉、嘌呤、苯胺及以上化合物的衍生物中的一种或多种。Further, the nitrogen-containing polymer precursor may be one or more of pyrrole, pyridine, pyrazole, imidazole, thiazole, pyrimidine, quinoline, purine, aniline and derivatives of the above compounds.
进一步地，所述模板剂、引发剂、含氮聚合物前驱体的摩尔浓度比为1:1～6:4～50。Further, the molar concentration ratio of the template agent, the initiator, and the nitrogen-containing polymer precursor is 1:1˜6:4˜50.
可以理解，可以通过改变聚合物前驱体的类型、用量，稀土元素种类、含量等调节高熵稀土单原子的配位环境，改善活性中心的电子结构，从而实现对稀土单原子催化剂性能的调节。It can be understood that the coordination environment of the high-entropy rare earth single atom can be adjusted by changing the type and amount of the polymer precursor, the type and content of the rare earth element, and the electronic structure of the active center can be improved, thereby realizing the adjustment of the performance of the rare earth single atom catalyst.
步骤S120：将所述第一混合物分散于含有稀土金属前驱体和碱金属盐的溶液中搅拌吸附得到第二混合物。Step S120: dispersing the first mixture in a solution containing rare earth metal precursors and alkali metal salts, stirring and adsorbing to obtain a second mixture.
在其中一些实施例中，将所述第一混合物用水和乙醇交替抽滤洗涤，以去除所述模板剂以及低聚合度前驱体后，分散于含有稀土金属前驱体和碱金属盐的溶液中，搅拌吸附得到第二混合物。In some of these embodiments, the first mixture is alternately suction-filtered and washed with water and ethanol to remove the template agent and the low-polymerization degree precursor, and then dispersed in a solution containing a rare earth metal precursor and an alkali metal salt, Stir and adsorb to obtain the second mixture.
具体地，所述的碱金属盐可以为任一种或多种可溶性碱金属盐，所述可溶性碱金属盐为氟化锂、氯化锂、溴化锂、碘化锂、硝酸锂、硫酸锂、碳酸锂、醋酸锂、高氯酸锂、六氟砷酸锂、六氟磷酸锂、四氟硼酸锂、磷酸铁锂、氟化钠、氯化钠、溴化钠、碘化钠、硝酸钠、硫酸钠、碳酸钠、醋酸钠、高氯酸钠、六氟砷酸钠、六氟磷酸钠、四氟硼酸钠、磷酸铁钠、氟化钾、氯化钾、溴化钾、碘化钾、硝酸钾、硫酸钾、碳酸钾、醋酸钾、高氯酸钾、六氟砷酸钾、六氟磷酸钾、四氟硼酸钾、磷酸铁钾中的一种或多种。Specifically, the alkali metal salt can be any one or more soluble alkali metal salts, and the soluble alkali metal salt is lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, lithium sulfate, carbonic acid Lithium, lithium acetate, lithium perchlorate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium iron phosphate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium nitrate, sodium sulfate, carbonic acid Sodium, sodium acetate, sodium perchlorate, sodium hexafluoroarsenate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium ferric phosphate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium nitrate, potassium sulfate, One or more of potassium carbonate, potassium acetate, potassium perchlorate, potassium hexafluoroarsenate, potassium hexafluorophosphate, potassium tetrafluoroborate, and potassium iron phosphate.
具体地，所述的稀土金属前驱体可以是：包含钪(Sc)、钇(Y)、镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)中至少5种金属的可溶性盐。Specifically, the rare earth metal precursor may be: containing scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium At least Soluble salts of 5 metals.
本申请提供的稀土金属前驱体，包括上述至少5种金属的可溶性盐，从而打破了碳环对称性，破坏大π键，增强碳基底调控活性，多元素协同增加催化性能。The rare earth metal precursor provided by this application includes soluble salts of at least five metals mentioned above, thereby breaking the symmetry of the carbon ring, destroying the large π bond, enhancing the regulation activity of the carbon substrate, and synergistically increasing the catalytic performance of the multi-element.
具体地，所述可溶性盐为MClx、MIx、MBrx、MFx、M(NO3)x、Mx(SO4)y、M(Ac)x、Mx(PO4)y、Mx(C2O4)y(其中M＝Sc,Y,La,Ce,Pr,Nd,Pm Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu；x＝2,3,4；y＝2,3,4)或以上稀土金属盐的水合物。Specifically, the soluble salts are MClx, MIx, MBrx, MFx, M(NO3)x, Mx(SO4)y, M(Ac)x, Mx(PO4)y, Mx(C2O4)y (wherein M=Sc , Y, La, Ce, Pr, Nd, Pm Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; x=2,3,4; y=2,3,4) or above Hydrates of rare earth metal salts.
