WO2024251306A1 - 载体材料及其制备方法 - Google Patents

载体材料及其制备方法 Download PDF

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Publication number
WO2024251306A1
WO2024251306A1 PCT/CN2024/108259 CN2024108259W WO2024251306A1 WO 2024251306 A1 WO2024251306 A1 WO 2024251306A1 CN 2024108259 W CN2024108259 W CN 2024108259W WO 2024251306 A1 WO2024251306 A1 WO 2024251306A1
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Prior art keywords
carrier material
product
characteristic value
ranges
heat treatment
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PCT/CN2024/108259
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English (en)
French (fr)
Inventor
马畅
颜聿聪
李子坤
黄友元
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Shenzhen BTR New Energy Technology Research Institute Co Ltd
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Shenzhen BTR New Energy Technology Research Institute Co Ltd
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Priority to KR1020247034258A priority Critical patent/KR102875363B1/ko
Priority to JP2024561579A priority patent/JP7795285B2/ja
Publication of WO2024251306A1 publication Critical patent/WO2024251306A1/zh
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • 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
    • H01M4/8605—Porous electrodes
    • 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
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/881—Electrolytic membranes
    • 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
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present application relates to the technical field of fuel cells, and in particular to a carrier material and a preparation method thereof.
  • the membrane electrode is the core component of the fuel cell.
  • the catalyst in the membrane electrode can convert chemical energy into electrical energy.
  • the three components of gas, electrons and protons undergo electrochemical reactions on the catalyst surface to generate water and supply energy to the connected load device.
  • the membrane electrode is provided with a carrier material that carries the catalyst. While carrying the catalyst, it also provides a continuous transmission channel for protons, reaction gases and water for the electrochemical reaction.
  • the microscopic particles of the support material are often constructed into a porous structure so that the support material has a larger specific surface area, which will provide more attachment points for the precious metal particles in the catalyst and provide a reaction site for the catalytic reaction.
  • the embodiments of the present application provide a carrier material and a preparation method thereof to solve the problem of large mass transfer resistance of existing membrane electrodes.
  • the present invention is implemented by providing a method for preparing a carrier material, comprising the following steps:
  • the microscopic particles of the carrier material are configured to have a plurality of pores and a plurality of cavities, wherein the pores are connected to the exterior of the microscopic particles and the cavities are isolated from the exterior of the microscopic particles;
  • the ratio of the mass of the carrier material to the total volume of the pores is defined as the pore characteristic value; the ratio of the mass of the carrier material to the total volume of the cavity is defined as the cavity characteristic value; the pore characteristic value of the carrier material is smaller than the cavity characteristic value of the carrier material.
  • the embodiment of the present application further provides a carrier material prepared by the above method for preparing the carrier material.
  • an embodiment of the present application also provides a membrane electrode for a fuel cell, comprising the aforementioned carrier material.
  • FIG1 is a schematic diagram of the structure of a fuel cell provided in an embodiment of the present application.
  • FIG2 is a schematic diagram of the main steps of a method for preparing a carrier material provided in an embodiment of the present application
  • FIG3 is a schematic diagram of the microstructure of a catalyst layer provided in an embodiment of the present application.
  • FIG4 is a schematic diagram of the structure of a carrier material and catalyst particles combined according to an embodiment of the present application.
  • FIG5 is a schematic diagram of the main steps of a method for preparing a catalytic layer provided in an embodiment of the present application.
  • FIG6 is a schematic diagram of the structure of an equivalent circuit of an EIS test
  • FIG7 is a schematic diagram showing the law of pore characteristic values and mass transfer impedance of a carrier material provided in an embodiment of the present application.
  • FIG8 is a schematic diagram of the law of cavity characteristic values and ECSA retention rates of a carrier material provided in an embodiment of the present application.
  • a and/or B can mean: A exists alone, A and B exist at the same time, and B exists alone.
  • a and B can be singular or plural.
  • At least one means one or more
  • plural means two or more.
  • “One or more”, “at least one of the following” or similar expressions refer to any combination of these items, including any combination of single or plural items.
  • “at least one of a, b, or c”, or “at least one of a, b, and c” can all mean: a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple, respectively.
  • the fuel cell of the present application includes: a membrane electrode with two plates 100 disposed therebetween.
  • the membrane electrode includes: a proton membrane 300, a catalyst layer 400 and a diffusion layer 200.
  • the functions, structures and preparation methods of each part of the fuel cell of the present application except the catalyst layer 400 are conventional solutions well known to those skilled in the art, and are not the focus of improvement of the present application, and will not be elaborated here.
