WO2022099793A1 - Orr catalyst material, preparation method therefor, and use thereof - Google Patents

Orr catalyst material, preparation method therefor, and use thereof Download PDF

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WO2022099793A1
WO2022099793A1 PCT/CN2020/131613 CN2020131613W WO2022099793A1 WO 2022099793 A1 WO2022099793 A1 WO 2022099793A1 CN 2020131613 W CN2020131613 W CN 2020131613W WO 2022099793 A1 WO2022099793 A1 WO 2022099793A1
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catalyst
ceo
orr
solution
catalyst material
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PCT/CN2020/131613
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French (fr)
Chinese (zh)
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类延华
谭宁
张玉良
常雪婷
范润华
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上海海事大学
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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
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • 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 first aspect of the present invention relates to a catalyst material, in particular to an ORR catalyst material; the second aspect of the present invention also relates to a preparation method of the ORR catalyst material; the third aspect of the present invention relates to the ORR catalyst material as a hydrogen-oxygen fuel cell or Use of a metal-air battery cathode material and a hydrogen-oxygen fuel cell or metal-air battery.
  • Pt precious metal platinum
  • the current commercial catalysts are mainly carbon-supported Pt nanoparticles.
  • Pt particles are prone to migration, agglomeration, etc., resulting in a decrease in activity.
  • transition metals and heteroatoms are introduced to improve the catalytic activity while preventing the agglomeration of Pt, thereby improving the stability of the catalyst.
  • Pt is deposited on CeO 2 /porous PANI by electrodeposition.
  • CeO 2 is synthesized firstly, and then CeO 2 /Pani composite material is synthesized and prepared, and then Pt is deposited electrochemically.
  • the preparation method is complicated in process, and the distribution of Pt is not uniform enough.
  • the Chinese invention patent application with application publication number CN 107394222 A and application publication date of 2017.11.24 discloses cerium oxide/precious metal/graphene ternary composite material and its preparation method and application.
  • the preparation method of cerium oxide/precious metal/graphene ternary composite material is to dissolve trivalent Ce salt in a reducing organic solvent, then add graphene oxide, and react at 180°C-200°C for 12 -After 48 hours, wash and dry to obtain a composite material of cerium oxide and graphene; disperse the composite material of cerium oxide and graphene in a reducing organic solvent, add a compound containing precious metal, and react at 100-160 ° C for 1-6 After hours, washing and drying gave the product.
  • the patent application uses graphene as a raw material, and the cost is high; and a variety of organic solvents are used in the preparation process, which is inconvenient for industrial production and is not environmentally friendly enough.
  • the use of reducing organic solvents also introduces impurity ions to affect performance.
  • the Chinese invention patent application with the application publication number of CN 104716347 A and the application publication date of 2015.06.17 discloses a Pt-based fuel cell catalyst containing CeO 2 and a preparation method thereof.
  • the catalyst is prepared by uniformly mixing chloroplatinic acid solution and cerium nitrate, adding ethylene glycol and carbon black, ultrasonically mixing uniformly, adding NaOH dropwise, and heating to reflux in an oil bath. After the reaction solution was lowered to room temperature, the product was obtained after washing and drying.
  • the catalytic performance of carbon black used in this patent application is not very good, and more Pt needs to be used to make up for the lack of catalytic performance of carbon black.
  • Pt is mainly distributed on the surface of carbon black.
  • the preparation method of the patent application is mainly used in the laboratory, and in the industry, it involves heating and refluxing an oil bath, which is inconvenient to produce.
  • the Chinese invention patent with the application publication number of CN 103078123 A and the application publication date of 2013.05.01 discloses a fuel cell catalyst and a preparation method thereof.
  • the catalyst is prepared by dispersing graphite oxide and cerium nitrate in water, adjusting the pH value with ammonia water, and reacting to obtain CeO 2 /GN; ultrasonically dispersing the prepared CeO 2 /GN in ethylene glycol solution , adding chloroplatinic acid solution, adjusting the pH value, and reacting to obtain a Pt-CeO 2 /GN catalyst.
  • This patent application uses graphite oxide, and the resulting catalyst has low porosity and small specific surface area.
  • the application publication number is CN 101733094 A
  • the Chinese invention patent application with the application publication date of 2010.06.16 discloses a Pt-CeO 2 /graphene electrocatalyst and a preparation method thereof.
  • the preparation method of the catalyst is to ultrasonically disperse graphite oxide nanosheets In ethylene glycol, then add chloroplatinic acid solution, ceric ammonium nitrate aqueous solution and sodium acetate aqueous solution, and mix thoroughly, transfer the mixture to microwave hydrothermal reaction kettle, after microwave heating reaction, filter, wash, dry, A Pt - CeO2/graphene electrocatalyst was obtained.
  • the patent application uses graphene as a raw material, and the cost is high; the preparation method of the patent application involves microwave hydrothermal reaction, and the process is complicated.
  • the purpose of the first aspect of the present invention is to provide an ORR catalyst material.
  • the preparation method of the ORR catalyst material is simple, environmentally friendly and low in cost, so as to solve the problems of uneven dispersion of precious metals in ORR catalyst materials in the prior art, large amount of precious metals, and pores of catalyst materials.
  • the technical problems are low rate, small specific surface area, poor stability, insufficient catalytic performance, and the preparation method of catalyst material is complicated, not environmentally friendly, and high cost.
  • the present invention solves the above technical problems through the following technical solutions, and achieves the purpose of the present invention.
  • An ORR catalyst material is composed of micro-nano-scale CeO 2 , noble metal M and nitrogen-doped carbon material, the doping amount of nitrogen in carbon is 0.05-0.1:1 in molar ratio, and CeO 2 in the ORR catalyst material and noble metal M are uniformly distributed in the nitrogen-doped carbon material, the ORR catalyst material conforms to the following general formula:
  • the precious metal M is one or more of Pt, Pd and Au, x and y are mass percentages, the range of x is 5%-6%, preferably 5.5%-5.7%, and the range of y is 4%-12 %, preferably 4%-5%; more preferably, the precious metal M is Pt, and the particle size of the precious metal Pt particles is 3-8 nm;
  • the ORR catalyst material is a porous material with a specific surface area of 40m 2 /g-800m 2 /g, more preferably 600m 2 /g-800m 2 /g.
  • the purpose of the second aspect of the present invention is to provide a preparation method of an ORR catalyst material, and the preparation method of the ORR catalyst material is simple, environmentally friendly and low in cost.
  • the method coats cerium oxide in situ with a conductive polymer.
  • a catalyst precursor with evenly dispersed precious metal is obtained by adding precious metal acid radicals and doping the conductive polymer with precious metal acid radicals. Carbonization under the protection of argon atmosphere to obtain a ternary hybrid catalyst of cerium oxide-precious metal-nitrogen-doped carbon.
  • the prepared ORR catalyst material has a uniform dispersion of precious metals, a small amount of precious metals, high porosity, and large specific surface area.
  • the present invention solves the above technical problems through the following technical solutions, and achieves the purpose of the present invention.
  • a preparation method of ORR catalyst material comprising the following steps:
  • the catalyst precursor material is a conductive polymer composite material doped with noble metal acid radicals, and the chemical formula of the catalyst precursor material is CeO 2 /CP-MX n- ( This chemical formula only shows the composition of the catalyst precursor material, not the proportional relationship between the components), X is an acid radical, and n is 1 or 2;
  • step 2) using the CeO 2 to prepare the catalyst precursor material includes the following steps:
  • the molar ratio of the CeO 2 to the acid or salt of the noble metal M is 8-70:1;
  • the molar ratio of the conductive polymer monomer to the acid or salt of the noble metal M is 16-128:1;
  • the molar ratio of the oxidant to the conductive polymer monomer is 2-3:1;
  • the acid solution of the oxidant is a hydrochloric acid solution of the oxidant, and the molar ratio of the oxidant to the HCl in the hydrochloric acid is 1:3-4.
  • the acid or salt of the noble metal M is H 2 PdCl 4 , Pd(NH 3 ) 4 Cl 2 , Pd(NH 3 ) 2 Cl 2 , Pd(NH 3 ) 4 SO 4 , Pd(NH 3 ) 4 (NO 3 ) 2 , H 2 PtCl 6 , H 2 PtCl 4 , K 2 PtCl 6 , (NH 4 ) 2 PtCl 6 , K 2 PtCl 4 , (NH 4 ) 2 PtCl 4 , (NH 4 ) 2 PtCl 4 , One or more of HAuCl 4 , NaAuCl 4 , KAuCl 4 and their hydrates.
  • the conductive polymer monomer is one or both of polyaniline and polypyrrole; and/or
  • the oxidant is APS or FeCl 3 .
  • the step 3) carbonizing the catalyst precursor material at high temperature to prepare the ORR catalyst material includes the following steps: placing the catalyst precursor material under the protection of an inert gas atmosphere , with a heating rate of 5-20° C./min, rising from room temperature to 600-1000° C., reacting for 2-4 hours, and naturally cooling to obtain the ORR catalyst material.
  • a third aspect of the present invention aims to propose the use of the aforementioned ORR catalyst materials.
  • the use of the ORR catalyst material as described above is as a cathode electrode for a hydrogen-oxygen fuel cell or a metal-air battery.
  • the purpose of the fourth aspect of the present invention is to provide a hydrogen-oxygen fuel cell or metal-air battery, in which the ORR catalyst material of the hydrogen-oxygen fuel cell or metal-air battery is evenly dispersed in precious metals, the amount of precious metals is small, the catalyst material has high porosity, and has a high specific gravity.
  • the preparation method of the ORR catalyst material of the hydrogen-oxygen fuel cell or metal-air battery is simple, environmentally friendly and low in cost, so as to solve the ORR of the hydrogen-oxygen fuel cell or metal-air battery in the prior art.
  • the catalyst materials have the technical problems of uneven dispersion of precious metals, large amount of precious metals, low porosity, small specific surface area, poor stability, poor catalytic performance, and complex preparation methods of catalyst materials, not environmentally friendly, and high cost.
  • the present invention solves the above technical problems through the following technical solutions, and achieves the purpose of the present invention.
  • a hydrogen-oxygen fuel cell includes a cathode electrode, and the catalyst of the cathode electrode adopts the ORR catalyst material as described above or the ORR catalyst material prepared by any of the technical solutions described above.
  • a metal-air battery includes a cathode electrode, and the catalyst of the cathode electrode adopts the ORR catalyst material as described above or the ORR catalyst material prepared by any of the technical solutions described above.
  • the conductive polymer is coated with cerium oxide in situ.
  • the catalyst precursor material is further carbonized under the protection of nitrogen or argon atmosphere to obtain a cerium oxide-precious metal-nitrogen-doped carbon ternary hybrid catalyst.
  • cerium oxide is added to the solution synthesized by polyaniline and/or polypyrrole, and at the same time of chemical in-situ polymerization of polyaniline and/or polypyrrole, noble metal-acid-doped polyaniline and/or polypyrrole-coated polyaniline and/or polypyrrole are obtained.
  • the cerium oxide-coated composite material is coated with cerium oxide by the high-temperature carbonization catalyst precursor polyaniline and/or polypyrrole.
  • the polyaniline and/or polypyrrole precursor is gradually transformed into an N-doped carbon material,
  • the noble metal oxides doped in the polyaniline structure are thermally reduced to form uniformly dispersed noble metal M nanoparticles.
  • the method obtains uniformly dispersed noble metal M nanoparticles, cerium oxide, and N-doped ternary carbon catalyst materials in one step.
  • the preparation method is simple, convenient, environmentally friendly, efficient and low in cost, and a ternary composite system catalyst with high porosity, high specific surface area and high performance is obtained by in-situ polymerization and high-temperature carbonization; no reducing agent is used in the preparation process (now There are techniques using reducing agents that introduce unwanted ions that affect performance).
  • the conductive polymer as the nitrogen source and carbon source of the catalyst, by adding precious metal acid radicals to the polymerization solution of the conductive polymer, and doping the precious metal acid radical in the conductive polymer during the polymerization process, a catalyst precursor with evenly dispersed precious metals can be obtained.
  • the bulk material; nanoparticles of noble metal M are obtained in one step by high-temperature carbonization, and the particle size is about 5 nm, which is uniformly dispersed on the surface of the material.
  • Polyaniline and/or polypyrrole are used as the carbon source and nitrogen source of the catalyst. Through high temperature carbonization, nitrogen-doped carbon is obtained. The incorporation of nitrogen increases the defect degree of the catalyst and has a certain targeting effect on the precious metal M. The particle size and distribution of the generated precious metal are effectively controlled, and the precious metal M is dispersed in the porous carbon material matrix, not only supported on the surface, thereby improving the catalytic performance stability of the material, improving the dispersion of the precious metal M particles and the catalyst. The conductivity of the catalyst further improves the catalytic activity of the catalyst, and reduces the amount of precious metal M to a certain extent.
  • the synergistic catalytic effect of transition metal oxide CeO2 and noble metal M nanoparticles further enhances the catalytic activity.
  • the three-way catalytic system designed in the present invention can greatly improve the catalytic performance of the material through the synergistic effect of the three.
  • the noble metal is effectively compounded with the transition metal oxide CeO 2 and the heteroatom N, which is helpful for the dispersion of the noble metal and the transfer of electrons on the surface of the catalyst, so it has high catalytic activity and stability.
  • Figure 1 is a flow diagram of a method of preparing an ORR catalyst material in an embodiment.
  • Example 2 is the XRD pattern of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% catalyst prepared in Example 1.
  • Example 3 is a TEM image of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% catalyst prepared in Example 1.
  • Example 4 is the STEM image of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% catalyst prepared in Example 1.
  • Figure 5 is a linear sweep voltammetry (LSV) comparison diagram of Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% prepared in Example 1 and commercial platinum carbon 20% (mass fraction, the same below) Pt/C catalyst.
  • LSV linear sweep voltammetry
  • Figure 6 is a comparison chart of the stability of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% prepared in Example 1 and the commercial platinum carbon 20% Pt/C catalyst.
  • Example 7 is a nitrogen adsorption and desorption isotherm curve diagram of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% catalyst prepared in Example 1 (specific surface area value: 636.96 m 2 /g).
  • Example 8 is the XRD pattern of the Pt 5.14% /NC 90.44% /(CeO 2 ) 4.42% catalyst prepared in Example 2.
  • Example 9 is a TEM image of the Pt 5.14% /NC 90.44% /(CeO 2 ) 4.42% catalyst prepared in Example 2.
  • FIG. 10 is a comparison diagram of linear sweep voltammetry (LSV) between the Pt 5.14% /NC 90.44% /(CeO 2 ) 4.42% catalyst prepared in Example 2 and the commercial platinum carbon 20% Pt/C catalyst.
  • LSV linear sweep voltammetry
  • Example 11 is a nitrogen adsorption and desorption isotherm curve diagram of the Pt 5.14% /NC 90.44% /(CeO 2 ) 4.42% catalyst prepared in Example 2 (specific surface area value: 603.75 m 2 /g).
  • FIG. 13 is a linear sweep voltammetry (LSV) comparison diagram of the Pt 6.8% /NC 89.36% /(CeO 2 ) 3.84% catalyst prepared in Example 3 and the commercial platinum carbon 20% Pt/C catalyst.
  • LSV linear sweep voltammetry
  • Example 14 is a nitrogen adsorption and desorption isotherm curve diagram of the Pt 6.8% /NC 89.36% /(CeO 2 ) 3.84% catalyst prepared in Example 3 (specific surface area value: 68.34 m 2 /g).