具体地，所述溶液中稀土金属前驱体和碱金属盐的摩尔浓度比为1:2～20，稀土金属前驱体摩尔浓度之和为1～1000mmol/L，且各稀土金属前驱体含量为不为0的任意比例。Specifically, the molar concentration ratio of the rare earth metal precursor and the alkali metal salt in the solution is 1:2 to 20, the sum of the molar concentrations of the rare earth metal precursor is 1 to 1000 mmol/L, and the content of each rare earth metal precursor is not Any ratio of 0.
可以理解，在该浓度范围内既能保证特定稀土单原子的存在，也能避免金属团簇或纳米颗粒的产生。It can be understood that within this concentration range, the existence of specific rare earth single atoms can be guaranteed, and the generation of metal clusters or nanoparticles can also be avoided.
步骤S130：将所述第二混合物于600℃-1000℃煅烧0.2-5h，得到烧结产物。Step S130: calcining the second mixture at 600°C-1000°C for 0.2-5h to obtain a sintered product.
在其中一些实施例中，将所述第二混合物抽滤并真空干燥后研磨均匀得到固体样品，将所述固体样品后在N 2气流下加热到600-1000℃，并煅烧0.2-5h；降到室温后，将得到的固体粉末放到NH 3气流下加热到600-1000℃，并煅烧0.2-5h，降到室温下得到烧结产物。 In some of these embodiments, the second mixture is suction-filtered and vacuum-dried to obtain a solid sample, and the solid sample is then heated to 600-1000° C. under N 2 airflow, and calcined for 0.2-5 h; After reaching room temperature, the obtained solid powder is heated to 600-1000° C. under NH 3 flow, and calcined for 0.2-5 h, and then lowered to room temperature to obtain a sintered product.
步骤S140：将所述烧结产物真空干燥得到所述燃料电池催化剂。Step S140: vacuum drying the sintered product to obtain the fuel cell catalyst.
在其中一些实施例中，将所述烧结产物在40-80℃下酸洗2-8h，洗涤完成后抽滤得到固体样品，将所述固体样品进行真空烘干，再将得到的产物进行酸洗，再次真空烘干得到所述燃料电池催化剂。In some of these embodiments, the sintered product is acid-washed at 40-80°C for 2-8 hours, and after the washing is completed, a solid sample is obtained by suction filtration, and the solid sample is vacuum-dried, and then the obtained product is acid-washed. Washing, vacuum drying again to obtain the fuel cell catalyst.
本申请上述实施例提供的燃料电池催化剂的制备方法，利用有机聚合和高温煅烧制备得到的高熵稀土单原子催化剂具有直径小、孔径小、孔隙率高，纤维均一性好等优点，且具有良好的ORR催化性能，可广泛应用于燃料电池、金属空气电池。The preparation method of the fuel cell catalyst provided by the above-mentioned embodiments of the present application, the high-entropy rare earth single-atom catalyst prepared by organic polymerization and high-temperature calcination has the advantages of small diameter, small pore size, high porosity, good fiber uniformity, etc., and has good ORR catalytic performance, can be widely used in fuel cells, metal-air batteries.
上述方法工艺简单，原料成本低廉、安全可靠且环境友好等优点；制备得到的燃料电池催化剂，将多种稀土元素以单原子的形式修饰材料以提高材料电催化活性，使得基底材料电催化活性大大提高；同时，在聚合物纤维上引入多种稀土元素，经过高温热解和酸处理后，得到具有高熵稀土单原子修饰且具有丰富表面缺陷的纳米电催化剂，在电催化ORR中表现出优异的性能。The above method has the advantages of simple process, low raw material cost, safety, reliability, and environmental friendliness; the prepared fuel cell catalyst modifies the material with a variety of rare earth elements in the form of single atoms to improve the electrocatalytic activity of the material, so that the electrocatalytic activity of the substrate material is greatly improved. At the same time, a variety of rare earth elements were introduced on the polymer fiber, and after high-temperature pyrolysis and acid treatment, a nano-electrocatalyst with high-entropy rare-earth single-atom modification and rich surface defects was obtained, which showed excellent performance in electrocatalytic ORR performance.