  • the present application embodiment provides a method for preparing a carrier material, comprising the following main steps:
  • the template includes one or a mixture of two or more of carbon quantum dots, nano-aluminum oxide, nano-silicon oxide, nano-magnesium oxide, nano-calcium oxide, and nano-calcium carbonate.
  • the metal salt in the metal salt mixed solution includes one or more of ferric nitrate, chromium nitrate, cobalt nitrate, nickel nitrate, zinc nitrate, magnesium nitrate, ferric chloride, cobalt chloride, nickel chloride, zinc chloride, magnesium chloride, ferric sulfate, ferric sulfate, ferric sulfate, zinc sulfate, and magnesium sulfate.
  • the mixed solvent in the metal salt mixed solution includes a mixture of one or more of isopropanol, ethylene glycol, n-butanol, N-methylpyrrolidone, ethanol and distilled water.
  • the volume ratio of distilled water to the organic solvent in the mixed solvent ranges from 1 to 20.
  • step S110 is to obtain a template with a specific arrangement and to make the metal salt evenly attached to the template.
  • the concentration of the metal salt mixed solution in step S110 ranges from 10 mg/mL to 100 mg/mL, and a further optional concentration range includes 20 mg/mL to 50 mg/mL.
  • the specific concentration range of the first product in step S110 includes 10 wt.% to 50 wt.%, and a further optional concentration range includes 20 wt.% to 40 wt.%.
  • the second product is a template metal salt mixture.
  • the temperature range of low-temperature vacuum drying includes -40°C to 10°C, and a further optional temperature range includes -30°C to -10°C.
  • the organic carbon source includes one or more substances such as asphalt, sugar, heavy oil, fatty acid, polyvinyl alcohol, polyamide, epoxy resin, phenolic resin, organic salt and their derivatives.
  • the mass ratio of the organic carbon source to the second product is 0.1 to 3.
  • step S130 The purpose of step S130 is to mix with the organic carbon source without destroying the arrangement of the template.
  • S140 performing a first heat treatment on the third product in a vacuum or inert gas condition to obtain a fourth product.
  • the first heat treatment in step S140 is performed under vacuum or inert gas conditions, and the inert gas includes one or both of argon and nitrogen.
  • the temperature rise rate of the first heat treatment in step S140 ranges from 1°C/min to 20°C/min, and the heat treatment temperature ranges from 200°C to 1000°C.
  • the temperature rise rate of the first heat treatment ranges from 5°C/min to 10°C/min, and the heat treatment temperature ranges from 500°C to 700°C.
  • step S140 is to carbonize the organic carbon source to obtain a specific pore or cavity structure, wherein the source of the pores includes the pore-forming effect of the template and the pore-forming catalysis of the metal salt, and the carbon source itself generates pores or cavities during the shrinkage and carbonization process.
  • the fourth product is a carbon powder with a specific pore or cavity structure.
  • step S140 is to enable the template agent and the metal salt to work together to form a product with a certain pore and cavity structure.
  • the pickling solution includes one or more of hydrochloric acid, nitric acid, perchloric acid, sulfuric acid, acetic acid, and hydrofluoric acid.
  • the molar concentration of the pickling solution ranges from 0.2 mol/L to 5 mol/L. Further optionally, the molar concentration of the pickling solution ranges from 0.5 mol/L to 2 mol/L.
  • step S150 is to remove most of the metal salt and the template.
  • S160 The fifth product is subjected to a second heat treatment to obtain a carrier material.
  • S160 The purpose of S160 is that some pores will be closed to form cavities during the graphitization process, and the metal salts remaining in some cavities will react with carbon to form a pore structure. At the same time, the metal will undergo catalytic graphitization to varying degrees, increasing the degree of graphitization of the material.
  • step S160 mainly includes the following steps:
  • S161 subjecting the fifth product to high-temperature heat treatment under an inert atmosphere to obtain an intermediate product.
  • the inert atmosphere gas includes one or both of argon and nitrogen.
  • the temperature rise rate of the high temperature heat treatment in step S161 ranges from 1°C/min to 20°C/min, and the heat treatment temperature ranges from 1000°C to 2600°C.
  • the range of the heating rate of the high temperature heat treatment includes 5°C/min to 10°C/min, and the range of the heat treatment temperature includes 1400°C to 1900°C.
  • the cooling process adopts a method of natural cooling to room temperature.
  • the oxidizing atmosphere gas includes one or more of carbon dioxide, oxygen-containing oxidizing atmosphere (air, water vapor, oxygen, ozone, etc.), and ammonia.
  • the temperature rise rate of the medium-temperature heat treatment in step S163 ranges from 1°C/min to 20°C/min, and the heat treatment temperature ranges from 150°C to 500°C.