  • Figure 15 is a linear scan obtained by testing the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% prepared in Example 4 with a commercial platinum-carbon 20% Pt/C catalyst in an oxygen-saturated 0.1 M HClO 4 solution Voltammetry (LSV) comparison chart.
  • Figure 16 shows Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% prepared in Example 1, Pt/NC prepared in Comparative Example 1, NC/CeO 2 prepared in Comparative Example 2 , and commercial platinum carbon 20 %Pt/C catalyst, line sweep voltammetry (LSV) comparison graph obtained by testing in an oxygen-saturated solution of 0.1M KOH.
  • LSV line sweep voltammetry
  • An ORR catalyst material is composed of micro-nano-scale (referring to micro-scale and/or nano-scale) CeO 2 , noble metal M and nitrogen-doped carbon material, and the doping amount of nitrogen in carbon is 0.05-0.1 in molar ratio: 1. CeO 2 and precious metal M in the ORR catalyst material are uniformly distributed in the nitrogen-doped carbon material, and the ORR catalyst material conforms to the following general formula:
  • the precious metal M is one or more of Pt, Pd and Au, x and y are mass fractions, and the range of x is 5%-8%, preferably 5.5%-5.7%, more preferably 5.6%-5.7%, The range of y is 4%-12%, preferably 4%-5%, more preferably 4.2%-4.3%; preferably, the precious metal M is Pt, and the particle size of the precious metal Pt particles is 3-8 nm.
  • the ORR catalyst material is a porous material with a specific surface area of 40m 2 /g-800m 2 /g.
  • a preparation method of the aforementioned ORR catalyst material comprises the following steps:
  • the catalyst precursor material is a conductive polymer composite material doped with noble metal acid radicals, and the chemical formula of the catalyst precursor material is CeO 2 /CP-MX n- , X is an acid radical, and n is 1 or 2;
  • micro-scale and/or nano-scale CeO 2 can be purchased, and can also be prepared by the following methods:
  • 1.1) dissolve cerium nitrate and sodium hydroxide in deionized water, adjust the pH value of the solution, and stir to obtain a reaction solution; preferably, in the step 1.1), the molar ratio of the cerium nitrate and the sodium hydroxide is 1:4, the pH value is 12, and the uniform stirring is magnetic stirring for 2h;
  • the ambient temperature of the reaction solution is adjusted to the reaction temperature for the reaction to obtain a solution containing CeO 2 ; preferably, the reaction temperature is 60° C., and the reaction time is 1 h;
  • CeO 2 is obtained after drying and annealing; preferably, the drying temperature is 130° C., and the annealing time is 4 h.
  • the step 2) utilizing the CeO 2 to prepare the catalyst precursor material includes the following steps:
  • the catalyst precursor material is prepared by in situ polymerization.
  • the molar ratio range of the CeO 2 to the acid or salt of the precious metal M is 8-70:1;
  • the molar ratio of the conductive polymer monomer to the acid or salt of the precious metal M is in the range of 16-128:1;
  • the molar ratio of the oxidant to the conductive polymer monomer is in the range of 2-3:1;
  • the acid solution of the oxidant is a hydrochloric acid solution of the oxidant, and the molar ratio of the oxidant to the HCl in the hydrochloric acid is 1:3-4.
  • the acid or salt of the noble metal M is H 2 PdCl 4 , Pd(NH 3 ) 4 Cl 2 , Pd(NH 3 ) 2 Cl 2 , Pd(NH 3 ) 4 SO 4 , Pd(NH 3 ) 4 (NO 3 ) ) 2 , H 2 PtCl 6 , H 2 PtCl 4 , K 2 PtCl 6 , (NH 4 ) 2 PtCl 6 , K 2 PtCl 4 , (NH 4 ) 2 PtCl 4 , (NH 4 ) 2 PtCl 4 , HAuCl 4 , NaAuCl 4 , KAuCl 4 and their hydrates one or more of them.
  • the conductive polymer monomer is one or both of polyaniline and polypyrrole; the oxidant is APS or FeCl 3 .
  • the step 3) carbonizing the catalyst precursor material at high temperature to obtain the ORR catalyst material includes the following steps:
  • the catalyst precursor material is raised from room temperature to 600-1000°C at a heating rate of 5-20°C/min, reacted for 2-4 hours, and naturally cooled to obtain the ORR catalyst material. .
  • ORR catalyst material as described above can be used as a cathode electrode for a hydrogen-oxygen fuel cell or a metal-air battery.
  • a fuel cell includes a cathode electrode, and the catalyst of the cathode electrode adopts the ORR catalyst material described in this specific embodiment or the ORR catalyst material prepared according to this specific embodiment.
  • a metal-air battery, the catalyst including the cathode electrode adopts the ORR catalyst material described in this specific embodiment or the ORR catalyst material prepared according to this specific embodiment.
  • the catalyst precursor material was heated at a rate of 10 °C/min, and the temperature was increased from room temperature to 800 °C, and the reaction was carried out for 2 hours. After natural cooling, the final product was obtained . NC 90.14% /(CeO 2 ) 4.22% .
  • the final product obtained above was used as a catalyst to conduct electrochemical tests in an electrolyte solution of 0.1 MKOH using a rotating disk electrode and an electrochemical workstation.
  • Figure 2 is the XRD pattern of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% catalyst (abbreviated as Pt 5.64% /NC/CeO 2 in the figure, the same below) prepared in Example 1, from which we can obtain The final product is known to contain Pt and CeO 2 .
  • the particle size of Pt is 3-8 nm from the XRD pattern according to Scherrerequation.
  • Figure 3 is a TEM image of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% catalyst prepared in Example 1, which was obtained at an accelerating voltage of 200kV. From this image, it can be known that the Pt ( The black or gray circles in the figure) are evenly distributed.
  • Figure 4 is the STEM image of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% catalyst prepared in Example 1, which was obtained at an accelerating voltage of 200kV. O, Pt, N, Ce are evenly distributed.
  • FIG. 5 is a comparison diagram of linear sweep voltammetry (LSV) between the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% prepared in Example 1 and the commercial platinum carbon 20% Pt/C catalyst. 20% Pt/C was purchased from Shanghai McLean Biochemical Technology Co., Ltd. (the same as in the following examples).
  • Example 1 By comparing the linear scanning curve of Example 1 and commercial platinum carbon 20%Pt/C, it is found that the initial potential of Example 1 is 0.95V (Vs.RHE), the half-wave potential is 0.88V (Vs.RHE), and the limiting current density 5.88mA/cm 2 , both of which are better than commercial platinum-carbon 20%Pt/C with an initial potential of 0.95V (Vs.RHE), a half-wave potential of 0.87V (Vs.RHE), and a limiting current density of 4.68mA/cm 2 .
  • Figure 6 is a comparison chart of the stability of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% prepared in Example 1 and the commercial platinum carbon 20% Pt/C catalyst.
  • the stability test results of Pt 5.64% /NC/CeO 2 prepared in Example 1 and commercial platinum carbon 20% Pt/C it is found that the half-wave potential of Example 1 is negatively shifted by 30mV, and the limiting current density is increased by 0.39mAcm -2 , and compared with the commercial platinum carbon 20% Pt/C, the half-wave potential is negatively shifted by 40mV, and the limiting current density is reduced by 0.36mAcm -2 . It can be seen that in the alkaline electrolyte 0.1M KOH, the stability of Example 1 is better. On commercial platinum carbon 20% Pt/C.
  • Example 7 is a nitrogen adsorption and desorption isotherm curve diagram of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% catalyst prepared in Example 1 (specific surface area value: 636.96 m 2 /g).
  • Embodiment 2 (different from embodiment 1 is that potassium chloroplatinate consumption is 0.05g)
  • the catalyst precursor material was heated at a rate of 10 °C/min, and the temperature was increased from room temperature to 800 °C, and the reaction was carried out for 2 hours. After natural cooling, the final product was obtained . NC 90.44% /(CeO 2 ) 4.42% .
  • the final product obtained above was made into a catalyst slurry, and the same electrochemical test as in Example 1 was carried out in an electrolyte solution of 0.1 MKOH using a rotating disk electrode and an electrochemical workstation.
  • Figure 8 is the XRD pattern of the Pt 5.14% /NC 90.44% /(CeO 2 ) 4.42% catalyst (abbreviated as Pt 5.14% /NC/CeO 2 in the figure, the same below) prepared in Example 2, from which we can obtain The final product is known to contain Pt and CeO 2 .
  • the particle size of Pt is 5-8 nm from the XRD pattern according to Scherrerequation.
  • Figure 9 is a TEM image of the Pt 5.14% /NC 90.44% /(CeO 2 ) 4.42% catalyst prepared in Example 2, which was obtained at an accelerating voltage of 200kV. From this image, it can be known that Pt in the product evenly distributed.
  • FIG. 10 is a comparison diagram of linear sweep voltammetry (LSV) between the Pt 5.14% /NC 90.44% /(CeO 2 ) 4.42% prepared in Example 2 and the commercial platinum carbon 20% Pt/C catalyst.
  • LSV linear sweep voltammetry
  • Example 11 is a nitrogen adsorption and desorption isotherm curve diagram of the Pt 5.14% /NC 90.44% /(CeO 2 ) 4.42% catalyst prepared in Example 2 (specific surface area value: 603.75 m 2 /g).
  • Embodiment 3 (different from embodiment 1 is that potassium chloroplatinate consumption is 0.2g)
  • the catalyst precursor material was heated at a rate of 10 °C/min, from room temperature to 800 °C, and reacted for 2 hours. After natural cooling, the final product was obtained. After testing, the final product was Pt 6.8% / NC 89.36% /(CeO 2 ) 3.84% .
  • the final product obtained above was made into a catalyst slurry, and the same electrochemical test as in Example 1 was carried out in an electrolyte solution of 0.1 MKOH using a rotating disk electrode and an electrochemical workstation.
  • Figure 12 is the XRD pattern of the Pt 6.8% /NC 89.36% /(CeO 2 ) 3.84% catalyst prepared in Example 3 (abbreviated as Pt 6.8% /NC/CeO 2 in the figure), from which the final product can be known Contains Pt and CeO 2 .
  • FIG. 13 is a linear sweep voltammetry (LSV) comparison diagram of the Pt 6.8% /NC 89.36% /(CeO 2 ) 3.84% catalyst prepared in Example 3 and the commercial platinum carbon 20% Pt/C catalyst.
  • the onset potential of Example 3 is 0.89V (Vs.RHE)
  • the half-wave potential is 0.77V (Vs.RHE)
  • the limiting current density is 4.24mA/cm 2 , which is inferior to the onset potential of Example 1, which is 0.95V (Vs.RHE).
  • the half-wave potential is 0.88V (Vs.RHE), and the limiting current density is 5.88mA/cm 2 ; it is also inferior to the onset potential of commercial platinum carbon 20%Pt/C of 0.95V (Vs.RHE), and the half-wave potential is 0.87V (Vs.RHE), limiting current density 4.68 mA/cm 2 .
  • Example 14 is a nitrogen adsorption and desorption isotherm diagram of the Pt 6.8% /NC 89.36% /(CeO 2 ) 3.84% catalyst prepared in Example 3 (specific surface area: 68.34 m 2 /g).
  • Example 4 (the difference from Example 1 is that it was tested in an acidic electrolyte)
  • 0.6g of cerium oxide and 0.1g of potassium chloroplatinate (K 2 PtCl 6 ) were added to 40ml of 1mol/L HCl solution to obtain solution I, after ultrasonic dispersion for 2 hours, 0.6ml of aniline monomer was added to solution I to obtain solution II .
  • 0.6 g of APS was dissolved in 10 ml of 1 mol/L HCl solution to obtain solution III, which was uniformly dispersed by ultrasound for 2 hours. The dripping speed of solution III was controlled so that it was slowly dripped into solution II. Keep at 5°C and react for 5 hours. The reaction was accompanied by magnetic stirring. After filtering and washing, a catalyst precursor material is obtained.
  • the catalyst precursor material was heated at a rate of 10 °C/min, and the temperature was increased from room temperature to 800 °C, and the reaction was carried out for 2 hours. After natural cooling, the final product was obtained . NC 90.14% /(CeO 2 ) 4.22% .
  • the electrolytic solution was changed in electrochemical tests.
  • the final product obtained above was made into a catalyst slurry, and the same electrochemical test as in Example 1 was carried out in an electrolyte solution of 0.1 M HClO 4 using a rotating disk electrode and an electrochemical workstation.
  • Figure 15 shows the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% (abbreviated as Pt 5.64% /NC/CeO 2 in the figure) prepared in Example 4 and the commercial platinum carbon 20% Pt/C catalyst in oxygen saturation Comparison of linear sweep voltammetry (LSV) obtained by testing in a solution of 0.1 M HClO 4 .
  • LSV linear sweep voltammetry
  • the catalyst precursor material was heated at a rate of 10 °C/min, from room temperature to 800 °C, and reacted for 2 hours. After natural cooling, the final product was obtained. The final product was detected as Pt/NC. Compared to Example 1, Example 2 did not add cerium oxide.
  • the final product obtained above was used as a catalyst to conduct electrochemical tests in an electrolyte solution of 0.1 MKOH using a rotating disk electrode and an electrochemical workstation.
  • Figure 16 shows Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% prepared in Example 1, Pt/NC prepared in Comparative Example 1, NC/CeO 2 prepared in Comparative Example 2 , and commercial platinum carbon 20 %Pt/C catalyst, line sweep voltammetry (LSV) comparison graph obtained by testing in an oxygen-saturated solution of 0.1M KOH.
  • LSV line sweep voltammetry
  • Comparative Example 1 According to the linear scanning curve of Comparative Example 1, it is found that the initial potential of Comparative Example 1 is 0.94V (Vs.RHE), the half-wave potential is 0.69V (Vs.RHE), and the limiting current density is 4.47mA/cm 2 , which are all inferior to The initial potential of Example 1 was 0.95V (Vs.RHE), the half-wave potential was 0.88V (Vs.RHE), and the limiting current density was 5.88mA/cm 2 .
  • Comparative Example 1 it is found from the linear scanning graph of Comparative Example 1 that the initial potential of Comparative Example 2 is 0.88V (Vs.RHE), the half-wave potential is 0.79V (Vs.RHE), and the limiting current density is 3.38mA/cm 2 , are inferior to the initial potential of Example 1 of 0.95V (Vs.RHE), the half-wave potential of 0.88V (Vs.RHE), and the limiting current density of 5.88mA/cm 2 .
  • RDE Rotating Disk Electrode
  • the preparation method of the working electrode is as follows: 10 ⁇ L of the electrocatalyst slurry is dropped onto the surface of the glassy carbon electrode using a pipette gun, and dried under an infrared lamp to obtain a uniformly dispersed electrocatalyst thin layer.
  • the electrocatalyst loading is 0.24 mg ⁇ cm -2 .
  • the test was carried out in 0.1 mol ⁇ L -1 KOH aqueous solution saturated with O 2 , the scanning speed was 10 mV ⁇ s -1 , the scanning interval was 0.2–1.2 V (vs RHE), and the electrode speed was 1600 r ⁇ min -1 .
  • the test was carried out in a 0.1 mol ⁇ L -1 KOH solution saturated with O 2 , the cyclic voltammetry potential range of the working electrode was set to be 0.2–1.2 V (vs RHE), the number of scan cycles was 2000, and the scan rate was 50 mV. ⁇ s -1 . After 2000 cycles, the cyclic voltammetry curve of the working electrode and the linear sweep voltammetry curve of the electrode rotating speed of 1600r ⁇ min -1 were recorded.