本发明上述实制备方法中应用到的原材料如前述实施例中所描述，此处不再赘述。The raw materials used in the above-mentioned practical preparation method of the present invention are as described in the foregoing embodiments, and will not be repeated here.
下面列举具体的实施例进一步说明上述高熵稀土单原子催化剂的制备方法。The following specific examples are listed to further illustrate the preparation method of the above-mentioned high-entropy rare earth single-atom catalyst.
实施例1Example 1
一种高熵稀土金属单原子催化剂的制备方法包括如下步骤：A preparation method of a high-entropy rare earth metal single-atom catalyst comprises the following steps:
S1：将0.1g CTAB(模板剂)溶解到1mol/L HCl中，后加入1.73g APS(引发剂)搅拌溶解后加入1mL吡咯(含氮聚合物前驱体)，持续搅拌24h；S1: Dissolve 0.1g CTAB (template agent) into 1mol/L HCl, then add 1.73g APS (initiator) and stir to dissolve, then add 1mL pyrrole (nitrogen-containing polymer precursor), and continue stirring for 24h;
S2：用水和乙醇交替清洗3次后将所得固体材料分散到100mL，分散于含有0.4mol/L LiCl和LaCl 3、CeCl 3、PrCl 3、NdCl 3以及PmCl 3浓度均为4mmol/L的溶液中，超声分散30min后搅拌吸附24h； S2: After alternately washing with water and ethanol for 3 times, disperse the obtained solid material into 100mL, and disperse in a solution containing 0.4mol/L LiCl and LaCl 3 , CeCl 3 , PrCl 3 , NdCl 3 and PmCl 3 with a concentration of 4mmol/L , ultrasonically dispersed for 30 minutes, then stirred and adsorbed for 24 hours;
S3：将S2所得产物抽滤并真空干燥后得到固体样品，将固体样品加热到900℃下，并先后在N 2和NH 3中煅烧0.5h； S3: Suction filter and vacuum dry the product obtained in S2 to obtain a solid sample, heat the solid sample to 900°C, and calcinate in N 2 and NH 3 successively for 0.5 h;
S4：将得到样品用150ml 1mol/L H 2SO 4清洗两次酸洗后抽滤并真空干燥即得到La/Ce/Pr/Nd/Pm高熵稀土单原子催化剂。 S4: The obtained sample was washed twice with 150ml 1mol/L H 2 SO 4 , acid-washed, filtered and vacuum-dried to obtain a La/Ce/Pr/Nd/Pm high-entropy rare earth single-atom catalyst.
对比例1Comparative example 1
以CTAB作为模板剂，APS作为引发剂，LiNO 3作为碱金属盐，以吡咯作为含氮聚合物前驱体以浓度均为4mmol/L的EuCl 3、GdCl 3、TbCl 3、DyCl 3以及HoCl 3作为稀土金属前驱体，电化学测试中KOH浓度为0.1mol/L，参照实施例1进行电化学测试。 CTAB was used as a template, APS was used as an initiator, LiNO 3 was used as an alkali metal salt, pyrrole was used as a nitrogen-containing polymer precursor, and EuCl 3 , GdCl 3 , TbCl 3 , DyCl 3 and HoCl 3 at a concentration of 4 mmol/L were used as For the rare earth metal precursor, the KOH concentration in the electrochemical test is 0.1mol/L, and the electrochemical test is performed with reference to Example 1.
对比例2Comparative example 2
以SDS作为模板剂，过硫酸钾作为引发剂，LiCl作为碱金属盐，以吡咯作为含氮聚合物前驱体以浓度均为4mmol/L的LaCl 3、CeCl 3、PrCl 3、NdCl 3以及PmCl 3作为稀土金属前驱体，电化学测试中KOH浓度为0.1mol/L，参照实施例1进行电化学测试。 Using SDS as a template, potassium persulfate as an initiator, LiCl as an alkali metal salt, pyrrole as a nitrogen-containing polymer precursor, and LaCl 3 , CeCl 3 , PrCl 3 , NdCl 3 and PmCl 3 at a concentration of 4 mmol/L As the rare earth metal precursor, the concentration of KOH in the electrochemical test was 0.1 mol/L, and the electrochemical test was performed with reference to Example 1.