  • the range of the heating rate of the medium-temperature heat treatment includes 1°C/min to 15°C/min, and the range of the heat treatment temperature includes 200°C to 400°C.
  • step S160 The heat treatment scheme of step S160 is adopted to control the hole characteristic value and cavity characteristic value of the carrier material 410 .
  • high-temperature heat treatment increases the crystallinity of carbon materials.
  • the higher the crystallinity the stronger the corrosion resistance and the lower the specific surface area.
  • the carbon materials will undergo structural reorganization under high temperature conditions.
  • the surface graphite micro-chip layer will polymerize and rearrange in this process.
  • the pore structure (pore size, pore volume, etc.) will change in the process, and some of the pores will become cavities.
  • high temperature will also cause some metal salts to escape, forming new pore and cavity structures.
  • the medium temperature heat treatment is used to oxidize and modify the material. This process will reduce the fixed carbon content of the material, increase the content of oxygen, hydrogen, and nitrogen (depending on the synthesis conditions), and increase the content of corresponding groups to facilitate the attachment of precious metal particles. It will also improve the connectivity of the pore structure, and some cavity structures will be converted into pore structures.
  • an embodiment of the present application provides a carrier material 410, which mainly provides a carrier for catalyst particles 420 (precious metal particles, such as Pt nanoparticles) in the catalytic layer 400, and the carrier material 410 is a powder material.
  • catalyst particles 420 precious metal particles, such as Pt nanoparticles
  • the microscopic particles of the carrier material 410 of the present application are constructed to have multiple pores and multiple cavities, wherein the pores are connected to the outside of the microscopic particles, and the cavities are isolated from the outside of the microscopic particles; the ratio of the mass of the carrier material 410 to the total volume of the pores is defined as the pore characteristic value; the ratio of the mass of the carrier material 410 to the total volume of the cavities is defined as the cavity characteristic value; wherein the pore characteristic value of the carrier material 410 is less than the cavity characteristic value of the carrier material 410.
  • the carrier material 410 consists at least of a carbon material.
  • the mass transfer capacity of carbon materials is related to the size and type of pores. Usually, when the pore diameter is 2nm or above, the space that can communicate with the outside world during the mass transfer process is more likely to react stably and continuously and can promptly drain the generated water to ensure the continuous reaction. These spaces are called pores, including cross-linked pores, through holes and blind holes. The surface area of these pores can be detected and analyzed by gas adsorption method.
  • pores there may be some closed spaces in the microscopic particles of the carrier material 410.
  • the pore diameters of these pores are small ( ⁇ 2nm) or they are not connected to the outer surface, so the fluid cannot penetrate. These spaces cannot be effectively measured by gas adsorption method, mercury injection method and other measurement methods. Under working conditions, it is difficult to use them as the place where sustained and stable electrochemical reactions occur.
  • the pores in the microscopic particles of the carrier material of the present application have a pore size of 2 nm or less, it is difficult for the fluid to enter. Therefore, the pores with a pore size of 2 nm or less can also be classified as the cavities defined in the present application. That is, the "isolation from the outside of the microscopic particles of the carrier material 410" referred to in the present application is based on the inability of the fluid to effectively flow into.
  • the "cavity" referred to in the present application as “isolation from the outside of the microscopic particles of the carrier material 410” includes both closed spaces that are completely not connected to the outside of the microscopic particles of the carrier material 410, and those pores (non-closed spaces) that are connected to the outside of the microscopic particles of the carrier material 410 but have a pore size of 2 nm or less.
  • Carbon materials with larger pore characteristic values can greatly improve mass transfer capacity and reduce mass transfer resistance under high current density conditions.
  • Suitable pore structures can delay catalyst flooding and gas diffusion channel blockage.
  • carrier materials 410 with high cavity characteristic values can show higher durability under start-stop and other operating conditions.
  • This porous carbon material with optimized pores and cavities may also be used in other fields involving mass transfer and charge transfer processes, such as lithium batteries, sodium ion batteries, drug delivery, etc.
  • the ratio of the pore characteristic value to the cavity characteristic value of the carrier material 410 ranges from 0.005 to 0.045.
  • the ratio of the pore characteristic value to the cavity characteristic value of the carrier material 410 ranges from 0.0102 to 0.0163, more specifically from 0.014 to 0.015, or from 0.0145 to 0.0148.
  • the ratio of the pore characteristic value to the cavity characteristic value of the carrier material 410 ranges from 0.0232 to 0.0384, more specifically, from 0.020 to 0.030, or from 0.025 to 0.028.