  • phase purity and crystal form of the synthesized samples were characterized using an X-ray diffractometer (XRD) (Model: X'Pert PRO Manufacturer: PANalytical, The Netherlands) at a voltage of 40kV, a current of 100mA, and a scan rate of 1° /min, the 2 ⁇ range is 10°-90°.
  • XRD X-ray diffractometer
  • TEM field emission transmission electron microscope
  • HAADF high-angle annular dark field
  • STEM scanning transmission electron microscopy
  • TEM field emission transmission electron microscope
  • HAADF high-angle annular dark field
  • STEM scanning transmission electron microscopy
  • the low-temperature nitrogen gas adsorption and desorption test was performed with a BELSORP-max instrument (MicrotracBEL, Japan), and the electrocatalyst specific surface area was calculated using the Brunauer-Emmett-Teller (BET) method.
  • BET Brunauer-Emmett-Teller
  • ICP-OES Inductively coupled plasma optical emission spectrometer (ICP-OES) (model: Agilent 720ES) is used to detect the accurate content of metals in the catalyst, thereby calculating the real mass activity of the catalyst .
  • Sample preparation Dissolve the catalyst in aqua regia, the mass concentration is between 5-10 mg L -1 , after the dissolution is complete, take the middle layer clear liquid and filter it for testing.

Abstract

An ORR catalyst material and a preparation method therefor. The present application also relates to a use of the ORR catalyst material as a cathode material of a hydrogen-oxygen fuel cell or a metal-air cell, and a hydrogen-oxygen fuel cell or a metal-air cell. The ORR catalyst material satisfies the following general formula: Mx/N-C(1-x-y)/(CeO2)y (I), wherein a precious metal M is one or more than two of Pt, Pd, and Au, x and y represent mass percentages, x is in the range of 5%-6%, and y is in the range of 4%-12%. The key point of the preparation method for the ORR catalyst material is that: a catalyst precursor material is a conductive polymer composite material doped with precious metal acid radicals. The catalyst material solves the technical problems in the prior art that ORR catalyst materials have uneven dispersion of precious metals and poor catalytic performance, and preparation methods for catalyst materials are complicated, not environmental-friendly, and high in costs.

Description

一种ORR催化剂材料及其制备方法和用途A kind of ORR catalyst material and preparation method and use thereof 技术领域technical field
本发明第一方面涉及一种催化剂材料，特别涉及一种ORR催化剂材料；本发明第二方面还涉及该ORR催化剂材料的制备方法；本发明第三方面涉及该ORR催化剂材料作为氢氧燃料电池或金属空气电池阴极材料的用途以及一种氢氧燃料电池或金属空气电池。The first aspect of the present invention relates to a catalyst material, in particular to an ORR catalyst material; the second aspect of the present invention also relates to a preparation method of the ORR catalyst material; the third aspect of the present invention relates to the ORR catalyst material as a hydrogen-oxygen fuel cell or Use of a metal-air battery cathode material and a hydrogen-oxygen fuel cell or metal-air battery.
背景技术Background technique
随着全球经济的迅速发展，环境污染和能源短缺日益严重，如何能够更有效和稳定地生产、利用可再生能源成为了目前人类亟待解决的课题。虽然风能、太阳能、水电和潮汐能作为绿色清洁能源，现已成为化石燃料的替代品，但这些严重依赖自然环境产生的能源存在间歇性和波动性的问题。随着不断探索，开发出的金属空气电池、燃料电池和电化学超级电容器都是非常有效和实用的电化学能量转换存储技术，并且在许多领域有着非常广泛的应用。其中，燃料电池引起了人们的极大关注，这是因为它们具有高功率密度和低污染的特点。氧气还原反应(ORR)作为燃料电池中最重要的阴极反应，其缓慢的反应动力学严重限制燃料电池的能量输出。With the rapid development of the global economy, environmental pollution and energy shortage are becoming more and more serious. How to produce and utilize renewable energy more efficiently and stably has become an urgent issue for human beings. Although wind, solar, hydroelectric and tidal energy are green and clean energy sources and have now become alternatives to fossil fuels, these sources of energy, which are heavily dependent on the natural environment, suffer from intermittent and fluctuating energy. With the continuous exploration, the developed metal-air batteries, fuel cells and electrochemical supercapacitors are very efficient and practical electrochemical energy conversion and storage technologies, and have a very wide range of applications in many fields. Among them, fuel cells have attracted great attention because of their high power density and low pollution. Oxygen reduction reaction (ORR) is the most important cathode reaction in fuel cells, and its slow reaction kinetics severely limits the energy output of fuel cells.
为了实现燃料电池的规模应用，目前亟待解决的问题之一就是提高电极中催化剂的活性，降低贵金属铂(Pt)的用量从而降低成本。目前商业化的催化剂以碳担载Pt纳米颗粒为主，然而在燃料电池运行过程中，Pt颗粒容易发生迁 移、团聚等导致活性降低。为了降低Pt用量、提高催化剂的活性，将过渡金属和杂原子引入，提高催化活性的同时，防止Pt发生团聚，从而提高催化剂的稳定性。In order to realize the large-scale application of fuel cells, one of the urgent problems to be solved is to improve the activity of the catalyst in the electrode and reduce the amount of precious metal platinum (Pt) to reduce the cost. The current commercial catalysts are mainly carbon-supported Pt nanoparticles. However, during the operation of fuel cells, Pt particles are prone to migration, agglomeration, etc., resulting in a decrease in activity. In order to reduce the amount of Pt and improve the activity of the catalyst, transition metals and heteroatoms are introduced to improve the catalytic activity while preventing the agglomeration of Pt, thereby improving the stability of the catalyst.
申请公布号为CN 108384046 A、申请公布日为2018.08.10的中国发明专利申请公开了一种Pt-CeO 2/多孔聚苯胺电极材料的制备。在该专利申请中，是利用电沉积的方法将Pt沉积在CeO 2/porous PANI上。该制备方法首先合成CeO 2,而后合成制备了CeO 2/Pani复合材料，再之后通过电化学的方式沉积了Pt。该制备方法工艺复杂，Pt的分布不够均匀。 The Chinese invention patent application with the application publication number of CN 108384046 A and the application publication date of 2018.08.10 discloses the preparation of a Pt-CeO 2 /porous polyaniline electrode material. In this patent application, Pt is deposited on CeO 2 /porous PANI by electrodeposition. In this preparation method, CeO 2 is synthesized firstly, and then CeO 2 /Pani composite material is synthesized and prepared, and then Pt is deposited electrochemically. The preparation method is complicated in process, and the distribution of Pt is not uniform enough.
申请公布号为CN 107394222 A、申请公布日为2017.11.24的中国发明专利申请公开了氧化铈/贵金属/石墨烯三元复合材料及其制备方法和应用。在该专利申请中，氧化铈/贵金属/石墨烯三元复合材料的制备方法是将三价Ce盐溶于还原性有机溶剂中，再加入氧化石墨烯，通过180℃-200℃条件下反应12-48小时后，洗涤干燥得到氧化铈和石墨烯的复合材料；将氧化铈及石墨烯的复合材料分散在还原性的有机溶剂中，加入含有贵金属的化合物，在100-160℃反应1-6小时后，洗涤干燥得到产物。该专利申请以石墨烯为原料，成本高；而且制备过程使用了多种有机溶剂，不便于工业化生产，而且不够环保。还原性有机溶剂的使用也引入了杂质离子影响性能。The Chinese invention patent application with application publication number CN 107394222 A and application publication date of 2017.11.24 discloses cerium oxide/precious metal/graphene ternary composite material and its preparation method and application. In this patent application, the preparation method of cerium oxide/precious metal/graphene ternary composite material is to dissolve trivalent Ce salt in a reducing organic solvent, then add graphene oxide, and react at 180℃-200℃ for 12 -After 48 hours, wash and dry to obtain a composite material of cerium oxide and graphene; disperse the composite material of cerium oxide and graphene in a reducing organic solvent, add a compound containing precious metal, and react at 100-160 ° C for 1-6 After hours, washing and drying gave the product. The patent application uses graphene as a raw material, and the cost is high; and a variety of organic solvents are used in the preparation process, which is inconvenient for industrial production and is not environmentally friendly enough. The use of reducing organic solvents also introduces impurity ions to affect performance.
申请公布号为CN 104716347 A、申请公布日为2015.06.17的中国发明专利申请公开了一种含CeO 2的Pt基燃料电池催化剂及其制备方法。该专利申请中，催化剂的制备方法是将氯铂酸溶液与硝酸铈均匀混合后，加入乙二醇和碳黑，超声混合均匀后，逐滴加入NaOH后，油浴加热回流。待反应溶液降至室温后，洗涤干燥后得到产物。该专利申请使用的炭黑催化性能不是很好，需要使用更 多的Pt弥补炭黑催化性能的不足。而且该专利申请中Pt主要分布在炭黑表面。该专利申请的制备方法主要用在实验室，用于工业则涉及油浴加热回流，生产不便。 The Chinese invention patent application with the application publication number of CN 104716347 A and the application publication date of 2015.06.17 discloses a Pt-based fuel cell catalyst containing CeO 2 and a preparation method thereof. In this patent application, the catalyst is prepared by uniformly mixing chloroplatinic acid solution and cerium nitrate, adding ethylene glycol and carbon black, ultrasonically mixing uniformly, adding NaOH dropwise, and heating to reflux in an oil bath. After the reaction solution was lowered to room temperature, the product was obtained after washing and drying. The catalytic performance of carbon black used in this patent application is not very good, and more Pt needs to be used to make up for the lack of catalytic performance of carbon black. Moreover, in this patent application, Pt is mainly distributed on the surface of carbon black. The preparation method of the patent application is mainly used in the laboratory, and in the industry, it involves heating and refluxing an oil bath, which is inconvenient to produce.
申请公布号为CN 103078123 A、申请公布日为2013.05.01的中国发明专利公开了一种燃料电池催化剂及其制备方法。在该专利申请中，催化剂的制备方法是将氧化石墨与硝酸铈分散在水中，用氨水调节pH值，反应得CeO 2/GN；将制得的CeO 2/GN超声分散在乙二醇溶液中，加入氯铂酸溶液，调节pH值，反应得到Pt-CeO 2/GN催化剂。该专利申请使用的是氧化石墨，最终得到的催化剂孔隙率不高，比表面积不大。 The Chinese invention patent with the application publication number of CN 103078123 A and the application publication date of 2013.05.01 discloses a fuel cell catalyst and a preparation method thereof. In this patent application, the catalyst is prepared by dispersing graphite oxide and cerium nitrate in water, adjusting the pH value with ammonia water, and reacting to obtain CeO 2 /GN; ultrasonically dispersing the prepared CeO 2 /GN in ethylene glycol solution , adding chloroplatinic acid solution, adjusting the pH value, and reacting to obtain a Pt-CeO 2 /GN catalyst. This patent application uses graphite oxide, and the resulting catalyst has low porosity and small specific surface area.
申请公布号为CN 101733094 A，申请公布日为2010.06.16的中国发明专利申请公开了一种Pt-CeO 2/石墨烯电催化剂及其制备方法，催化剂的制备方法是将氧化石墨纳米片超声分散在乙二醇中，然后加入氯铂酸溶液，硝酸铈铵水溶液和醋酸钠水溶液，并充分混合，将混合物转移到微波水热反应釜中，微波加热反应后，经过滤、洗涤、烘干，得到Pt-CeO 2/石墨烯电催化剂。该专利申请以石墨烯为原料，成本高；该专利申请的制备方法涉及微波水热反应，过程复杂。 The application publication number is CN 101733094 A, and the Chinese invention patent application with the application publication date of 2010.06.16 discloses a Pt-CeO 2 /graphene electrocatalyst and a preparation method thereof. The preparation method of the catalyst is to ultrasonically disperse graphite oxide nanosheets In ethylene glycol, then add chloroplatinic acid solution, ceric ammonium nitrate aqueous solution and sodium acetate aqueous solution, and mix thoroughly, transfer the mixture to microwave hydrothermal reaction kettle, after microwave heating reaction, filter, wash, dry, A Pt - CeO2/graphene electrocatalyst was obtained. The patent application uses graphene as a raw material, and the cost is high; the preparation method of the patent application involves microwave hydrothermal reaction, and the process is complicated.
发明内容SUMMARY OF THE INVENTION
本发明第一方面目的在于提出一种ORR催化剂材料，该ORR催化剂材料的制备方法简单、环保、成本低，以解决现有技术中ORR催化剂材料存在贵金属分散不均匀，贵金属用量大，催化剂材料孔隙率低、比表面积小、稳定性差、催化性能不够好，及催化剂材料的制备方法复杂、不环保、成本高的技术问题。The purpose of the first aspect of the present invention is to provide an ORR catalyst material. The preparation method of the ORR catalyst material is simple, environmentally friendly and low in cost, so as to solve the problems of uneven dispersion of precious metals in ORR catalyst materials in the prior art, large amount of precious metals, and pores of catalyst materials. The technical problems are low rate, small specific surface area, poor stability, insufficient catalytic performance, and the preparation method of catalyst material is complicated, not environmentally friendly, and high cost.
本发明通过以下技术方案解决上述技术问题，达到本发明的目的。The present invention solves the above technical problems through the following technical solutions, and achieves the purpose of the present invention.
一种ORR催化剂材料，由微纳米级CeO 2、贵金属M和氮掺杂的碳材料组成，氮在碳中的掺杂量按摩尔比为0.05-0.1：1，所述ORR催化剂材料中CeO 2和贵金属M均匀地分布在氮掺杂的碳材料中，所述ORR催化剂材料符合以下通式： An ORR catalyst material is composed of micro-nano-scale CeO 2 , noble metal M and nitrogen-doped carbon material, the doping amount of nitrogen in carbon is 0.05-0.1:1 in molar ratio, and CeO 2 in the ORR catalyst material and noble metal M are uniformly distributed in the nitrogen-doped carbon material, the ORR catalyst material conforms to the following general formula:
M x/N-C (1-x-y)/(CeO 2) y          (I) M x /NC (1-xy) /(CeO 2 ) y (I)
其中贵金属M为Pt、Pd和Au中的一种或两种以上，x、y为质量百分数，x的范围为5％-6％，优选5.5％-5.7％，y的范围为4％-12％，优选4％-5％；更优选地，贵金属M为Pt,贵金属Pt颗粒的粒径为3-8nm；Wherein the precious metal M is one or more of Pt, Pd and Au, x and y are mass percentages, the range of x is 5%-6%, preferably 5.5%-5.7%, and the range of y is 4%-12 %, preferably 4%-5%; more preferably, the precious metal M is Pt, and the particle size of the precious metal Pt particles is 3-8 nm;
优选地，所述ORR催化剂材料是多孔材料，比表面积是40m 2/g-800m 2/g，更优选600m 2/g-800m 2/g。 Preferably, the ORR catalyst material is a porous material with a specific surface area of 40m 2 /g-800m 2 /g, more preferably 600m 2 /g-800m 2 /g.
本发明第二方面目的在于提出一种ORR催化剂材料的制备方法，该ORR催化剂材料的制备方法简单、环保、成本低。The purpose of the second aspect of the present invention is to provide a preparation method of an ORR catalyst material, and the preparation method of the ORR catalyst material is simple, environmentally friendly and low in cost.