对比例3Comparative example 3
以CTAB作为模板剂，过硫酸钾作为引发剂，NaNO 3作为碱金属盐，以苯胺作为含氮聚合物前驱体，以浓度均为4mmol/L的LaNO 3、CeNO 3、PrNO 3、NdNO 3以及PmNO 3作为稀土金属前驱体，电化学测试中KOH浓度为0.1mol/L，参照实施例1进行电化学测试。 CTAB was used as template, potassium persulfate was used as initiator, NaNO 3 was used as alkali metal salt, aniline was used as nitrogen-containing polymer precursor, LaNO 3 , CeNO 3 , PrNO 3 , NdNO 3 and PmNO 3 is used as a rare earth metal precursor, and the KOH concentration in the electrochemical test is 0.1 mol/L, and the electrochemical test is performed with reference to Example 1.
对比例4Comparative example 4
以CTAB作为模板剂，APS作为引发剂，NaCl作为碱金属盐，以苯胺作为含氮聚合物前驱体，以浓度均为4mmol/L的ScCl 3、PrCl 3、EuCl 3、HoCl 3以 及YbCl 3作为稀土金属前驱体，电化学测试中KOH浓度为1mol/L，参照实施例1进行电化学测试。 CTAB was used as a template, APS was used as an initiator, NaCl was used as an alkali metal salt, aniline was used as a nitrogen-containing polymer precursor, and ScCl 3 , PrCl 3 , EuCl 3 , HoCl 3 and YbCl 3 with a concentration of 4 mmol/L were used as For the rare earth metal precursor, the KOH concentration in the electrochemical test was 1mol/L, and the electrochemical test was performed with reference to Example 1.
请参阅图2、图3及图4，本发明将上述实施例所得高熵稀土金属单原子催化剂组装到三电极体系中，以催化剂为工作电极，以碳棒作为对电极，以饱和甘汞电极为参比电极，电解液为0.1mol/L的KOH溶液，进行了ORR测试，催化剂负载量为0.22mg/cm2，电压范围为1.0V-0.4V vs.RHE(本发明后续实施例均采用相同的测试方法获得电化学性能结果)。测试结果及其他各参数如表1所示。Please refer to Fig. 2, Fig. 3 and Fig. 4, the present invention assembles the high-entropy rare earth metal single-atom catalyst obtained in the above embodiments into a three-electrode system, with the catalyst as the working electrode, the carbon rod as the counter electrode, and the saturated calomel electrode For reference electrode, electrolytic solution is the KOH solution of 0.1mol/L, has carried out ORR test, and catalyst load is 0.22mg/cm , and voltage range is 1.0V-0.4V vs.RHE (subsequent embodiments of the present invention all adopt the same The test method to obtain electrochemical performance results). The test results and other parameters are shown in Table 1.
表1Table 1
Figure PCTCN2021138101-appb-000001
Figure PCTCN2021138101-appb-000001
由表1可知，本发明实施例1选用CTAB为模板剂、APS为引发剂、La、Ce、Pr、Nd、Pm的氯盐作为稀土金属前驱体，表现出了较高的起始电位和较高的半波电位，ORR性能良好。It can be seen from Table 1 that in Example 1 of the present invention, CTAB is used as template agent, APS is used as initiator, and chloride salts of La, Ce, Pr, Nd, and Pm are used as rare earth metal precursors, showing a higher initial potential and a higher High half-wave potential, good ORR performance.
实施例2-76Example 2-76
实施例2-76与实施例1的区别仅在于稀土金属前驱体的种类或含量不同，具体如表2所示，将实施例5-76所得的高熵稀土金属单原子催化剂进行ORR 测试，其测试结果如表2所示：The difference between embodiment 2-76 and embodiment 1 is that the type or content of the rare earth metal precursor is different, specifically as shown in table 2, the high entropy rare earth metal single-atom catalyst obtained in embodiment 5-76 is tested for ORR, and its The test results are shown in Table 2:
表2Table 2
Figure PCTCN2021138101-appb-000002
Figure PCTCN2021138101-appb-000002
Figure PCTCN2021138101-appb-000003
Figure PCTCN2021138101-appb-000003
Figure PCTCN2021138101-appb-000004
Figure PCTCN2021138101-appb-000004
由表2可知，添加Ce或Y的可溶性盐时，催化剂具有更好的ORR性能，表现出更高的起始电位和半波电位。It can be seen from Table 2 that when the soluble salt of Ce or Y is added, the catalyst has better ORR performance, showing higher onset potential and half-wave potential.