  • the ratio of the pore characteristic value to the cavity characteristic value of the carrier material 410 ranges from 0.0090 to 0.0180, more specifically, from 0.012 to 0.013, or from 0.0125 to 0.0129.
  • the pore characteristic value of the carrier material 410 may range from 0.250 g/cm 3 to 0.450 g/cm 3 .
  • the pore characteristic value of the carrier material 410 may range from 0.260 g/cm 3 to 0.350 g/cm 3 .
  • the cavity characteristic value of the carrier material 410 may range from 10.00 g/cm 3 to 50.00 g/cm 3 .
  • the cavity characteristic value of the carrier material 410 may range from 20.00 g/cm 3 to 40.00 g/cm 3 .
  • the pore characteristic value of the carrier material 410 may range from 0.256 g/cm 3 to 0.298 g/cm 3 ; meanwhile, the cavity characteristic value of the carrier material 410 may range from 18.306 g/cm 3 to 24.902 g/cm 3 .
  • the pore characteristic value of the carrier material 410 may range from 0.375 g/cm 3 to 0.418 g/cm 3 ; meanwhile, the cavity characteristic value of the carrier material 410 may range from 10.897 g/cm 3 to 16.105 g/cm 3 .
  • the pore characteristic value of the carrier material 410 may range from 0.260 g/cm 3 to 0.350 g/cm 3 ; meanwhile, the cavity characteristic value of the carrier material 410 may range from 19.306 g/cm 3 to 30.026 g/cm 3 .
  • the pore characteristic value of the carrier material 410 may be 0.284, 0.319, or 0.399.
  • the cavity characteristic value of the carrier material 410 may be 14.298, 19.306, or 24.902.
  • the specific surface area of the support material 410 may range from 400 m 2 /g to 1500 m 2 /g. As a further option, the specific surface area of the support material 410 may range from 500 m 2 /g to 1100 m 2 /g.
  • the particle size of the carrier material 410 may range from 100 nm to 2 ⁇ m. As a further option, the particle size of the carrier material 410 may range from 200 nm to 800 nm.
  • the compacted density of the carrier material 410 may range from 0.05 g/mL to 0.80 g/mL. As a further option, the compacted density of the carrier material 410 may range from 0.10 g/mL to 0.50 g/mL.
  • the conductivity of the carrier material 410 may range from 6.4 S/cm to 26.5 S/cm.
  • the fixed carbon content of the support material 410 may range from 84.5% to 97.2%.
  • the present application sets the pore characteristic value ⁇ A as a characteristic value that can represent the content of pores in the carrier material where mass transfer reactions can occur stably, and sets the cavity characteristic value ⁇ Ir as a characteristic value that can represent the content of cavities in the carrier material where mass transfer reactions cannot occur stably;
  • ⁇ Id refers to the theoretical true density of ideal single crystal graphite (2.266 g/cm 3 ), m refers to the mass of the ideal single crystal graphite, and V Id refers to the volume of the ideal single crystal graphite with a mass of m.
  • ⁇ T refers to the true density of the carrier material
  • m refers to the mass of the carrier material
  • V Id refers to the volume of an ideal single crystal graphite with a mass of m
  • V Ir refers to the cavity volume of the carrier material with a mass of m.
  • ⁇ C refers to the compacted density of the carrier material
  • m refers to the mass of the carrier material
  • V Id refers to the volume of an ideal single crystal graphite with a mass of m
  • VA refers to the pore volume of the carrier material with a mass of m
  • V Ir refers to the cavity volume of the carrier material with a mass of m.
  • the calculation formulas for the pore characteristic value and cavity characteristic value in the present application are introduced above, so the pore characteristic value and cavity characteristic value in the present application can be calculated by the true density ⁇ T of the carrier material, the compacted density ⁇ C of the carrier material and the theoretical true density ⁇ Id of the ideal single crystal graphite.
  • an embodiment of the present application provides a method for preparing a catalytic layer using the above-mentioned carrier material, comprising the following steps:
  • the organic solvent in S210 includes one or more of ethanol, isopropanol, ethylene glycol, and n-butanol.
  • the noble metal precursor includes one or more of chloroplatinic acid, potassium chloroplatinate, potassium chloroplatinite, platinum dichloride, platinum tetrachloride, tetraammine dichloroplatinum, and platinum di(acetylacetonate).
  • the molar concentration of the noble metal precursor in step S210 ranges from 0.1 mol/L to 5 mol/L, and further optionally ranges from 1 mol/L to 2 mol/L.
  • the rotation speed of the vigorous stirring in S210 is 300-1000 rpm/min.
  • S220 Take the sixth product and heat and reduce it in a mixed gas atmosphere of H2 and inert gas at a specific concentration to obtain carbon powder with a specific precious metal content (seventh product).