该方法通过导电聚合物原位包覆氧化铈，导电聚合物制备过程中，通过添加贵金属酸根，通过贵金属酸根在导电聚合物中的掺杂，获取贵金属分散均匀的催化剂前驱体，进而通过氮气或者氩气气氛保护下碳化，获取氧化铈-贵金属-氮掺杂碳的三元杂化催化剂，制得的ORR催化剂材料中贵金属分散均匀，贵金属用量少，催化剂材料孔隙率高、比表面积大、稳定性好、催化性能好，以解决现有技术中ORR催化剂材料存在贵金属分散不均匀，贵金属用量大，催化剂材料孔隙率低、比表面积小、稳定性差、催化性能不够好，及催化剂材料的制备方法复杂、不环保、成本高的技术问题。The method coats cerium oxide in situ with a conductive polymer. During the preparation of the conductive polymer, a catalyst precursor with evenly dispersed precious metal is obtained by adding precious metal acid radicals and doping the conductive polymer with precious metal acid radicals. Carbonization under the protection of argon atmosphere to obtain a ternary hybrid catalyst of cerium oxide-precious metal-nitrogen-doped carbon. The prepared ORR catalyst material has a uniform dispersion of precious metals, a small amount of precious metals, high porosity, and large specific surface area. Good stability and good catalytic performance, in order to solve the problem of uneven dispersion of precious metals in ORR catalyst materials in the prior art, large amount of precious metals, low porosity of catalyst materials, small specific surface area, poor stability, and insufficient catalytic performance, and the preparation of catalyst materials The method is complicated, not environmentally friendly, and the technical problem of high cost.
本发明通过以下技术方案解决上述技术问题，达到本发明的目的。The present invention solves the above technical problems through the following technical solutions, and achieves the purpose of the present invention.
一种ORR催化剂材料的制备方法，包括以下步骤：A preparation method of ORR catalyst material, comprising the following steps:
1)获取CeO 2； 1) Obtain CeO 2 ;
2)利用所述CeO 2制得催化剂前驱体材料,所述催化剂前躯体材料是由贵金属酸根掺杂的导电高分子复合材料，所述催化剂前躯体材料化学式为CeO 2/CP-MX n-(本化学式仅表明催化剂前躯体材料的组成成分，不代表各成分之间的比例关系)，X为酸根，n为1或2； 2) using the CeO 2 to prepare a catalyst precursor material, the catalyst precursor material is a conductive polymer composite material doped with noble metal acid radicals, and the chemical formula of the catalyst precursor material is CeO 2 /CP-MX n- ( This chemical formula only shows the composition of the catalyst precursor material, not the proportional relationship between the components), X is an acid radical, and n is 1 or 2;
3)高温碳化所述催化剂前驱体材料制得所述ORR催化剂材料。3) Carbonizing the catalyst precursor material at high temperature to obtain the ORR catalyst material.
进一步，所述步骤2)利用所述CeO 2制得催化剂前驱体材料包括以下步骤： Further, the step 2) using the CeO 2 to prepare the catalyst precursor material includes the following steps:
2.1)将所述CeO 2分散于贵金属M的酸或盐溶液中，得到溶液I； 2.1 ) the CeO is dispersed in the acid or salt solution of the precious metal M to obtain solution I;
2.2)将导电高分子单体加入所述溶液I中得到溶液II；2.2) adding the conductive polymer monomer into the solution I to obtain solution II;
2.3)将氧化剂或氧化剂的酸溶液加入所述溶液II中，进行原位聚合反应制得所述催化剂前驱体材料。2.3) Adding an oxidizing agent or an acid solution of an oxidizing agent into the solution II, and performing an in-situ polymerization reaction to obtain the catalyst precursor material.
又进一步，所述步骤2.1)中，所述CeO 2与所述贵金属M的酸或盐的摩尔比值为8-70：1；和/或 Still further, in the step 2.1), the molar ratio of the CeO 2 to the acid or salt of the noble metal M is 8-70:1; and/or
所述步骤2.2)中，所述导电高分子单体与所述贵金属M的酸或盐的摩尔比值为16-128：1；和/或In the step 2.2), the molar ratio of the conductive polymer monomer to the acid or salt of the noble metal M is 16-128:1; and/or
所述步骤2.3)中，所述氧化剂与所述导电高分子单体的摩尔比值为2-3：1；和/或In the step 2.3), the molar ratio of the oxidant to the conductive polymer monomer is 2-3:1; and/or
所述步骤2.3)中，所述氧化剂的酸溶液是氧化剂的盐酸溶液，所述氧化剂与所述盐酸中的HCl的摩尔比为1：3-4。In the step 2.3), the acid solution of the oxidant is a hydrochloric acid solution of the oxidant, and the molar ratio of the oxidant to the HCl in the hydrochloric acid is 1:3-4.
在前述任一技术方案的基础上优选地，所述贵金属M的酸或盐为H 2PdCl 4、Pd(NH 3) 4Cl 2、Pd(NH 3) 2Cl 2、Pd(NH 3) 4SO 4、Pd(NH 3) 4(NO 3) 2、H 2PtCl 6、H 2PtCl 4、K 2PtCl 6、(NH 4) 2PtCl 6、K 2PtCl 4、(NH4) 2PtCl 4、HAuCl 4、NaAuCl 4、KAuCl 4及其水合物中的一种或两种以上。 On the basis of any of the foregoing technical solutions, preferably, the acid or salt of the noble metal M is H 2 PdCl 4 , Pd(NH 3 ) 4 Cl 2 , Pd(NH 3 ) 2 Cl 2 , Pd(NH 3 ) 4 SO 4 , Pd(NH 3 ) 4 (NO 3 ) 2 , H 2 PtCl 6 , H 2 PtCl 4 , K 2 PtCl 6 , (NH 4 ) 2 PtCl 6 , K 2 PtCl 4 , (NH 4 ) 2 PtCl 4 , One or more of HAuCl 4 , NaAuCl 4 , KAuCl 4 and their hydrates.
在前述任一技术方案的基础上优选地，所述导电高分子单体为聚苯胺、聚吡咯中的一种或两种；和/或On the basis of any of the foregoing technical solutions, preferably, the conductive polymer monomer is one or both of polyaniline and polypyrrole; and/or
所述氧化剂为APS或FeCl 3。 The oxidant is APS or FeCl 3 .
在前述ORR催化剂材料的制备方法的基础上进一步，所述步骤3)高温碳化所述催化剂前驱体材料制得所述ORR催化剂材料包括以下步骤：将所述催化剂前驱体材料在惰性气体氛围保护下，以升温速率为5-20℃/min,由室温升至600-1000℃，反应2-4小时，自然冷却后得到所述ORR催化剂材料。On the basis of the aforementioned preparation method of ORR catalyst material, the step 3) carbonizing the catalyst precursor material at high temperature to prepare the ORR catalyst material includes the following steps: placing the catalyst precursor material under the protection of an inert gas atmosphere , with a heating rate of 5-20° C./min, rising from room temperature to 600-1000° C., reacting for 2-4 hours, and naturally cooling to obtain the ORR catalyst material.
本发明的第三方面目的在于提出前述ORR催化剂材料的用途。如前文所述的ORR催化剂材料的用途，是用作氢氧燃料电池或金属空气电池的阴极电极。A third aspect of the present invention aims to propose the use of the aforementioned ORR catalyst materials. The use of the ORR catalyst material as described above is as a cathode electrode for a hydrogen-oxygen fuel cell or a metal-air battery.
本发明的第四方面目的在于提出一种氢氧燃料电池或金属空气电池，该氢氧燃料电池或金属空气电池的ORR催化剂材料中贵金属分散均匀，贵金属用量少，催化剂材料孔隙率高、比表面积大、稳定性好、催化性能好，该氢氧燃料电池或金属空气电池的ORR催化剂材料的制备方法简单、环保、成本低，以解决现有技术中氢氧燃料电池或金属空气电池的ORR催化剂材料存在贵金属分散 不均匀，贵金属用量大，催化剂材料孔隙率低、比表面积小、稳定性差、催化性能不够好，及催化剂材料的制备方法复杂、不环保、成本高的技术问题。The purpose of the fourth aspect of the present invention is to provide a hydrogen-oxygen fuel cell or metal-air battery, in which the ORR catalyst material of the hydrogen-oxygen fuel cell or metal-air battery is evenly dispersed in precious metals, the amount of precious metals is small, the catalyst material has high porosity, and has a high specific gravity. Large surface area, good stability and good catalytic performance, the preparation method of the ORR catalyst material of the hydrogen-oxygen fuel cell or metal-air battery is simple, environmentally friendly and low in cost, so as to solve the ORR of the hydrogen-oxygen fuel cell or metal-air battery in the prior art. The catalyst materials have the technical problems of uneven dispersion of precious metals, large amount of precious metals, low porosity, small specific surface area, poor stability, poor catalytic performance, and complex preparation methods of catalyst materials, not environmentally friendly, and high cost.
本发明通过以下技术方案解决上述技术问题，达到本发明的目的。The present invention solves the above technical problems through the following technical solutions, and achieves the purpose of the present invention.
一种氢氧燃料电池，包括阴极电极，所述阴极电极的催化剂采用如前文所述的ORR催化剂材料或采用如前文所述的任一技术方案制备得到的ORR催化剂材料。A hydrogen-oxygen fuel cell includes a cathode electrode, and the catalyst of the cathode electrode adopts the ORR catalyst material as described above or the ORR catalyst material prepared by any of the technical solutions described above.
一种金属空气电池，包括阴极电极，所述阴极电极的催化剂采用如前文所述的ORR催化剂材料或者采用如前文所述的任一技术方案制备得到的ORR催化剂材料。A metal-air battery includes a cathode electrode, and the catalyst of the cathode electrode adopts the ORR catalyst material as described above or the ORR catalyst material prepared by any of the technical solutions described above.
本发明的ORR催化剂材料的制备方法，通过导电聚合物原位包覆氧化铈，导电聚合物制备过程中，通过添加贵金属酸根，通过贵金属酸根在导电聚合物中的掺杂，获取贵金属分散均匀的催化剂前驱体材料，进而通过氮气或者氩气气氛保护下碳化，获取氧化铈-贵金属-氮掺杂碳的三元杂化催化剂。具体而言，将氧化铈添加到聚苯胺和/或聚吡咯合成的溶液中，在化学原位聚合聚苯胺和/或聚吡咯的同时，得到贵金属酸根掺杂的聚苯胺和/或聚吡咯包覆氧化铈的复合材料，经过高温碳化催化剂前驱体聚苯胺和/或聚吡咯包覆氧化铈，在高温碳化过程中，聚苯胺和/或聚吡咯前驱体逐渐转变化成N掺杂的碳材料，而掺杂于聚苯胺结构中贵金属酸根被热还原生成分散均匀的贵金属M纳米颗粒。该方法一步得到了均匀分散的贵金属M纳米颗粒与氧化铈，N掺杂杂碳的三元催化材料。In the preparation method of the ORR catalyst material of the present invention, the conductive polymer is coated with cerium oxide in situ. The catalyst precursor material is further carbonized under the protection of nitrogen or argon atmosphere to obtain a cerium oxide-precious metal-nitrogen-doped carbon ternary hybrid catalyst. Specifically, cerium oxide is added to the solution synthesized by polyaniline and/or polypyrrole, and at the same time of chemical in-situ polymerization of polyaniline and/or polypyrrole, noble metal-acid-doped polyaniline and/or polypyrrole-coated polyaniline and/or polypyrrole are obtained. The cerium oxide-coated composite material is coated with cerium oxide by the high-temperature carbonization catalyst precursor polyaniline and/or polypyrrole. During the high-temperature carbonization process, the polyaniline and/or polypyrrole precursor is gradually transformed into an N-doped carbon material, The noble metal oxides doped in the polyaniline structure are thermally reduced to form uniformly dispersed noble metal M nanoparticles. The method obtains uniformly dispersed noble metal M nanoparticles, cerium oxide, and N-doped ternary carbon catalyst materials in one step.
与现有技术相比，本发明的技术效果如下：Compared with the prior art, the technical effect of the present invention is as follows:
1.制备方法简单、便捷、环保、高效、成本低，通过原位聚合以及高温碳化的方法得到高孔隙率、高比表面积、高性能的三元复合体系催化剂；制备过 程没有使用还原剂(现有技术使用还原剂会引入不必要的离子影响性能)。1. The preparation method is simple, convenient, environmentally friendly, efficient and low in cost, and a ternary composite system catalyst with high porosity, high specific surface area and high performance is obtained by in-situ polymerization and high-temperature carbonization; no reducing agent is used in the preparation process (now There are techniques using reducing agents that introduce unwanted ions that affect performance).
2.借助于导电聚合物作为催化剂的氮源及碳源，通过在导电聚合物的聚合溶液中添加贵金属酸根，聚合过程中贵金属酸根在导电聚合物中的掺杂，获取贵金属分散均匀的催化剂前驱体材料；通过高温碳化的方式一步得到了贵金属M的纳米颗粒，且粒径在5nm左右，均匀的分散在材料表面。2. With the help of the conductive polymer as the nitrogen source and carbon source of the catalyst, by adding precious metal acid radicals to the polymerization solution of the conductive polymer, and doping the precious metal acid radical in the conductive polymer during the polymerization process, a catalyst precursor with evenly dispersed precious metals can be obtained. The bulk material; nanoparticles of noble metal M are obtained in one step by high-temperature carbonization, and the particle size is about 5 nm, which is uniformly dispersed on the surface of the material.
3.聚苯胺和/或聚吡咯作为催化剂的碳源氮源，通过高温碳化，得到了氮掺杂的碳，氮的掺入增加了催化剂的缺陷程度，对贵金属M有一定的瞄定作用，生成的贵金属的颗粒大小以及分布得到有效的控制，而且贵金属M分散在多孔的碳材料基体中，不仅仅在表面负载，从而提升材料的催化性能稳定性,提高了贵金属M颗粒的分散性以及催化剂的导电性，进一步提高了催化剂的催化活性,并且在一定程度上降低了贵金属M的用量。3. Polyaniline and/or polypyrrole are used as the carbon source and nitrogen source of the catalyst. Through high temperature carbonization, nitrogen-doped carbon is obtained. The incorporation of nitrogen increases the defect degree of the catalyst and has a certain targeting effect on the precious metal M. The particle size and distribution of the generated precious metal are effectively controlled, and the precious metal M is dispersed in the porous carbon material matrix, not only supported on the surface, thereby improving the catalytic performance stability of the material, improving the dispersion of the precious metal M particles and the catalyst. The conductivity of the catalyst further improves the catalytic activity of the catalyst, and reduces the amount of precious metal M to a certain extent.
4.过渡金属氧化物CeO 2与贵金属M纳米颗粒的协同催化作用，进一步提高了催化活性。本发明设计的三元催化体系，通过三者的协同效应可以大幅提升材料的催化性能。同时贵金属与过渡金属氧化物CeO 2,杂原子N有效复合，有助于贵金属的分散和电子在催化剂表面转移，从而具有高催化活性和稳定性。 4. The synergistic catalytic effect of transition metal oxide CeO2 and noble metal M nanoparticles further enhances the catalytic activity. The three-way catalytic system designed in the present invention can greatly improve the catalytic performance of the material through the synergistic effect of the three. At the same time, the noble metal is effectively compounded with the transition metal oxide CeO 2 and the heteroatom N, which is helpful for the dispersion of the noble metal and the transfer of electrons on the surface of the catalyst, so it has high catalytic activity and stability.