实施例77-103Example 77-103
实施例77-103与实施例1的区别仅在于模板剂的种类不同，具体如表3所示，将实施例77-103所得的高熵稀土金属单原子催化剂进行ORR测试，其测试结果如表3所示：The only difference between Examples 77-103 and Example 1 is the type of templating agent, which is specifically shown in Table 3. The high-entropy rare earth metal single-atom catalyst obtained in Example 77-103 was tested for ORR, and the test results are shown in the table 3 shows:
Sc/Y/La/Ce/Pr/Nd/Pm/Sm/Eu/Gd/Tb/Dy/Ho/Er/Tm/Yb/LuSc/Y/La/Ce/Pr/Nd/Pm/Sm/Eu/Gd/Tb/Dy/Ho/Er/Tm/Yb/Lu
表3table 3
Figure PCTCN2021138101-appb-000005
Figure PCTCN2021138101-appb-000005
Figure PCTCN2021138101-appb-000006
Figure PCTCN2021138101-appb-000006
由表3可知，CTAB作为模板剂时，催化剂具有更好的ORR性能，表现出更高的起始电位和半波电位。It can be seen from Table 3 that when CTAB is used as a template, the catalyst has better ORR performance, showing higher onset potential and half-wave potential.
实施例104-122Examples 104-122
实施例104-122与实施例1的区别仅在于引发剂的种类不同，具体如表4所示，将实施例104-122所得的高熵稀土金属单原子催化剂进行ORR测试，其测试结果如表4所示：The difference between Examples 104-122 and Example 1 is that the types of initiators are different, as shown in Table 4. The high-entropy rare earth metal single-atom catalysts obtained in Examples 104-122 were tested for ORR, and the test results are shown in the table 4 shows:
表4Table 4
Figure PCTCN2021138101-appb-000007
Figure PCTCN2021138101-appb-000007
由表4可知，APS作为引发剂时，催化剂具有更好的ORR性能，表现出更高的起始电位和半波电位。It can be seen from Table 4 that when APS is used as the initiator, the catalyst has better ORR performance, showing higher onset potential and half-wave potential.
实施例123-152Examples 123-152
实施例123-152与实施例1的区别仅在于含氮聚合物前驱体的种类不同， 具体如表5所示，将实施例123-所得的高熵稀土金属单原子催化剂进行ORR测试，其测试结果如表5所示：The only difference between Examples 123-152 and Example 1 is that the type of nitrogen-containing polymer precursor is different, specifically as shown in Table 5, the ORR test was performed on the high-entropy rare earth metal single-atom catalyst obtained in Example 123-, and the test The results are shown in Table 5:
表5table 5
Figure PCTCN2021138101-appb-000008
Figure PCTCN2021138101-appb-000008
由表5可知，吡咯作为含氮聚合物前驱体时，催化剂具有更好的ORR性能，表现出更高的起始电位和半波电位。It can be seen from Table 5 that when pyrrole is used as the precursor of nitrogen-containing polymer, the catalyst has better ORR performance, showing higher onset potential and half-wave potential.
实施例153-Example 153-
实施例153-与实施例1的区别仅在于碱金属盐的种类不同，具体如表6所 示，将实施例153-所得的高熵稀土金属单原子催化剂进行ORR测试，其测试结果如表6所示：Example 153-The only difference from Example 1 is that the type of alkali metal salt is different, as shown in Table 6. The high-entropy rare earth metal single-atom catalyst obtained in Example 153-was subjected to an ORR test, and the test results are shown in Table 6 Shown:
表6Table 6
Figure PCTCN2021138101-appb-000009
Figure PCTCN2021138101-appb-000009
Figure PCTCN2021138101-appb-000010
Figure PCTCN2021138101-appb-000010
由表6可知，碱金属盐选用氯化锂，催化剂具有更好的ORR性能，表现出更高的起始电位和半波电位。It can be seen from Table 6 that the catalyst has better ORR performance when the alkali metal salt is lithium chloride, showing higher onset potential and half-wave potential.
本发明实施例涉及的高熵稀土单原子催化剂在应用时不局限于三电极***，也在燃料电池中得到应用。本发明实施例的重要成分是以多种稀土元素合成高熵分布的稀土单原子电催化剂，保持良好ORR性能的同时具有良好的稳定性。这也是稀土金属首次以高熵单原子形式制备电催化剂，使得电催化剂具有较低成本的同时也开拓了单原子催化剂的又一重要制备方法和应用。The application of the high-entropy rare earth single-atom catalyst involved in the embodiment of the present invention is not limited to the three-electrode system, and is also applied in fuel cells. The important component of the embodiment of the present invention is to synthesize a rare earth single-atom electrocatalyst with high entropy distribution from a variety of rare earth elements, which maintains good ORR performance and has good stability. This is also the first time that rare earth metals have prepared electrocatalysts in the form of high-entropy single atoms, which makes electrocatalysts have a lower cost and opens up another important preparation method and application of single-atom catalysts.