  • the specific concentration of H2 in S220 can be a mixed gas of any ratio of H2 and Ar or H2 and N2 .
  • the range of the heating rate for heating reduction in step S220 includes 1°C/min to 20°C/min, and a further optional range of 5°C/min to 10°C/min; the temperature range for heating reduction is 200°C to 900°C, and a further optional range of 300°C to 400°C.
  • the pickling solution in S230 includes one or more of nitric acid, perchloric acid, and acetic acid.
  • the molar concentration of the pickling solution in S230 ranges from 0.2 mol/L to 5 mol/L, and a further optional range includes 0.5 mol/L to 2 mol/L.
  • the mass transfer capacity of the fuel cell catalyst layer 400 is related to the size and type of the carbon material pores.
  • the cavities and pores connected to the outside world react continuously and stably, and the generated water can be discharged in time to ensure the continuous progress of the reaction.
  • the organic biomass precursor treated at high temperature is decomposed and carbonized by heat, and the corresponding pore structure is generated under the action of the template agent.
  • the molecules of the surface graphite micro-chip layer are polymerized and rearranged, and the regularity and order are continuously improved and tend to graphitization, and finally a porous carbon structure with a certain degree of graphitization is formed.
  • the pore characteristic value ⁇ A is used as a characteristic value that can represent the content of pores in the carrier material in which mass transfer reactions can occur stably.
  • the water generated by the reaction of the catalytic layer 400 is easier to discharge, thereby reducing the risk of the reaction site being flooded and inhibiting the entry of oxygen.
  • cavities in the carrier material 410 that are not connected to the outer surface and cannot be penetrated by fluid. These cavities do not directly affect the performance of the catalytic layer 400 in the early stage of the electrochemical reaction, and cannot be detected and analyzed by gas adsorption method. However, under high potential conditions such as starting and stopping, the existence of these cavities will aggravate the corrosion of the carrier material.
  • the cavity characteristic value ⁇ Ir is used as a characteristic parameter that can represent the structure. It is used to evaluate the condition of the cavity that is not connected to the outer surface and cannot be penetrated by the fluid.
  • the larger the cavity characteristic value ⁇ Ir the fewer cavity structures there are, and the more corresponding corrosion-resistant high-graphitized components.
  • the carrier material has stronger corrosion resistance under high-potential conditions such as starting and stopping.
  • the application of the above-mentioned carrier material in the membrane electrode of a fuel cell enables the membrane electrode to have excellent mass transfer capability.
  • the beneficial effect of the present application is that it provides a carrier material and a preparation method thereof for improving the mass transfer resistance of a membrane electrode composed of the carrier material by controlling the pore characteristic value and the cavity characteristic value.
  • the third product was subjected to a first heat treatment in nitrogen using a KSL-1700L box-type furnace from Hefei Kejing.
  • the heating rate for the first heat treatment was 1°C/min and the temperature was 200°C. After cooling and taking out, the fourth product was obtained.
  • the fifth product is subjected to a second heat treatment (high temperature heat treatment) in an argon atmosphere.
  • the equipment used is a Vlad graphitization furnace.
  • the heating rate of the high temperature heat treatment is 10°C/min, and the temperature is 1600°C. It is naturally cooled to room temperature.
  • a medium temperature heat treatment is carried out in a carbon dioxide atmosphere.
  • the heating rate of the medium temperature heat treatment is 10°C/min, and the temperature is 200°C.
  • a carrier material is obtained.
  • the carrier material of this embodiment is defined as C1.
  • the carrier material was added to a 1 mol/L chloroplatinic acid ethanol solution at a rotation speed of 500 rpm/min, sealed, stirred evenly, and dried to obtain the sixth product.
  • the sixth product was heated and reduced in a H 2 (20% Ar) gas atmosphere to obtain the seventh product.
  • the equipment used was a tube furnace from Zhengzhou Bona.
  • the heating rate of the heating reduction was 5° C./min and the temperature was 200° C.
  • the seventh product is acid-washed in a 1 mol/L hydrochloric acid solution, purified, filtered and dried to obtain a platinum-containing catalyst.
  • the platinum-containing catalyst of this embodiment is defined as C1-cat.
  • Example 2-10 The difference between Example 2-10 and Example 1 is that the mass concentration of the template mixed solution (first product) obtained in (1) is different.
  • Example 11-19 The difference between Examples 11-19 and Example 1 is that the concentration of the isopropanol mixed solution of ferric nitrate in (1) is different.
  • the ASAP2460 Micrometer tester is used to measure the adsorption amount of gas on the solid surface at different relative pressures. Based on the Brownauer-Etter-Taylor adsorption theory and its formula (BET formula), the monolayer adsorption amount of the sample is obtained, thereby calculating the specific surface area SA of the material.