附图说明Description of drawings
图1是具体实施方式中制备ORR催化剂材料的方法的流程图。Figure 1 is a flow diagram of a method of preparing an ORR catalyst material in an embodiment.
图2是实施例1制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％催化剂的XRD图谱。 2 is the XRD pattern of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% catalyst prepared in Example 1.
图3是实施例1制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％催化剂的TEM图。 3 is a TEM image of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% catalyst prepared in Example 1.
图4是实施例1制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％催化剂的STEM图。 4 is the STEM image of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% catalyst prepared in Example 1.
图5是实施例1制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％与商业铂碳20％(质 量分数，下同)Pt/C催化剂线性扫描伏安(LSV)对比图。 Figure 5 is a linear sweep voltammetry (LSV) comparison diagram of Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% prepared in Example 1 and commercial platinum carbon 20% (mass fraction, the same below) Pt/C catalyst.
图6是实施例1制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％与商业铂碳20％Pt/C催化剂稳定性对比图。 Figure 6 is a comparison chart of the stability of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% prepared in Example 1 and the commercial platinum carbon 20% Pt/C catalyst.
图7是实施例1中制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％催化剂的氮气吸脱附等温曲线图(比表面积值为：636.96m 2/g)。 7 is a nitrogen adsorption and desorption isotherm curve diagram of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% catalyst prepared in Example 1 (specific surface area value: 636.96 m 2 /g).
图8是实施例2制备得到的Pt 5.14％/N-C 90.44％/(CeO 2) 4.42％催化剂的XRD图谱。 8 is the XRD pattern of the Pt 5.14% /NC 90.44% /(CeO 2 ) 4.42% catalyst prepared in Example 2.
图9是实施例2制备得到的Pt 5.14％/N-C 90.44％/(CeO 2) 4.42％催化剂的TEM图。 9 is a TEM image of the Pt 5.14% /NC 90.44% /(CeO 2 ) 4.42% catalyst prepared in Example 2.
图10是实施例2制备得到的Pt 5.14％/N-C 90.44％/(CeO 2) 4.42％催化剂与商业铂碳20％Pt/C催化剂线性扫描伏安(LSV)对比图。 FIG. 10 is a comparison diagram of linear sweep voltammetry (LSV) between the Pt 5.14% /NC 90.44% /(CeO 2 ) 4.42% catalyst prepared in Example 2 and the commercial platinum carbon 20% Pt/C catalyst.
图11是实施例2制备得到的Pt 5.14％/N-C 90.44％/(CeO 2) 4.42％催化剂的氮气吸脱附等温曲线图(比表面积值为：603.75m 2/g)。 11 is a nitrogen adsorption and desorption isotherm curve diagram of the Pt 5.14% /NC 90.44% /(CeO 2 ) 4.42% catalyst prepared in Example 2 (specific surface area value: 603.75 m 2 /g).
图12是实施例3制备得到的Pt 6.8％/N-C 89.36％/(CeO 2) 3.84％催化剂的XRD图谱。 12 is the XRD pattern of the Pt 6.8% /NC 89.36% /(CeO 2 ) 3.84% catalyst prepared in Example 3.
图13是实施例3制备得到的Pt 6.8％/N-C 89.36％/(CeO 2) 3.84％催化剂与商业铂碳20％Pt/C催化剂线性扫描伏安(LSV)对比图。 FIG. 13 is a linear sweep voltammetry (LSV) comparison diagram of the Pt 6.8% /NC 89.36% /(CeO 2 ) 3.84% catalyst prepared in Example 3 and the commercial platinum carbon 20% Pt/C catalyst.
图14是实施例3制备得到的Pt 6.8％/N-C 89.36％/(CeO 2) 3.84％催化剂的氮气吸脱附等温曲线图(比表面积值为：68.34m 2/g)。 14 is a nitrogen adsorption and desorption isotherm curve diagram of the Pt 6.8% /NC 89.36% /(CeO 2 ) 3.84% catalyst prepared in Example 3 (specific surface area value: 68.34 m 2 /g).
图15是实施例4制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％与商业铂碳20％Pt/C催化剂在氧气饱和的0.1M HClO 4的溶液中进行测试得到的线性扫描伏安(LSV)对比图。 Figure 15 is a linear scan obtained by testing the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% prepared in Example 4 with a commercial platinum-carbon 20% Pt/C catalyst in an oxygen-saturated 0.1 M HClO 4 solution Voltammetry (LSV) comparison chart.
图16是实施例1制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％，对比例1制备得到的Pt/N-C，对比例2制备得到的N-C/CeO 2，以及商业铂碳20％Pt/C催化剂，在氧气饱和的0.1M KOH的溶液中进行测试得到的线性扫描伏安(LSV)对比图。 Figure 16 shows Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% prepared in Example 1, Pt/NC prepared in Comparative Example 1, NC/CeO 2 prepared in Comparative Example 2 , and commercial platinum carbon 20 %Pt/C catalyst, line sweep voltammetry (LSV) comparison graph obtained by testing in an oxygen-saturated solution of 0.1M KOH.
具体实施方式Detailed ways
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合本发明的具体实施方式作详细说明。In order to make it easy to understand the technical means, creative features, achieved goals and effects of the present invention, the following detailed description is given in conjunction with the specific embodiments of the present invention.
一种ORR催化剂材料，由微纳米级(指微米级和/或纳米级)CeO 2、贵金属M和氮掺杂的碳材料组成，氮在碳中的掺杂量按摩尔比为0.05-0.1：1，所述ORR催化剂材料中CeO 2和贵金属M均匀地分布在氮掺杂的碳材料中，所述ORR催化剂材料符合以下通式： An ORR catalyst material is composed of micro-nano-scale (referring to micro-scale and/or nano-scale) CeO 2 , noble metal M and nitrogen-doped carbon material, and the doping amount of nitrogen in carbon is 0.05-0.1 in molar ratio: 1. CeO 2 and precious metal M in the ORR catalyst material are uniformly distributed in the nitrogen-doped carbon material, and the ORR catalyst material conforms to the following general formula:
M x/N-C (1-x-y)/(CeO 2) y                  (I) M x /NC (1-xy) /(CeO 2 ) y (I)
其中贵金属M为Pt、Pd和Au中的一种或两种以上，x、y为质量分数，x的范围为5％-8％，优选5.5％-5.7％，更优选5.6％-5.7％，y的范围为4％-12％，优选4％-5％，更优选4.2％-4.3％；优选地，贵金属M为Pt,贵金属Pt颗粒的粒径为3-8nm。Wherein the precious metal M is one or more of Pt, Pd and Au, x and y are mass fractions, and the range of x is 5%-8%, preferably 5.5%-5.7%, more preferably 5.6%-5.7%, The range of y is 4%-12%, preferably 4%-5%, more preferably 4.2%-4.3%; preferably, the precious metal M is Pt, and the particle size of the precious metal Pt particles is 3-8 nm.
优选地，所述ORR催化剂材料是多孔材料，比表面积是40m 2/g-800m 2/g。 Preferably, the ORR catalyst material is a porous material with a specific surface area of 40m 2 /g-800m 2 /g.
参见图1，一种前述ORR催化剂材料的制备方法，包括以下步骤：Referring to Fig. 1, a preparation method of the aforementioned ORR catalyst material comprises the following steps:
1)获取CeO 2； 1) Obtain CeO 2 ;
2)利用所述CeO 2制得催化剂前驱体材料,所述催化剂前躯体材料是由贵金属酸根掺杂的导电高分子复合材料，所述催化剂前躯体材料化学式为CeO 2/CP-MX n-，X为酸根，n为1或2； 2) using the CeO 2 to prepare a catalyst precursor material, the catalyst precursor material is a conductive polymer composite material doped with noble metal acid radicals, and the chemical formula of the catalyst precursor material is CeO 2 /CP-MX n- , X is an acid radical, and n is 1 or 2;
3)高温碳化所述催化剂前驱体材料制得所述ORR催化剂材料。3) Carbonizing the catalyst precursor material at high temperature to obtain the ORR catalyst material.
所述步骤1)获取Ce0 2,，可以购买市售的微米级和/或纳米级Ce0 2，也可以按以下方法制备： In the step 1) to obtain CeO 2 , commercially available micro-scale and/or nano-scale CeO 2 can be purchased, and can also be prepared by the following methods:
1.1)将硝酸铈和氢氧化钠溶于去离子水中，调节溶液pH值，搅拌均匀得反应溶液；优选地，所述步骤1.1)中，所述硝酸铈和所述氢氧化钠的摩尔比为1:4，所述pH值为12，所述搅拌均匀为磁力搅拌2h；1.1) dissolve cerium nitrate and sodium hydroxide in deionized water, adjust the pH value of the solution, and stir to obtain a reaction solution; preferably, in the step 1.1), the molar ratio of the cerium nitrate and the sodium hydroxide is 1:4, the pH value is 12, and the uniform stirring is magnetic stirring for 2h;
1.2)将所述反应溶液的环境温度调节至反应温度进行反应，得到含有CeO 2的溶液；优选地，所述反应温度为60℃，反应的时间为1h； 1.2) The ambient temperature of the reaction solution is adjusted to the reaction temperature for the reaction to obtain a solution containing CeO 2 ; preferably, the reaction temperature is 60° C., and the reaction time is 1 h;
1.3)将所述含有CeO 2的溶液过滤洗涤后，干燥、退火后得到CeO 2；优选地，所述干燥温度为130℃，所述退火时间为4h。 1.3) After filtering and washing the solution containing CeO 2 , CeO 2 is obtained after drying and annealing; preferably, the drying temperature is 130° C., and the annealing time is 4 h.
所述步骤2)利用所述CeO 2制得催化剂前驱体材料包括以下步骤： The step 2) utilizing the CeO 2 to prepare the catalyst precursor material includes the following steps:
2.1)将所述CeO 2分散于贵金属M的酸或盐溶液中，得到溶液I； 2.1 ) the CeO is dispersed in the acid or salt solution of the precious metal M to obtain solution I;
2.2)将导电高分子单体加入所述溶液I中得到溶液II；2.2) adding the conductive polymer monomer into the solution I to obtain solution II;
2.3)将氧化剂或氧化剂的酸溶液(因为在质子酸性溶液中聚合，聚合的导电聚合物性能好一些，所以可以将氧化剂溶于酸中)加入所述溶液II中，加入时搅拌均匀，进行原位聚合反应制得所述催化剂前驱体材料。2.3) Add the oxidant or the acid solution of the oxidant (because it is polymerized in a protic acid solution, the polymerized conductive polymer has better performance, so the oxidant can be dissolved in the acid) into the solution II, stir evenly when adding, and carry out the original process. The catalyst precursor material is prepared by in situ polymerization.
所述步骤2.1)中，所述CeO 2与所述贵金属M的酸或盐的摩尔比值范围为8-70：1； In the step 2.1), the molar ratio range of the CeO 2 to the acid or salt of the precious metal M is 8-70:1;
所述步骤2.2)中，所述导电高分子单体与所述贵金属M的酸或盐的摩尔比值范围为16-128：1；In the step 2.2), the molar ratio of the conductive polymer monomer to the acid or salt of the precious metal M is in the range of 16-128:1;
所述步骤2.3)中，所述氧化剂与所述导电高分子单体的摩尔比值范围为2-3：1；和/或In the step 2.3), the molar ratio of the oxidant to the conductive polymer monomer is in the range of 2-3:1; and/or
所述氧化剂的酸溶液是氧化剂的盐酸溶液，所述氧化剂与所述盐酸中的HCl的摩尔比为1：3-4。The acid solution of the oxidant is a hydrochloric acid solution of the oxidant, and the molar ratio of the oxidant to the HCl in the hydrochloric acid is 1:3-4.
所述贵金属M的酸或盐为H 2PdCl 4、Pd(NH 3) 4Cl 2、Pd(NH 3) 2Cl 2、Pd(NH 3) 4SO 4、 Pd(NH 3) 4(NO 3) 2、H 2PtCl 6、H 2PtCl 4、K 2PtCl 6、(NH 4) 2PtCl 6、K 2PtCl 4、(NH4) 2PtCl 4、HAuCl 4、NaAuCl 4、KAuCl 4及其水合物中的一种或两种以上。 The acid or salt of the noble metal M is H 2 PdCl 4 , Pd(NH 3 ) 4 Cl 2 , Pd(NH 3 ) 2 Cl 2 , Pd(NH 3 ) 4 SO 4 , Pd(NH 3 ) 4 (NO 3 ) ) 2 , H 2 PtCl 6 , H 2 PtCl 4 , K 2 PtCl 6 , (NH 4 ) 2 PtCl 6 , K 2 PtCl 4 , (NH 4 ) 2 PtCl 4 , HAuCl 4 , NaAuCl 4 , KAuCl 4 and their hydrates one or more of them.
所述导电高分子单体为聚苯胺、聚吡咯中的一种或两种；所述氧化剂为APS或FeCl 3。 The conductive polymer monomer is one or both of polyaniline and polypyrrole; the oxidant is APS or FeCl 3 .
所述步骤3)高温碳化所述催化剂前驱体材料制得所述ORR催化剂材料包括以下步骤：The step 3) carbonizing the catalyst precursor material at high temperature to obtain the ORR catalyst material includes the following steps:
将所述催化剂前驱体材料在惰性气体氛围保护下，以升温速率为5-20℃/min,由室温升至600-1000℃，反应2-4小时，自然冷却后得到所述ORR催化剂材料。Under the protection of an inert gas atmosphere, the catalyst precursor material is raised from room temperature to 600-1000°C at a heating rate of 5-20°C/min, reacted for 2-4 hours, and naturally cooled to obtain the ORR catalyst material. .
如前文所述的ORR催化剂材料的用途，可以用作氢氧燃料电池或金属空气电池的阴极电极。The use of the ORR catalyst material as described above can be used as a cathode electrode for a hydrogen-oxygen fuel cell or a metal-air battery.
一种燃料电池，包括阴极电极，所述阴极电极的催化剂采用如本具体实施方式所述的ORR催化剂材料或者采用如本具体实施方式制备得到的ORR催化剂材料。A fuel cell includes a cathode electrode, and the catalyst of the cathode electrode adopts the ORR catalyst material described in this specific embodiment or the ORR catalyst material prepared according to this specific embodiment.
一种金属空气电池，包括阴极电极的催化剂采用如本具体实施方式所述的ORR催化剂材料或者采用如本具体实施方式制备得到的ORR催化剂材料。A metal-air battery, the catalyst including the cathode electrode adopts the ORR catalyst material described in this specific embodiment or the ORR catalyst material prepared according to this specific embodiment.
下面举例说明，以下实施例在以上述具体实施方式为前提下进行实施，给出了详细的实施方式和过程，但本发明的保护范围不限于下述的实施例。The following examples are illustrated below, and the following examples are implemented on the premise of the above-mentioned specific implementation manner, and provide detailed implementation manners and processes, but the protection scope of the present invention is not limited to the following examples.
实施例1Example 1
配置浓度为0.1M的硝酸铈溶液，并用氢氧化钠调节至溶液的pH＝12，磁力 搅拌2小时后，将溶液放置烘箱中60℃保持1h，过滤洗涤后将黄色固体放置烘箱中保持130℃退火4h,待冷却2h至室温后制得氧化铈。A 0.1M cerium nitrate solution was prepared and adjusted to pH=12 with sodium hydroxide. After magnetic stirring for 2 hours, the solution was placed in an oven at 60°C for 1 hour. After filtering and washing, the yellow solid was placed in an oven and kept at 130°C. After annealing for 4h, cerium oxide was obtained after cooling to room temperature for 2h.