以上仅为本申请的较佳实施例而已，仅具体描述了本申请的技术原理，这些描述只是为了解释本申请的原理，不能以任何方式解释为对本申请保护范围的限制。基于此处解释，凡在本申请的精神和原则之内所作的任何修改、等同替换和改进，及本领域的技术人员不需要付出创造性的劳动即可联想到本申请的其他具体实施方式，均应包含在本申请的保护范围之内。The above are only preferred embodiments of the present application, and only specifically describe the technical principle of the present application. These descriptions are only for explaining the principle of the present application, and cannot be interpreted as limiting the protection scope of the present application in any way. Based on the explanations here, any modifications, equivalent replacements and improvements made within the spirit and principles of the application, and those skilled in the art who can think of other specific implementation methods of the application without creative work are all It should be included within the scope of protection of this application.

Claims (14)

  1. 一种燃料电池催化剂的制备方法，其特征在于，包括下述步骤：A method for preparing a fuel cell catalyst, characterized in that it comprises the steps of:
    将模板剂、引发剂及含氮聚合物前驱体溶解于水溶液中得到第一混合物；Dissolving the templating agent, the initiator and the nitrogen-containing polymer precursor in the aqueous solution to obtain the first mixture;
    将所述第一混合物分散于含有稀土金属前驱体和碱金属盐的溶液中搅拌吸附得到第二混合物；Dispersing the first mixture in a solution containing a rare earth metal precursor and an alkali metal salt, stirring and adsorbing to obtain a second mixture;
    将所述第二混合物于600℃-1000℃煅烧0.2-5h，得到烧结产物；及calcining the second mixture at 600°C-1000°C for 0.2-5h to obtain a sintered product; and
    将所述烧结产物真空干燥得到所述燃料电池催化剂。The sintered product is vacuum-dried to obtain the fuel cell catalyst.
  2. 如权利要求1所述的燃料电池催化剂的制备方法，其特征在于，在将模板剂、引发剂及含氮聚合物前驱体溶解于水溶液中得到第一混合物的步骤中，具体为：The preparation method of the fuel cell catalyst according to claim 1, wherein, in the step of dissolving the template agent, the initiator and the nitrogen-containing polymer precursor in the aqueous solution to obtain the first mixture, specifically:
    将模板剂溶解于水溶液中，超声溶解后加入引发剂，搅拌溶解后加入含氮聚合物前驱体，再将所得的溶续搅拌老化至少24h以上得到第一混合物；当所述模板剂或引发剂在水溶液溶解受限时，所述水溶液添加有酸溶液，所述酸溶液包括盐酸或硫酸或硝酸。Dissolving the template agent in an aqueous solution, adding an initiator after ultrasonic dissolution, adding a nitrogen-containing polymer precursor after stirring and dissolving, and then continuing to stir and age the obtained solution for at least 24 hours to obtain a first mixture; when the template agent or initiator When the aqueous solution is limited in solubility, the aqueous solution is added with an acid solution, and the acid solution includes hydrochloric acid or sulfuric acid or nitric acid.
  3. 如权利要求2所述的燃料电池催化剂的制备方法，其特征在于，所述的模板剂包括十六烷基三甲基溴化铵、十二烷基硫酸钠、十二烷基苯磺酸钠、十八烷基羟磺甜菜碱、聚丙烯酞胺、聚乙二醇、聚乙烯吡咯烷酮、聚葡萄糖、聚山黎酯、各种有机胺、季铵盐类化合物中的一种或多种。The preparation method of fuel cell catalyst as claimed in claim 2, is characterized in that, described templating agent comprises hexadecyltrimethylammonium bromide, sodium lauryl sulfate, sodium dodecylbenzenesulfonate , octadecyl sulfobetaine, polypropylene amide, polyethylene glycol, polyvinylpyrrolidone, polydextrose, polybehenate, various organic amines, one or more of quaternary ammonium compounds.