  • the carrier material was randomly obtained, and ⁇ T was measured by Pentapyctm5200e true density tester, and ⁇ C was measured by GeoPyc-1365 Micrometer tap density tester (the pressure was 1 MPa, the same as the membrane electrode preparation pressure). According to formulas 6 and 7 and the theoretical true density ⁇ Id of ideal single crystal graphite (2.266 g/cm 3 ), the pore characteristic value ⁇ A and the cavity characteristic value ⁇ Ir of the carbon material were obtained.
  • the particle size of the carrier material is tested by Malvern 3000 laser particle size analyzer.
  • the intensity distribution of scattered light generated by the particles in all directions depends on the size of the particles. Large particles have small scattering angles, and small particles have large scattering angles.
  • the particle size distribution of the particles can be obtained by using the scattered light intensity distribution of laser diffraction.
  • the quantitative catalyst sample is digested by adding aqua regia, filtered, and fixed to volume, and the element content ICP-Pt is tested by ICP spectrometer.
  • the performance of the catalyst prepared by the carrier material was tested by a three-electrode system.
  • a certain amount of catalyst was weighed and 5% Nafion solution, deionized water and isopropanol were added in sequence. Ultrasound was used to mix the slurry evenly.
  • the dispersed slurry was evenly added to the surface of the disc electrode and used as the working electrode after drying.
  • the working electrode, reference electrode and counter electrode were placed in an electrolytic cell to form a three-electrode system.
  • the reference electrode was a RHE reversible hydrogen electrode
  • the counter electrode was a large-area Pt sheet
  • the electrolyte was a saturated 0.1M HClO4 solution.
  • ECSA refers to the electrochemically active area, with the unit of square meters per gram (m/g)
  • S refers to the integrated area of the hydrogen desorption zone, with the unit of ampere-volt (A*V)
  • C refers to the adsorption charge constant of hydrogen hydroxide adsorbed on the smooth Pt surface, which is 0.21 millicoulombs per square centimeter (0.21mC/ cm2 )
  • V refers to the scanning speed, with the unit of millivolts per second (mV/s)
  • M refers to the mass of Pt on the electrode, with the unit of gram (g).
  • the electrode was cycled for 10,000 cycles in the range of 1.0 V to 1.5 V vs RHE, and the electrochemical active area retention rate before and after the cyclic voltammetry test of the working electrode was recorded.
  • the performance of the single cell prepared with the catalyst layer made of carbon materials was tested on a battery test bench.
  • the anode catalyst loading of the membrane electrode used was 0.2mg/ cm2
  • the cathode catalyst loading was 0.4mg/ cm2 .
  • the impedance test was carried out under the conditions of battery operating temperature of 80°C, humidity of 100RH%, battery back pressure of 150kPa/150kPa, and the load was connected to make the current reach 2A/ cm2 . In the current control mode, a 10% disturbance current was applied, and the frequency was 10000Hz ⁇ 0.5Hz.
  • the sources of the pores of the support material include the pore formation of the template agent and the catalytic pore formation of the metal salt.
  • the examples of the present application mainly change the mass concentration of the template agent mixed solution and the concentration of the metal salt mixed solution. The two work together to play a role in pore formation/cavity formation.
  • the pore characteristic value of the obtained support material is 0.15-0.52 g/cm 3
  • the cavity characteristic value is about 7-60 g/cm 3
  • the achievable ICP-Pt is 46.2-49.2 wt.%
  • the ECSA is 66.7-96.2 g/cm 3
  • the ECSA retention rate is 62.54-83.84%
  • the mass transfer impedance is 0.553-1.1312 A/cm 2 @ ⁇ .cm 2.
  • the pore characteristic value and cavity characteristic value suitable for the present application are screened, so as to achieve the use of the pore characteristic value and the cavity characteristic value to represent the mass transfer capacity of the membrane electrode.
  • Example 6 and Example 9 belong to carrier materials with similar specific surface areas, but the ECSA retention rates and mass transfer impedances of the two are significantly different, indicating that the mass transfer of the membrane electrode composed of the carrier materials is quite different.
  • the prepared carrier material helps to attach more uniform metal salts to the template so that it can fully contact with the carbon source during the first heat treatment process to form certain template-connected or close pores or cavities. If the mass concentration of the template mixture is too high, the metal salt may not be dispersed uniformly on the template, and the above-mentioned pore-forming process cannot be achieved. If the metal salt acts directly on the carbon source without the template, a large number of unconnected micropores and cavities will be generated.