将0.6g(3.5mmol)氧化铈，0.1g(0.2mmol)氯铂酸钾(K 2PtCl 6)加入40ml的1mol/LHCl溶液中，得到溶液I，超声分散2小时后，取0.6ml苯胺单体(6.4mmol)加入溶液I中得到溶液II；将0.6g APS(4mmol)溶于10ml的1mol/LHCl溶液中，得到溶液III，超声2小时使其分散均匀；控制溶液III的滴速，使其慢速滴入溶液II中；保持5℃，反应5小时。反应过程中伴随磁力搅拌；过滤洗涤后得到催化剂前驱体材料。 Add 0.6g (3.5mmol) of cerium oxide and 0.1g (0.2mmol) of potassium chloroplatinate (K 2 PtCl 6 ) to 40ml of 1mol/L HCl solution to obtain solution I, after ultrasonic dispersion for 2 hours, take 0.6ml of aniline monohydrate Body (6.4mmol) was added in solution I to obtain solution II; 0.6g APS (4mmol) was dissolved in 10ml of 1mol/L HCl solution to obtain solution III, which was uniformly dispersed by ultrasonic for 2 hours; It was slowly dropped into solution II; kept at 5°C, the reaction was carried out for 5 hours. The reaction process is accompanied by magnetic stirring; the catalyst precursor material is obtained after filtering and washing.
将催化剂前驱体材料在惰性气体Ar 2氛围保护下，升温速率为10℃/min,由室温升至800℃，反应2小时，自然冷却后得到最终产物，经检测最终产物为Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％。将上述所得最终产物作为催化剂利用旋转圆盘电极、电化学工作站在电解质溶液0.1MKOH中进行电化学测试。 Under the protection of the inert gas Ar 2 atmosphere, the catalyst precursor material was heated at a rate of 10 °C/min, and the temperature was increased from room temperature to 800 °C, and the reaction was carried out for 2 hours. After natural cooling, the final product was obtained . NC 90.14% /(CeO 2 ) 4.22% . The final product obtained above was used as a catalyst to conduct electrochemical tests in an electrolyte solution of 0.1 MKOH using a rotating disk electrode and an electrochemical workstation.
图2是实施例1制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％催化剂(图中简写为Pt 5.64％/N-C/CeO 2，下同)的XRD图谱，从该图谱可以得知最终产物包含Pt和CeO 2。从XRD图谱中根据谢尔公式(Scherrerequation)得出Pt的颗粒大小为3-8nm。 Figure 2 is the XRD pattern of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% catalyst (abbreviated as Pt 5.64% /NC/CeO 2 in the figure, the same below) prepared in Example 1, from which we can obtain The final product is known to contain Pt and CeO 2 . The particle size of Pt is 3-8 nm from the XRD pattern according to Scherrerequation.
图3是实施例1制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％催化剂的TEM图，该图是在200kV的加速电压下获得的从该图可以得知最终产物中Pt(图中黑色或灰色的圆点)分布均匀。 Figure 3 is a TEM image of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% catalyst prepared in Example 1, which was obtained at an accelerating voltage of 200kV. From this image, it can be known that the Pt ( The black or gray circles in the figure) are evenly distributed.
图4是实施例1制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％催化剂的STEM图，该图是在200kV的加速电压下获得的从该图可以得知最终产物中C、O、Pt、N、Ce分布均匀。 Figure 4 is the STEM image of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% catalyst prepared in Example 1, which was obtained at an accelerating voltage of 200kV. O, Pt, N, Ce are evenly distributed.
图5是实施例1制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％与商业铂碳20％Pt/C 催化剂线性扫描伏安(LSV)对比图。20％Pt/C购于上海麦克林生化科技有限公司(以下实施例同)。通过对比实施例1与商业铂碳20％Pt/C的线性扫描曲线图发现，实施例1的起始电位0.95V(Vs.RHE)，半波电位0.88V(Vs.RHE)，极限电流密度5.88mA/cm 2,均优于商业铂碳20％Pt/C的起始电位0.95V(Vs.RHE)，半波电位0.87V(Vs.RHE)，极限电流密度4.68mA/cm 2。 FIG. 5 is a comparison diagram of linear sweep voltammetry (LSV) between the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% prepared in Example 1 and the commercial platinum carbon 20% Pt/C catalyst. 20% Pt/C was purchased from Shanghai McLean Biochemical Technology Co., Ltd. (the same as in the following examples). By comparing the linear scanning curve of Example 1 and commercial platinum carbon 20%Pt/C, it is found that the initial potential of Example 1 is 0.95V (Vs.RHE), the half-wave potential is 0.88V (Vs.RHE), and the limiting current density 5.88mA/cm 2 , both of which are better than commercial platinum-carbon 20%Pt/C with an initial potential of 0.95V (Vs.RHE), a half-wave potential of 0.87V (Vs.RHE), and a limiting current density of 4.68mA/cm 2 .
图6是实施例1制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％与商业铂碳20％Pt/C催化剂稳定性对比图。通过对比实施例1制备得到的Pt 5.64％/N-C/CeO 2与商业铂碳20％Pt/C的稳定性测测试结果发现，实施例1半波电位负移30mV，极限电流密度增加了0.39mAcm -2，而对比商业铂碳20％Pt/C,半波电位负移了40mV，极限电流密度减少了0.36mAcm -2，可见在碱性电解质0.1M KOH中，实施例1的稳定性要优于商业铂碳20％Pt/C。 Figure 6 is a comparison chart of the stability of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% prepared in Example 1 and the commercial platinum carbon 20% Pt/C catalyst. By comparing the stability test results of Pt 5.64% /NC/CeO 2 prepared in Example 1 and commercial platinum carbon 20% Pt/C, it is found that the half-wave potential of Example 1 is negatively shifted by 30mV, and the limiting current density is increased by 0.39mAcm -2 , and compared with the commercial platinum carbon 20% Pt/C, the half-wave potential is negatively shifted by 40mV, and the limiting current density is reduced by 0.36mAcm -2 . It can be seen that in the alkaline electrolyte 0.1M KOH, the stability of Example 1 is better. On commercial platinum carbon 20% Pt/C.
图7是实施例1制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％催化剂的氮气吸脱附等温曲线图(比表面积值为：636.96m 2/g)。 7 is a nitrogen adsorption and desorption isotherm curve diagram of the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% catalyst prepared in Example 1 (specific surface area value: 636.96 m 2 /g).
实施例2(与实施例1区别在于氯铂酸钾用量为0.05g)Embodiment 2 (different from embodiment 1 is that potassium chloroplatinate consumption is 0.05g)
配置浓度为0.1M的硝酸铈溶液，并用氢氧化钠调节至溶液的pH＝12，磁力搅拌2小时后，将溶液放置烘箱中60℃保持1h，过滤洗涤后将黄色固体放置烘箱中保持130℃退火4h,待冷却2h至室温后制得氧化铈。A 0.1M cerium nitrate solution was prepared and adjusted to pH=12 with sodium hydroxide. After magnetic stirring for 2 hours, the solution was placed in an oven at 60°C for 1 hour. After filtering and washing, the yellow solid was placed in an oven and kept at 130°C. After annealing for 4h, cerium oxide was obtained after cooling to room temperature for 2h.
将0.6g(3.5mmol mol)氧化铈，0.05g(0.1mmol)氯铂酸钾(K 2PtCl 6)加入40ml的1mol/LHCl溶液中，得到溶液I，超声分散2小时后，取0.6ml(6.4mmol)苯胺单体加入溶液I中得到溶液II；将0.6g(4mmol)APS溶于10ml的1mol/LHCl溶液中，得到溶液III，超声2小时使其分散均匀；控制溶液III的滴速，使其 慢速滴入溶液II中；保持5℃，反应5小时；反应过程中伴随磁力搅拌；过滤洗涤后得到催化剂前驱体材料。 Add 0.6g (3.5mmol mol) cerium oxide, 0.05g (0.1mmol) potassium chloroplatinate (K 2 PtCl 6 ) to 40ml of 1mol/L HCl solution to obtain solution I, after ultrasonic dispersion for 2 hours, take 0.6ml ( 6.4mmol) aniline monomer is added in solution I to obtain solution II; 0.6g (4mmol) APS is dissolved in the 1mol/L HCl solution of 10ml to obtain solution III, which is uniformly dispersed by ultrasonic for 2 hours; the dripping speed of solution III is controlled, It was slowly dropped into the solution II; kept at 5° C. and reacted for 5 hours; magnetic stirring was accompanied during the reaction; after filtration and washing, the catalyst precursor material was obtained.
将催化剂前驱体材料在惰性气体Ar 2氛围保护下，升温速率为10℃/min,由室温升至800℃，反应2小时，自然冷却后得到最终产物，经检测最终产物为Pt 5.14％/N-C 90.44％/(CeO 2) 4.42％。将上述所得最终产物制成催化剂浆料利用旋转圆盘电极、电化学工作站在电解质溶液0.1MKOH中进行与实例1相同电化学测试。 Under the protection of the inert gas Ar 2 atmosphere, the catalyst precursor material was heated at a rate of 10 °C/min, and the temperature was increased from room temperature to 800 °C, and the reaction was carried out for 2 hours. After natural cooling, the final product was obtained . NC 90.44% /(CeO 2 ) 4.42% . The final product obtained above was made into a catalyst slurry, and the same electrochemical test as in Example 1 was carried out in an electrolyte solution of 0.1 MKOH using a rotating disk electrode and an electrochemical workstation.
图8是实施例2制备得到的Pt 5.14％/N-C 90.44％/(CeO 2) 4.42％催化剂(图中简写为Pt 5.14％/N-C/CeO 2，下同)的XRD图谱，从该图谱可以得知最终产物包含Pt和CeO 2。从XRD图谱中根据谢尔公式(Scherrerequation)得出Pt的颗粒大小为5-8nm。 Figure 8 is the XRD pattern of the Pt 5.14% /NC 90.44% /(CeO 2 ) 4.42% catalyst (abbreviated as Pt 5.14% /NC/CeO 2 in the figure, the same below) prepared in Example 2, from which we can obtain The final product is known to contain Pt and CeO 2 . The particle size of Pt is 5-8 nm from the XRD pattern according to Scherrerequation.
图9是实施例2制备得到的Pt 5.14％/N-C 90.44％/(CeO 2) 4.42％催化剂的TEM图，该图是在200kV的加速电压下下获得的，从该图可以得知产物中Pt分布均匀。 Figure 9 is a TEM image of the Pt 5.14% /NC 90.44% /(CeO 2 ) 4.42% catalyst prepared in Example 2, which was obtained at an accelerating voltage of 200kV. From this image, it can be known that Pt in the product evenly distributed.
图10是实施例2制备得到的Pt 5.14％/N-C 90.44％/(CeO 2) 4.42％与商业铂碳20％Pt/C催化剂线性扫描伏安(LSV)对比图。通过对比实施例2与商业铂碳20％Pt/C的线性扫描曲线图发现，实施例2的起始电位0.91V(Vs.RHE)，半波电位0.83V(Vs.RHE)，极限电流密度3.52mA/cm 2,劣于实施例1的起始电位0.95V(Vs.RHE)，半波电位0.88V(Vs.RHE)，极限电流密度5.88mA/cm 2；也劣于商业20％Pt/C的起始电位0.95V(Vs.RHE)，半波电位0.87V(Vs.RHE)，极限电流密度4.68mA/cm 2。 FIG. 10 is a comparison diagram of linear sweep voltammetry (LSV) between the Pt 5.14% /NC 90.44% /(CeO 2 ) 4.42% prepared in Example 2 and the commercial platinum carbon 20% Pt/C catalyst. By comparing the linear scanning curve of Example 2 and commercial platinum carbon 20% Pt/C, it is found that the initial potential of Example 2 is 0.91V (Vs.RHE), the half-wave potential is 0.83V (Vs.RHE), and the limiting current density 3.52mA/cm 2 , inferior to the starting potential of Example 1 0.95V (Vs.RHE), half-wave potential 0.88V (Vs.RHE), limiting current density 5.88mA/cm 2 ; also inferior to commercial 20% Pt The initial potential of /C was 0.95V (Vs.RHE), the half-wave potential was 0.87V (Vs.RHE), and the limiting current density was 4.68mA/cm 2 .
图11是实施例2制备得到的Pt 5.14％/N-C 90.44％/(CeO 2) 4.42％催化剂的氮气吸脱附等温曲线图(比表面积值为：603.75m 2/g)。 11 is a nitrogen adsorption and desorption isotherm curve diagram of the Pt 5.14% /NC 90.44% /(CeO 2 ) 4.42% catalyst prepared in Example 2 (specific surface area value: 603.75 m 2 /g).
实施例3(与实施例1区别在于氯铂酸钾用量为0.2g)Embodiment 3 (different from embodiment 1 is that potassium chloroplatinate consumption is 0.2g)
配置浓度为0.1M的硝酸铈溶液，并用氢氧化钠调节至溶液的pH＝12，磁力搅拌2小时后，将溶液放置烘箱中60℃保持1h，过滤洗涤后将黄色固体放置烘箱中保持130℃退火4h,待冷却2h至室温后制得氧化铈。A 0.1M cerium nitrate solution was prepared and adjusted to pH=12 with sodium hydroxide. After magnetic stirring for 2 hours, the solution was placed in an oven at 60°C for 1 hour. After filtering and washing, the yellow solid was placed in an oven and kept at 130°C. After annealing for 4h, cerium oxide was obtained after cooling to room temperature for 2h.
将0.6g(3.5mmol)氧化铈，0.2g(0.4mmol)氯铂酸钾(K 2PtCl 6)加入40ml的1mol/LHCl溶液中，得到溶液I，超声分散2小时后，取0.6ml(6.4mmol)苯胺单体加入溶液I中得到溶液II；将0.6gAPS(4mmol)溶于10ml的1mol/LHCL溶液中，得到溶液III，超声2小时使其分散均匀；控制溶液III的滴速，使其慢速滴入溶液II中；保持5℃，反应5小时；反应过程中伴随磁力搅拌；过滤洗涤后得到催化剂前驱体材料。 Add 0.6g (3.5mmol) of cerium oxide and 0.2g (0.4mmol) of potassium chloroplatinate (K 2 PtCl 6 ) to 40ml of 1mol/L HCl solution to obtain solution I, after ultrasonic dispersion for 2 hours, take 0.6ml (6.4 mmol) aniline monomer was added in solution I to obtain solution II; 0.6g APS (4mmol) was dissolved in 10ml of 1mol/LHCL solution to obtain solution III, which was uniformly dispersed by ultrasonic for 2 hours; the dripping speed of solution III was controlled to make it Slowly drop into solution II; keep at 5° C. and react for 5 hours; magnetic stirring is accompanied during the reaction; after filtration and washing, the catalyst precursor material is obtained.
将催化剂前驱体材料在惰性气体Ar 2氛围保护下，升温速率为10℃/min,由室温升至800℃，反应2小时，自然冷却后得到最终产物，经检测最终产物为Pt 6.8％/N-C 89.36％/(CeO 2) 3.84％。将上述所得最终产物制成催化剂浆料利用旋转圆盘电极、电化学工作站在电解质溶液0.1MKOH中进行与实例1相同的电化学测试。 Under the protection of the inert gas Ar 2 atmosphere, the catalyst precursor material was heated at a rate of 10 °C/min, from room temperature to 800 °C, and reacted for 2 hours. After natural cooling, the final product was obtained. After testing, the final product was Pt 6.8% / NC 89.36% /(CeO 2 ) 3.84% . The final product obtained above was made into a catalyst slurry, and the same electrochemical test as in Example 1 was carried out in an electrolyte solution of 0.1 MKOH using a rotating disk electrode and an electrochemical workstation.