  4. 如权利要求2所述的燃料电池催化剂的制备方法，其特征在于，所述的引发剂为过氧化物引发剂或偶氮类引发剂中的至少一种，所述过氧化物引发剂包括有机过氧化物或无机过氧化物，所述有机过氧化物包括结构通式为R-O-O-H或R-O-O-R的有机过氧化物，其中，R为烷基、酰基、碳酸酯基；所述无机过氧化物包括过硫酸铵或过硫酸钾或过硫酸钠；所述偶氮类引发剂包括偶氮二异丁腈或偶氮二异庚腈或偶氮二异丁酸二甲酯。The preparation method of fuel cell catalyst as claimed in claim 2, is characterized in that, described initiator is at least one in peroxide initiator or azo initiator, and described peroxide initiator comprises organic Peroxides or inorganic peroxides, the organic peroxides include organic peroxides with a general structural formula of R-O-O-H or R-O-O-R, wherein R is an alkyl group, an acyl group, a carbonate group; the inorganic peroxides include peroxides Ammonium sulfate or potassium persulfate or sodium persulfate; the azo initiator includes azobisisobutyronitrile or azobisisoheptanonitrile or dimethyl azobisisobutyrate.
  5. 如权利要求2所述的燃料电池催化剂的制备方法，其特征在于，所述的 含氮聚合物前驱体可以是吡咯、吡啶、吡唑、咪唑、噻唑、嘧啶、喹啉、嘌呤、苯胺及以上化合物的衍生物中的一种或多种。The preparation method of fuel cell catalyst as claimed in claim 2, is characterized in that, described nitrogen-containing polymer precursor can be pyrrole, pyridine, pyrazole, imidazole, thiazole, pyrimidine, quinoline, purine, aniline and above One or more of the derivatives of the compound.
  6. 如权利要求2所述的燃料电池催化剂的制备方法，其特征在于，所述模板剂、引发剂、含氮聚合物前驱体的摩尔浓度比为1:1～6:4～50。The preparation method of fuel cell catalyst according to claim 2, characterized in that the molar concentration ratio of the template agent, the initiator, and the nitrogen-containing polymer precursor is 1:1-6:4-50.
  7. 如权利要求1所述的燃料电池催化剂的制备方法，其特征在于，在将所述第一混合物分散于含有稀土金属前驱体和碱金属盐的溶液中搅拌吸附得到第二混合物的步骤中，具体为：The method for preparing a fuel cell catalyst according to claim 1, wherein, in the step of dispersing the first mixture in a solution containing a rare earth metal precursor and an alkali metal salt, stirring and adsorbing to obtain a second mixture, specifically for:
    将所述第一混合物用水和乙醇交替抽滤洗涤，以去除所述模板剂以及低聚合度前驱体后，再分散于含有稀土金属前驱体和碱金属盐的溶液中，搅拌吸附得到第二混合物。The first mixture is alternately sucked and washed with water and ethanol to remove the template agent and the low-polymerization degree precursor, and then dispersed in a solution containing a rare earth metal precursor and an alkali metal salt, and stirred and adsorbed to obtain a second mixture .
  8. 如权利要求7所述的燃料电池催化剂的制备方法，其特征在于，所述的碱金属盐可以为任一种或多种可溶性碱金属盐，所述可溶性碱金属盐为氟化锂、氯化锂、溴化锂、碘化锂、硝酸锂、硫酸锂、碳酸锂、醋酸锂、高氯酸锂、六氟砷酸锂、六氟磷酸锂、四氟硼酸锂、磷酸铁锂、氟化钠、氯化钠、溴化钠、碘化钠、硝酸钠、硫酸钠、碳酸钠、醋酸钠、高氯酸钠、六氟砷酸钠、六氟磷酸钠、四氟硼酸钠、磷酸铁钠、氟化钾、氯化钾、溴化钾、碘化钾、硝酸钾、硫酸钾、碳酸钾、醋酸钾、高氯酸钾、六氟砷酸钾、六氟磷酸钾、四氟硼酸钾、磷酸铁钾中的一种或多种。The preparation method of fuel cell catalyst as claimed in claim 7, is characterized in that, described alkali metal salt can be any one or more soluble alkali metal salts, and described soluble alkali metal salt is lithium fluoride, chloride Lithium, lithium bromide, lithium iodide, lithium nitrate, lithium sulfate, lithium carbonate, lithium acetate, lithium perchlorate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium iron phosphate, sodium fluoride, sodium chloride, Sodium bromide, sodium iodide, sodium nitrate, sodium sulfate, sodium carbonate, sodium acetate, sodium perchlorate, sodium hexafluoroarsenate, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium iron phosphate, potassium fluoride, chlorine One or more of potassium chloride, potassium bromide, potassium iodide, potassium nitrate, potassium sulfate, potassium carbonate, potassium acetate, potassium perchlorate, potassium hexafluoroarsenate, potassium hexafluorophosphate, potassium tetrafluoroborate, potassium iron phosphate .