  • the metal salt can catalyze graphitization during the second heat treatment, which helps to improve the stability of the mass transfer process; in addition, the residual metal salt can also act as a pore-forming agent, opening up some tiny micropores to form holes, reducing the cavity structure ratio, increasing the cavity characteristic value, and facilitating the improvement of the degree of graphitization.
  • the carrier material When used under high potential conditions such as start-stop, the carrier material has stronger corrosion resistance.
  • the mass transfer impedance rises sharply, resulting in a rapid decrease in the current density on the membrane electrode polarization curve, which in turn leads to a decrease in the membrane electrode power density; and when the pore characteristic value is less than 0.25g/cm 3 , the change in mass transfer impedance is not obvious enough.
  • the cavity characteristic value and ECSA retention rate of the carrier material prepared in the present application have a certain regularity. With the increase of the cavity characteristic value, the ECSA retention rate first increases and then gradually decreases. Therefore, the preferred range of the cavity characteristic value is 10-50 g/cm 3 .
  • the mass transfer capacity of the membrane electrode is related to the size and type of the carbon material pores.
  • the cavities and channels connected to the outside world react continuously and stably, and the generated water can be discharged in time to ensure the continuous progress of the reaction.
  • the organic biomass precursor treated at high temperature is decomposed and carbonized by heat, and the corresponding pore structure is generated under the action of the template agent.
  • the surface graphite micro-chip layer molecules are polymerized and rearranged, and the regularity and order are continuously improved and tend to graphitization, and finally a porous carbon structure with a certain degree of graphitization is formed, which makes the mass transfer capacity of the membrane electrode excellent.

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Abstract

一种载体材料及其制备方法。其中，制备方法包括如下步骤：将模板剂分散于金属盐混合溶液中以获得特定浓度的第一产物；对第一产物进行低温真空干燥以获得第二产物；将有机碳源与第二产物混合以获得第三产物；在真空或惰性气体的条件中对第三产物进行第一次热处理以获得第四产物；对第四产物在酸洗液中进行洗涤并干燥以获得第五产物；对第五产物进行第二次热处理以获得载体材料；其中，载体材料的微观颗粒被构造为具有多个孔和多个腔，其中，孔与微观颗粒的外部连通，腔与微观颗粒的外部隔绝；将载体材料的质量与孔的总体积的比值定义为孔特征值；将载体材料的质量与腔的总体积的比值定义为腔特征值；载体材料的孔特征值小于载体材料的腔特征值。

Description

载体材料及其制备方法
本申请要求于2024年6月27日提交的申请号为202410874263.9的中国专利申请以及2023年9月28日提交的申请号为202311295382.0的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及燃料电池的技术领域，尤其涉及一种载体材料及其制备方法。
背景技术