图12是实施例3制备得到的Pt 6.8％/N-C 89.36％/(CeO 2) 3.84％催化剂(图中简写为Pt 6.8％/N-C/CeO 2)的XRD图谱，从该图谱可以得知最终产物包含Pt和CeO 2。 Figure 12 is the XRD pattern of the Pt 6.8% /NC 89.36% /(CeO 2 ) 3.84% catalyst prepared in Example 3 (abbreviated as Pt 6.8% /NC/CeO 2 in the figure), from which the final product can be known Contains Pt and CeO 2 .
图13是实施例3制备得到的Pt 6.8％/N-C 89.36％/(CeO 2) 3.84％催化剂与商业铂碳20％Pt/C催化剂线性扫描伏安(LSV)对比图。实施例3的起始电位0.89V(Vs.RHE)，半波电位0.77V(Vs.RHE)，极限电流密度4.24mA/cm 2，劣于实施例1的起始电位0.95V(Vs.RHE)，半波电位0.88V(Vs.RHE)，极限电流密度5.88mA/cm 2；也劣于商业铂碳20％Pt/C的起始电位0.95V(Vs.RHE)，半波电位0.87V(Vs.RHE)，极限电流密度4.68mA/cm 2。 FIG. 13 is a linear sweep voltammetry (LSV) comparison diagram of the Pt 6.8% /NC 89.36% /(CeO 2 ) 3.84% catalyst prepared in Example 3 and the commercial platinum carbon 20% Pt/C catalyst. The onset potential of Example 3 is 0.89V (Vs.RHE), the half-wave potential is 0.77V (Vs.RHE), and the limiting current density is 4.24mA/cm 2 , which is inferior to the onset potential of Example 1, which is 0.95V (Vs.RHE). ), the half-wave potential is 0.88V (Vs.RHE), and the limiting current density is 5.88mA/cm 2 ; it is also inferior to the onset potential of commercial platinum carbon 20%Pt/C of 0.95V (Vs.RHE), and the half-wave potential is 0.87V (Vs.RHE), limiting current density 4.68 mA/cm 2 .
图14是实施例3制备得到的Pt 6.8％/N-C 89.36％/(CeO 2) 3.84％催化剂的氮气吸脱附等 温曲线图(比表面积为：68.34m 2/g)。 14 is a nitrogen adsorption and desorption isotherm diagram of the Pt 6.8% /NC 89.36% /(CeO 2 ) 3.84% catalyst prepared in Example 3 (specific surface area: 68.34 m 2 /g).
实施例4(与实施例1的区别是在酸性的电解质中测试)Example 4 (the difference from Example 1 is that it was tested in an acidic electrolyte)
将硝酸铈和氢氧化钠按照摩尔比1:4溶于一定量的去离水中，使溶液的pH＝12，磁力搅拌2小时后，将溶液放置烘箱中60℃保持1h，过滤洗涤后将黄色固体放置烘箱中保持130℃退火4h制得氧化铈。Dissolve cerium nitrate and sodium hydroxide in a certain amount of deionized water in a molar ratio of 1:4 to make the pH of the solution = 12. After magnetic stirring for 2 hours, place the solution in an oven at 60 °C for 1 hour, filter and wash the yellow The solid was placed in an oven and kept at 130 °C for 4 h to obtain cerium oxide.
将0.6g氧化铈，0.1g氯铂酸钾(K 2PtCl 6)加入40ml的1mol/LHCl溶液中，得到溶液I，超声分散2小时后，取0.6ml苯胺单体加入溶液I中得到溶液II。将0.6gAPS溶于10ml的1mol/LHCl溶液中，得到溶液III，超声2小时使其分散均匀。控制溶液III的滴速，使其慢速滴入溶液II中。保持5℃，反应5小时。反应过程中伴随磁力搅拌。过滤洗涤后得到催化剂前驱体材料。 0.6g of cerium oxide and 0.1g of potassium chloroplatinate (K 2 PtCl 6 ) were added to 40ml of 1mol/L HCl solution to obtain solution I, after ultrasonic dispersion for 2 hours, 0.6ml of aniline monomer was added to solution I to obtain solution II . 0.6 g of APS was dissolved in 10 ml of 1 mol/L HCl solution to obtain solution III, which was uniformly dispersed by ultrasound for 2 hours. The dripping speed of solution III was controlled so that it was slowly dripped into solution II. Keep at 5°C and react for 5 hours. The reaction was accompanied by magnetic stirring. After filtering and washing, a catalyst precursor material is obtained.
将催化剂前驱体材料在惰性气体Ar 2氛围保护下，升温速率为10℃/min,由室温升至800℃，反应2小时，自然冷却后得到最终产物，经检测最终产物为Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％。与实例1相比，电化学测试得电解质溶液有所改变。将上述所得最终产物制成催化剂浆料利用旋转圆盘电极、电化学工作站在电解质溶液0.1M HClO 4中进行与实例1相同电化学测试。 Under the protection of the inert gas Ar 2 atmosphere, the catalyst precursor material was heated at a rate of 10 °C/min, and the temperature was increased from room temperature to 800 °C, and the reaction was carried out for 2 hours. After natural cooling, the final product was obtained . NC 90.14% /(CeO 2 ) 4.22% . Compared with Example 1, the electrolytic solution was changed in electrochemical tests. The final product obtained above was made into a catalyst slurry, and the same electrochemical test as in Example 1 was carried out in an electrolyte solution of 0.1 M HClO 4 using a rotating disk electrode and an electrochemical workstation.
图15是实施例4制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％(图中简写为Pt 5.64％/N-C/CeO 2)与商业铂碳20％Pt/C催化剂在氧气饱和的0.1M HClO 4的溶液中进行测试得到的线性扫描伏安(LSV)对比图。通过对比实施例4制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％与商业玻碳20％Pt/C的线性扫描曲线图发现，实施例4的起始电位0.88V(Vs.RHE)，半波电位0.83V(Vs.RHE),均优于商业铂碳20％Pt/C的起始电位0.87V(Vs.RHE)，半波电位0.79V(Vs.RHE)。 Figure 15 shows the Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% (abbreviated as Pt 5.64% /NC/CeO 2 in the figure) prepared in Example 4 and the commercial platinum carbon 20% Pt/C catalyst in oxygen saturation Comparison of linear sweep voltammetry (LSV) obtained by testing in a solution of 0.1 M HClO 4 . By comparing the linear scan curve of Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% prepared in Example 4 and commercial glassy carbon 20% Pt/C, it is found that the onset potential of Example 4 is 0.88V (Vs. RHE), half-wave potential of 0.83V (Vs.RHE), which are better than the initial potential of commercial platinum carbon 20%Pt/C 0.87V (Vs.RHE) and half-wave potential of 0.79V (Vs.RHE).
对比例1(没有氧化铈)Comparative Example 1 (without cerium oxide)
将0.1g氯铂酸钾(K 2PtCl 6)加入40ml的1mol/LHCl溶液中，得到溶液I，超声分散2小时后，取0.6ml苯胺单体加入溶液I中得到溶液II。将0.6gAPS溶于10ml的1mol/LHCl溶液中，得到溶液III，超声2小时使其分散均匀。控制溶液III的滴速，使其慢速滴入溶液II中。保持5℃，反应5小时。反应过程中伴随磁力搅拌。过滤洗涤后得到催化剂前驱体材料。将催化剂前驱体材料在惰性气体Ar 2氛围保护下，升温速率为10℃/min,由室温升至800℃，反应2小时，自然冷却后得到最终产物，经检测最终产物为Pt/N-C。与实例1相比，实例2没有添加氧化铈。将上述所得最终产物作为催化剂利用旋转圆盘电极、电化学工作站在电解质溶液0.1MKOH中进行电化学测试。 Add 0.1 g potassium chloroplatinate (K 2 PtCl 6 ) to 40 ml of 1 mol/L HCl solution to obtain solution I. After ultrasonic dispersion for 2 hours, add 0.6 ml of aniline monomer to solution I to obtain solution II. 0.6 g of APS was dissolved in 10 ml of 1 mol/L HCl solution to obtain solution III, which was uniformly dispersed by ultrasound for 2 hours. The dripping speed of solution III was controlled so that it was slowly dripped into solution II. Keep at 5°C and react for 5 hours. The reaction was accompanied by magnetic stirring. After filtering and washing, a catalyst precursor material is obtained. Under the protection of inert gas Ar 2 atmosphere, the catalyst precursor material was heated at a rate of 10 °C/min, from room temperature to 800 °C, and reacted for 2 hours. After natural cooling, the final product was obtained. The final product was detected as Pt/NC. Compared to Example 1, Example 2 did not add cerium oxide. The final product obtained above was used as a catalyst to conduct electrochemical tests in an electrolyte solution of 0.1 MKOH using a rotating disk electrode and an electrochemical workstation.
图16是实施例1制备得到的Pt 5.64％/N-C 90.14％/(CeO 2) 4.22％，对比例1制备得到的Pt/N-C，对比例2制备得到的N-C/CeO 2，以及商业铂碳20％Pt/C催化剂，在氧气饱和的0.1M KOH的溶液中进行测试得到的线性扫描伏安(LSV)对比图。通过对比实施例1的线性扫描曲线图发现，对比例1的起始电位0.94V(Vs.RHE)，半波电位0.69V(Vs.RHE)，极限电流密度4.47mA/cm 2,均劣于实施例1的起始电位0.95V(Vs.RHE)，半波电位0.88V(Vs.RHE)，极限电流密度5.88mA/cm 2。 Figure 16 shows Pt 5.64% /NC 90.14% /(CeO 2 ) 4.22% prepared in Example 1, Pt/NC prepared in Comparative Example 1, NC/CeO 2 prepared in Comparative Example 2 , and commercial platinum carbon 20 %Pt/C catalyst, line sweep voltammetry (LSV) comparison graph obtained by testing in an oxygen-saturated solution of 0.1M KOH. According to the linear scanning curve of Comparative Example 1, it is found that the initial potential of Comparative Example 1 is 0.94V (Vs.RHE), the half-wave potential is 0.69V (Vs.RHE), and the limiting current density is 4.47mA/cm 2 , which are all inferior to The initial potential of Example 1 was 0.95V (Vs.RHE), the half-wave potential was 0.88V (Vs.RHE), and the limiting current density was 5.88mA/cm 2 .
对比例2(没有Pt)Comparative Example 2 (without Pt)
将硝酸铈和氢氧化钠按照摩尔比1:4溶于一定量的去离水中，使溶液的pH＝12，磁力搅拌2小时后，将溶液放置烘箱中60℃保持1h，过滤洗涤后将黄 色固体放置烘箱中保持130℃退火4h制得氧化铈。将0.6g氧化铈加入40ml的1mol/LHCl溶液中，得到溶液I，超声分散2小时后，取0.6ml苯胺单体加入溶液I中得到溶液II。将0.6gAPS溶于10ml的1mol/LHCl溶液中，得到溶液III，超声2小时使其分散均匀。控制溶液III的滴速，使其慢速滴入溶液II中。保持5℃，反应5小时。反应过程中伴随磁力搅拌。过滤洗涤后得到催化剂前驱体材料。将催化剂前驱体材料在惰性气体Ar 2氛围保护下，升温速率为10℃/min,由室温升至800℃，反应2小时，自然冷却后得到最终产物，经检测最终产物为N-C/CeO 2。与实例1相比，对比例2没有添加氯铂酸钾。将上述所得最终产物取2mg，加入400微升乙醇，25微升全氟磺酸，制得催化剂浆料，取10微升催化剂浆料涂到玻碳电极上。采用三电极体系，负载有催化剂浆料的玻碳电极为工作电极，铂丝电极为对电极，银氯化银电极为参比电极在电解质溶液0.1MKOH中进行电化学测试。 Dissolve cerium nitrate and sodium hydroxide in a certain amount of deionized water in a molar ratio of 1:4 to make the pH of the solution = 12. After magnetic stirring for 2 hours, place the solution in an oven at 60 °C for 1 hour. After filtering and washing, the yellow The solid was placed in an oven and kept annealed at 130 °C for 4 h to obtain cerium oxide. 0.6 g of cerium oxide was added to 40 ml of 1 mol/L HCl solution to obtain solution I. After ultrasonic dispersion for 2 hours, 0.6 ml of aniline monomer was added to solution I to obtain solution II. 0.6 g of APS was dissolved in 10 ml of 1 mol/L HCl solution to obtain solution III, which was uniformly dispersed by ultrasound for 2 hours. The dripping speed of solution III was controlled so that it was slowly dripped into solution II. Keep at 5°C and react for 5 hours. The reaction was accompanied by magnetic stirring. After filtering and washing, a catalyst precursor material is obtained. Under the protection of the inert gas Ar 2 atmosphere, the catalyst precursor material was heated at a rate of 10 ° C/min, from room temperature to 800 ° C, and reacted for 2 hours. After natural cooling, the final product was obtained. After testing, the final product was NC/CeO 2 . Compared to Example 1, Comparative Example 2 did not add potassium chloroplatinate. Take 2 mg of the final product obtained above, add 400 microliters of ethanol and 25 microliters of perfluorosulfonic acid to prepare a catalyst slurry, and take 10 microliters of the catalyst slurry and apply it to the glassy carbon electrode. A three-electrode system was used, the glassy carbon electrode loaded with the catalyst slurry was the working electrode, the platinum wire electrode was the counter electrode, and the silver-silver chloride electrode was the reference electrode. Electrochemical tests were carried out in an electrolyte solution of 0.1 MKOH.
参见图16，通过对比实施例1的线性扫描曲线图发现，对比例2的起始电位0.88V(Vs.RHE)，半波电位0.79V(Vs.RHE)，极限电流密度3.38mA/cm 2,均劣于实施例1的起始电位0.95V(Vs.RHE)，半波电位0.88V(Vs.RHE)，极限电流密度5.88mA/cm 2。 Referring to FIG. 16 , it is found from the linear scanning graph of Comparative Example 1 that the initial potential of Comparative Example 2 is 0.88V (Vs.RHE), the half-wave potential is 0.79V (Vs.RHE), and the limiting current density is 3.38mA/cm 2 , are inferior to the initial potential of Example 1 of 0.95V (Vs.RHE), the half-wave potential of 0.88V (Vs.RHE), and the limiting current density of 5.88mA/cm 2 .
本发明各实施例、对比例中提到的各项检测的具体方法如下：The specific methods of each detection mentioned in each embodiment of the present invention and the comparative example are as follows:
1、电化学测试1. Electrochemical test
电催化剂浆液配制：将2.0mg电催化剂粉末与400μL无水乙醇和25μL 5％(质量分数)Nafion溶液混合，超声60min分散均匀。Preparation of electrocatalyst slurry: 2.0 mg of electrocatalyst powder was mixed with 400 μL of absolute ethanol and 25 μL of 5% (mass fraction) Nafion solution, and dispersed uniformly by ultrasonic for 60 min.