  9. 如权利要求7所述的燃料电池催化剂的制备方法，其特征在于，所述的稀土金属前驱体包含钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥中至少5种金属的可溶性盐，所述可溶性盐为MClx、MI x、MBr x、MF x、M(NO 3) x、M x(SO 4) y、M(Ac) x、Mx(PO 4) y、M x(C 2O 4) y中的至少一种，其中M＝Sc,Y,La,Ce,Pr,Nd,Pm Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu；x＝2,3,4；y＝2,3,4或以上稀土金属盐的水合物。 The preparation method of fuel cell catalyst as claimed in claim 7, is characterized in that, described rare earth metal precursor comprises scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, Soluble salts of at least five metals among holmium, erbium, thulium, ytterbium, and lutetium, the soluble salts are MClx, MIx , MBrx , MFx , M( NO3 ) x , Mx ( SO4 ) y , M At least one of (Ac) x , Mx(PO 4 ) y , M x (C 2 O 4 ) y , where M=Sc, Y, La, Ce, Pr, Nd, Pm Sm, Eu, Gd, Tb , Dy, Ho, Er, Tm, Yb, Lu; x = 2, 3, 4; y = 2, 3, 4 or more hydrates of rare earth metal salts.
  10. 如权利要求9所述的燃料电池催化剂的制备方法，其特征在于，所述溶液中稀土金属前驱体和碱金属盐的摩尔浓度比为1:2～20，稀土金属前驱体摩尔浓度之和为1～1000mmol/L，且各稀土金属前驱体含量为不为0的任意比例。The preparation method of fuel cell catalyst as claimed in claim 9, is characterized in that, the molar concentration ratio of rare earth metal precursor and alkali metal salt in described solution is 1:2～20, and the sum of molar concentration of rare earth metal precursor is 1-1000mmol/L, and the content of each rare earth metal precursor is in any ratio other than zero.
  11. 如权利要求1所述的燃料电池催化剂的制备方法，其特征在于，在将所述第二混合物于600℃-1000℃温度下，先在N 2中煅烧0.2-5h，再在NH 3中煅烧0.2-5h，，得到烧结产物的步骤中，具体为： The preparation method of fuel cell catalyst according to claim 1, characterized in that, at the temperature of 600°C-1000°C, the second mixture is first calcined in N for 0.2-5h , and then calcined in NH 0.2-5h, in the step of obtaining the sintered product, specifically:
    将所述第二混合物抽滤并真空干燥后研磨均匀得到固体样品，将所述固体样品后在N 2气流下加热到600-1000℃，并煅烧0.2-5h；降到室温后，将得到的固体粉末放到NH 3气流下加热到600-1000℃，并煅烧0.2-5h，降到室温下得到烧结产物。 The second mixture was suction-filtered and vacuum-dried to obtain a solid sample, which was then heated to 600-1000°C under N2 flow and calcined for 0.2-5h; after cooling down to room temperature, the obtained The solid powder is heated to 600-1000°C under NH 3 flow, and calcined for 0.2-5h, and then cooled to room temperature to obtain a sintered product.
  12. 如权利要求1所述的燃料电池催化剂的制备方法，其特征在于，在将所述烧结产物真空干燥得到所述燃料电池催化剂的步骤中，具体包括：The preparation method of the fuel cell catalyst according to claim 1, characterized in that, in the step of vacuum drying the sintered product to obtain the fuel cell catalyst, specifically comprising:
    将所述烧结产物在40-80℃下酸洗2-8h，洗涤完成后抽滤得到固体样品，将所述固体样品进行真空烘干，再将得到的产物进行酸洗，再次真空烘干得到所述燃料电池催化剂。Pickling the sintered product at 40-80°C for 2-8 hours, suction filtering to obtain a solid sample after washing, vacuum-drying the solid sample, then acid-washing the obtained product, and vacuum-drying again to obtain The fuel cell catalyst.
  13. 一种燃料电池催化剂，其特征在于，由权利要求1至12任一项所述的燃料电池催化剂的制备方法制备得到。A fuel cell catalyst, characterized in that it is prepared by the method for preparing a fuel cell catalyst according to any one of claims 1 to 12.
  14. 一种燃料电池，其特征在于，添加有权利要求13所述的燃料电池催化剂。A fuel cell, characterized in that the fuel cell catalyst according to claim 13 is added.
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