商业铂碳20％(质量分数)Pt/C电催化剂浆液制备方法：将2.0mg 20％(质 量分数)Pt/C电催化剂粉末与与400μL无水乙醇和25μL 5％(质量分数)Nafion溶液混合，超声60min分散均匀。Preparation method of commercial platinum-carbon 20% (mass fraction) Pt/C electrocatalyst slurry: Mix 2.0 mg 20% (mass fraction) Pt/C electrocatalyst powder with 400 μL absolute ethanol and 25 μL 5% (mass fraction) Nafion solution , ultrasonic 60min dispersed uniformly.
旋转圆盘电极(RDE)测试：使用电化学工作站(型号：Interface 1010E，美国Gamry，美国)以及电极旋转装置(型号：AFMSRCE，PINE公司，美国)在三电极体系下对电催化剂的ORR性能进行评价。Ag/AgCl为参比电极，铂丝为对电极，以涂有电催化剂的玻碳电极为工作电极(型号：E5GC，玻碳盘面积为0.196cm 2，PINE公司，美国)。工作电极制备方法如下，使用移液枪取10μL电催化剂浆液滴至玻碳电极表面，红外灯烤干，得到分散均匀的电催化剂薄层，电催化剂的载量为0.24mg·cm -2。测试在O 2饱和的0.1mol·L -1KOH水溶液中进行，扫描速度10mV·s -1，扫描区间为0.2–1.2V(vs RHE)，电极转速1600r·min -1。稳定性测试测试于O 2饱和的0.1mol·L -1KOH溶液中进行，设置工作电极的循环伏安扫描电位区间为0.2–1.2V(vs RHE)，扫描圈数2000圈，扫描速率为50mV·s -1。记录2000圈后工作电极的循环伏安曲线图和电极转速为1600r·min -1线性扫描伏安曲线。 Rotating Disk Electrode (RDE) Test: The ORR performance of the electrocatalyst was tested in a three-electrode system using an electrochemical workstation (Model: Interface 1010E, Gamry, USA) and an electrode rotating device (Model: AFMSRCE, PINE Corporation, USA) Evaluation. Ag/AgCl was used as reference electrode, platinum wire was used as counter electrode, and glassy carbon electrode coated with electrocatalyst was used as working electrode (model: E5GC, glassy carbon disk area was 0.196 cm 2 , PINE Company, USA). The preparation method of the working electrode is as follows: 10 μL of the electrocatalyst slurry is dropped onto the surface of the glassy carbon electrode using a pipette gun, and dried under an infrared lamp to obtain a uniformly dispersed electrocatalyst thin layer. The electrocatalyst loading is 0.24 mg·cm -2 . The test was carried out in 0.1 mol·L -1 KOH aqueous solution saturated with O 2 , the scanning speed was 10 mV·s -1 , the scanning interval was 0.2–1.2 V (vs RHE), and the electrode speed was 1600 r·min -1 . Stability test The test was carried out in a 0.1 mol·L -1 KOH solution saturated with O 2 , the cyclic voltammetry potential range of the working electrode was set to be 0.2–1.2 V (vs RHE), the number of scan cycles was 2000, and the scan rate was 50 mV. ·s -1 . After 2000 cycles, the cyclic voltammetry curve of the working electrode and the linear sweep voltammetry curve of the electrode rotating speed of 1600r·min -1 were recorded.
2、XRD图谱分析2. XRD pattern analysis
使用X射线衍射仪(XRD)(型号：X’Pert PRO厂家：PANalytical，荷兰)对合成样品的物相纯度的和晶型进行了表征，在电压为40kV，电流为100mA，扫描速率为1°/min，2θ范围为为10°-90°的条件进行测试。The phase purity and crystal form of the synthesized samples were characterized using an X-ray diffractometer (XRD) (Model: X'Pert PRO Manufacturer: PANalytical, The Netherlands) at a voltage of 40kV, a current of 100mA, and a scan rate of 1° /min, the 2θ range is 10°-90°.
3、TEM图3. TEM image
使用型号为JEOL JEM2010的场发射透射电子显微镜(Transmission Electron Microscopy,TEM)来观察催化剂的围观形貌及结构，加速电压为200kV。同时利用高分辨(Highresolution,HR)TEM,高角度环形暗场(high angle  annular dark field,HAADF)及扫描TEM(scanning transmission electron microscopy,STEM)深入分析催化剂内部结构及元素分布情况。The morphology and structure of the catalysts were observed using a field emission transmission electron microscope (TEM), model JEOL JEM2010, with an accelerating voltage of 200 kV. At the same time, high-resolution (HR) TEM, high-angle annular dark field (HAADF) and scanning TEM (scanning transmission electron microscopy, STEM) were used to deeply analyze the internal structure and element distribution of the catalyst.
4、STEM图4. STEM image
使用型号为JEOL JEM2010的场发射透射电子显微镜(Transmission Electron Microscopy,TEM)来观察催化剂的围观形貌及结构，加速电压为200kV。同时利用高分辨(Highresolution,HR)TEM,高角度环形暗场(high angle annular dark field,HAADF)及扫描TEM(scanning transmission electron microscopy,STEM)深入分析催化剂内部结构及元素分布情况。The morphology and structure of the catalysts were observed using a field emission transmission electron microscope (TEM), model JEOL JEM2010, with an accelerating voltage of 200 kV. At the same time, high-resolution (HR) TEM, high-angle annular dark field (HAADF) and scanning TEM (scanning transmission electron microscopy, STEM) were used to deeply analyze the internal structure and element distribution of the catalyst.
5、低温氮气吸脱附测试5. Low temperature nitrogen adsorption and desorption test
低温氮气吸脱附测试用BELSORP-max型仪器(MicrotracBEL公司，日本)，使用Brunauer-Emmett-Teller(BET)方法对电催化剂比表面积进行计算。The low-temperature nitrogen gas adsorption and desorption test was performed with a BELSORP-max instrument (MicrotracBEL, Japan), and the electrocatalyst specific surface area was calculated using the Brunauer-Emmett-Teller (BET) method.
6、Pt含量以及CeO 2含量的测试 6. Test of Pt content and CeO 2 content
Pt含量以及CeO 2含量的测试方法：ICP-OES：使用电感耦合等离子体发射光谱仪(ICP-OES)(型号：Agilent 720ES)来检测催化剂中金属的准确含量，由此来计算催化剂的真实质量活性。样品制备：将催化剂溶于王水中，质量浓度在5-10mg L -1之间，待溶解完全后，取中层澄清液过滤后测试。 Test method for Pt content and CeO 2 content: ICP-OES: Inductively coupled plasma optical emission spectrometer (ICP-OES) (model: Agilent 720ES) is used to detect the accurate content of metals in the catalyst, thereby calculating the real mass activity of the catalyst . Sample preparation: Dissolve the catalyst in aqua regia, the mass concentration is between 5-10 mg L -1 , after the dissolution is complete, take the middle layer clear liquid and filter it for testing.
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等同物。The foregoing has shown and described the basic principles, main features and advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited by the above-mentioned embodiments. The above-mentioned embodiments and descriptions only illustrate the principle of the present invention. Such changes and improvements fall within the scope of the claimed invention. The scope of the claimed invention is determined by the appended claims and their equivalents.

Claims (10)

  1. 一种ORR催化剂材料，其特征在于，由微纳米级CeO 2、贵金属M和氮掺杂的碳材料组成，氮在碳中的掺杂量按摩尔比为0.05-0.1：1，所述ORR催化剂材料中CeO 2和贵金属M均匀地分布在氮掺杂的碳材料中，所述ORR催化剂材料符合以下通式： An ORR catalyst material, characterized in that it is composed of micro-nano-scale CeO 2 , noble metal M and nitrogen-doped carbon material, and the doping amount of nitrogen in carbon is 0.05-0.1:1 in molar ratio, and the ORR catalyst is In the material, CeO 2 and noble metal M are uniformly distributed in the nitrogen-doped carbon material, and the ORR catalyst material conforms to the following general formula:
    M x/N-C (1-x-y)/(CeO 2) y     (I) M x /NC (1-xy) /(CeO 2 ) y (I)
    其中贵金属M为Pt、Pd和Au中的一种或两种以上，x、y为质量百分数，x的范围为5％-6％，优选5.5％-5.7％，y的范围为4％-12％，优选4％-5％；更优选地，贵金属M为Pt,贵金属Pt颗粒的粒径为3-8nm；Wherein the precious metal M is one or more of Pt, Pd and Au, x and y are mass percentages, the range of x is 5%-6%, preferably 5.5%-5.7%, and the range of y is 4%-12 %, preferably 4%-5%; more preferably, the precious metal M is Pt, and the particle size of the precious metal Pt particles is 3-8 nm;
    优选地，所述ORR催化剂材料是多孔材料，比表面积是40m 2/g-800m 2/g。 Preferably, the ORR catalyst material is a porous material with a specific surface area of 40m 2 /g-800m 2 /g.
  2. 一种如权利要求1所述的ORR催化剂材料的制备方法，其特征在于，包括以下步骤：A kind of preparation method of ORR catalyst material as claimed in claim 1, is characterized in that, comprises the following steps:
    1)获取CeO 2； 1) Obtain CeO 2 ;
    2)利用所述CeO 2制得催化剂前驱体材料,所述催化剂前躯体材料是由贵金属酸根掺杂的导电高分子复合材料，所述催化剂前躯体材料化学式为CeO 2/CP-MX n-，X为酸根，n为1或2； 2) using the CeO 2 to prepare a catalyst precursor material, the catalyst precursor material is a conductive polymer composite material doped with noble metal acid radicals, and the chemical formula of the catalyst precursor material is CeO 2 /CP-MX n- , X is an acid radical, and n is 1 or 2;
    3)高温碳化所述催化剂前驱体材料制得所述ORR催化剂材料。3) Carbonizing the catalyst precursor material at high temperature to obtain the ORR catalyst material.
  3. 如权利要求2所述的ORR催化剂材料的制备方法，其特征在于，所述步骤2)利用所述CeO 2制得催化剂前驱体材料包括以下步骤： The method for preparing an ORR catalyst material according to claim 2, wherein the step 2) using the CeO 2 to prepare a catalyst precursor material comprises the following steps:
    2.1)将所述CeO 2分散于贵金属M的酸或盐溶液中，得到溶液I； 2.1 ) the CeO is dispersed in the acid or salt solution of the precious metal M to obtain solution I;
    2.2)将导电高分子单体加入所述溶液I中得到溶液II；2.2) adding the conductive polymer monomer into the solution I to obtain solution II;
    2.3)将氧化剂或氧化剂的酸溶液加入所述溶液II中，进行原位聚合反应制得所述催化剂前驱体材料。2.3) Add an oxidant or an acid solution of an oxidant to the solution II, and perform in-situ polymerization to obtain the catalyst precursor material.
  4. 如权利要求3所述的ORR催化剂材料的制备方法，其特征在于，所述步骤2.1)中，所述CeO 2与所述贵金属M的酸或盐的摩尔比值范围为8-70：1；和/或 The method for preparing an ORR catalyst material according to claim 3, wherein in the step 2.1), the molar ratio of the CeO 2 to the acid or salt of the noble metal M is in the range of 8-70:1; and /or
    所述步骤2.2)中，所述导电高分子单体与所述贵金属M的酸或盐的摩尔比值范围为16-128：1；和/或In the step 2.2), the molar ratio of the conductive polymer monomer to the acid or salt of the noble metal M is in the range of 16-128:1; and/or
    所述步骤2.3)中，所述氧化剂与所述导电高分子单体的摩尔比值范围为2-3：1；和/或In the step 2.3), the molar ratio of the oxidant to the conductive polymer monomer is in the range of 2-3:1; and/or
    所述步骤2.3)中，所述氧化剂的酸溶液是氧化剂的盐酸溶液，所述氧化剂与所述盐酸中的HCl的摩尔比为1：3-4。In the step 2.3), the acid solution of the oxidant is a hydrochloric acid solution of the oxidant, and the molar ratio of the oxidant to the HCl in the hydrochloric acid is 1:3-4.
  5. 如权利要求3或4所述的ORR催化剂材料的制备方法，其特征在于，所述贵金属M的酸或盐为H 2PdCl 4、Pd(NH 3) 4Cl 2、Pd(NH 3) 2Cl 2、Pd(NH 3) 4SO 4、Pd(NH 3) 4(NO 3) 2、H 2PtCl 6、H 2PtCl 4、K 2PtCl 6、(NH 4) 2PtCl 6、K 2PtCl 4、(NH4) 2PtCl 4、HAuCl 4、NaAuCl 4、KAuCl 4及其水合物中的一种或两种以上。 The method for preparing an ORR catalyst material according to claim 3 or 4, wherein the acid or salt of the noble metal M is H 2 PdCl 4 , Pd(NH 3 ) 4 Cl 2 , and Pd(NH 3 ) 2 Cl 2 , Pd(NH 3 ) 4 SO 4 , Pd(NH 3 ) 4 (NO 3 ) 2 , H 2 PtCl 6 , H 2 PtCl 4 , K 2 PtCl 6 , (NH 4 ) 2 PtCl 6 , K 2 PtCl 4 One or more of (NH4) 2 PtCl 4 , HAuCl 4 , NaAuCl 4 , KAuCl 4 and their hydrates.
  6. 如权利要求3或4所述的ORR催化剂材料的制备方法，其特征在于，所述导电高分子单体为聚苯胺、聚吡咯中的一种或两种；和/或The method for preparing an ORR catalyst material according to claim 3 or 4, wherein the conductive polymer monomer is one or both of polyaniline and polypyrrole; and/or
    所述氧化剂为APS或FeCl 3。 The oxidant is APS or FeCl 3 .
  7. 如权利要求2所述的ORR催化剂材料的制备方法，其特征在于，所述步骤2)高温碳化所述催化剂前驱体材料制得所述ORR催化剂材料包括以下步骤：将所述催化剂前驱体材料在惰性气体氛围保护下，以升温速率为5-20℃/min,由室温升至600-1000℃，反应2-4小时，自然冷却后得到所述ORR催化剂材料。The method for preparing an ORR catalyst material according to claim 2, wherein the step 2) carbonizing the catalyst precursor material at a high temperature to obtain the ORR catalyst material comprises the following steps: placing the catalyst precursor material in a Under the protection of an inert gas atmosphere, at a heating rate of 5-20° C./min, the temperature is raised from room temperature to 600-1000° C., the reaction is performed for 2-4 hours, and the ORR catalyst material is obtained after natural cooling.
  8. 一种如权利要求1所述的ORR催化剂材料的用途，其特征在于，用作氢氧燃料电池或金属空气电池的阴极电极。A use of the ORR catalyst material according to claim 1, characterized in that it is used as a cathode electrode of a hydrogen-oxygen fuel cell or a metal-air battery.
  9. 一种氢氧燃料电池，包括阴极电极，其特征在于，所述阴极电极的催化剂采用如权利要求1所述的ORR催化剂材料或者采用如权利要求2-7任一项制备得到的ORR催化剂材料。A hydrogen-oxygen fuel cell, comprising a cathode electrode, characterized in that the catalyst of the cathode electrode adopts the ORR catalyst material according to claim 1 or the ORR catalyst material prepared according to any one of claims 2-7.
  10. 一种金属空气电池，包括阴极电极，其特征在于，所述阴极电极的催化剂采用如权利要求1所述的ORR催化剂材料或者采用如权利要求2-7任一项制备得到的ORR催化剂材料。A metal-air battery, comprising a cathode electrode, characterized in that, the catalyst of the cathode electrode adopts the ORR catalyst material according to claim 1 or the ORR catalyst material prepared according to any one of claims 2-7.
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