膜电极是燃料电池中的核心部件，膜电极中的催化剂能将化学能转化为电能。气体、电子、质子三种组分在催化剂表面发生电化学反应生成水并向连接负载器件供能。膜电极中设置有承载催化剂的载体材料，其在承载催化剂同时为电化学反应提供质子、反应气体和水的连续传输通道。
载体材料的微观颗粒往往被构造为多孔结构以使载体材料具有较大的比表面积，这样就会为催化剂中的贵金属颗粒提供更多的附着点位，同时为催化反应提供反应场所。
技术问题
本申请实施例提供一种载体材料及其制备方法，以解决现有膜电极的传质阻力较大的问题。
技术解决方案
本申请实施例是这样实现的，提供一种载体材料的制备方法，包括如下步骤：
将模板剂分散于金属盐混合溶液中以获得特定浓度的第一产物；
对第一产物进行低温真空干燥以获得第二产物；
将有机碳源与第二产物混合以获得第三产物；
在真空或惰性气体的条件中对第三产物进行第一次热处理以获得第四产物；
对第四产物在酸洗液中进行洗涤并干燥以获得第五产物；
对第五产物进行第二次热处理以获得载体材料；
其中，载体材料的微观颗粒被构造为具有多个孔和多个腔，其中，孔与微观颗粒的外部连通，腔与微观颗粒的外部隔绝；
将载体材料的质量与孔的总体积的比值定义为孔特征值；将载体材料的质量与腔的总体积的比值定义为腔特征值；载体材料的孔特值小于载体材料的腔特征值。
依据本申请上述实施例提供的载体材料的制备方法，本申请实施例还提供一种载体材料，由上述的载体材料的制备方法所制备。
相应的，本申请实施例还提供一种燃料电池的膜电极，包括前述的载体材料。
附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图。
图1是本申请实施例提供的一种的燃料电池的结构示意图；
图2是本申请实施例提供的一种载体材料的制备方法的主要步骤示意图；
图3是本申请实施例提供的一种催化层的微观结构示意图；
图4是本申请实施例提供的一种载体材料和催化剂粒子结合时的结构示意图；
图5是本申请实施例提供的一种催化层的制备方法的主要步骤示意图；
图6是EIS测试的等效电路的结构示意图；
图7是本申请实施例提供的一种载体材料的孔特征值与质量传输阻抗的规律示意图；
图8是本申请实施例提供的一种载体材料的腔特征值与ECSA保持率的规律示意图。
附图标记的含义：
100、极板；
200、扩散层；
300、质子膜；
400、催化层；410、载体材料；420、催化剂颗粒。
具体实施方式
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域技术人员在没有做出创造性劳动的前提下所获得的所有其它实施例，都属于本申请保护的范围。此外，应当理解的是，此处所描述的具体实施方式仅用于说明和解释本申请，并不用于限制本申请。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
在本申请中，在未作相反说明的情况下，使用的方位词如“上”和“下”通常是指装置实际使用或工作状态下的上和下，具体为附图中的图面方向；而“内”和“外”则是针对装置的轮廓而言的。另外，在本申请的描述中，术语“包括”是指“包括但不限于”。用语第一、第二、第三等仅仅作为标示使用，并没有强加数字要求或建立顺序。
在本申请中，“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。
在本申请中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“一种或多种”、“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。例如，“a，b，或c中的至少一项(个)”，或，“a，b，和c中的至少一项(个)”，均可以表示：a，b，c，a-b(即a和b)，a-c，b-c，或a-b-c，其中a，b，c分别可以是单个，也可以是多个。
本申请的各种实施例可以以一个范围的形式存在；应当理解，以一范围形式的描述仅仅是因为方便及简洁，不应理解为对本申请范围的硬性限制；因此，应当认为所述的范围描述已经具体公开所有可能的子范围以及该范围内的单一数值。例如，应当认为从1到6的范围描述已经具体公开子范围，例如从1到3，从1到4，从1到5，从2到4，从2到6，从3到6等，以及所述范围内的单一数字，例如1、2、3、4、5及6，此不管范围为何皆适用。另外，每当在本文中指出数值范围，是指包括所指范围内的任何引用的数字(分数或整数)。
参照图1所示，本申请的燃料电池包括：两个极板100设置于它们之间的膜电极。其中，膜电极包括：质子膜300、催化层400和扩散层200。本申请的燃料电池中除了催化层400以外的各部分的功能、构成和制备方法为本领域一般技术人员所熟知的常规方案，亦非本申请改进的重点，在此不加赘述。
本申请的技术方案如下：
第一方面，参照图2所示，本申请实施例提供一种载体材料的制备方法，包括如下主要步骤：
S110：将模板剂分散于金属盐混合溶液中以获得特定浓度的第一产物。
具体而言，模板剂包括碳量子点、纳米氧化铝、纳米氧化硅、纳米氧化镁、纳米氧化钙、纳米碳酸钙中的一种或两种以上混合物。
金属盐混合溶液中金属盐包括硝酸铁、硝酸铬、硝酸钴、硝酸镍、硝酸锌、硝酸镁、氯化铁、氯化钴、氯化镍、氯化锌、氯化镁、硫酸铁、硫酸铁、硫酸铁、硫酸锌、硫酸镁的一种或多种。
金属盐混合溶液中混合溶剂包括异丙醇、乙二醇、正丁醇、N-甲基吡咯烷酮、乙醇中的一种或多种与蒸馏水的混合物。
更具体的，混合溶剂中蒸馏水与有机溶剂的体积比的取值范围包括1至20。
模板剂与金属盐混合溶液在室温中密封搅拌均匀获得第一产物，步骤S110的作用在于获得特定排列方式的模板剂，同时使得模板剂上面均匀附着金属盐。
步骤S110中的金属盐混合溶液的溶液浓度范围包括10mg/mL至100mg/mL，进一步可选的浓度范围包括20mg/mL至50mg/mL。
步骤S110中的第一产物的特定浓度范围包括10wt.％至50wt.％，进一步可选的浓度范围包括20wt.％至40wt.％。
S120：对第一产物进行低温真空干燥以获得第二产物。
具体的，第二产物为模板剂金属盐混合物。
低温真空干燥的温度范围包括-40℃至10℃，进一步可选的温度范围包括-30℃至-10℃。
S130：将有机碳源与第二产物混合以获得第三产物。
具体而言，有机碳源包括沥青、糖、重油、脂肪酸、聚乙烯醇、聚酰胺、环氧树脂、酚醛树脂、有机盐等物质及其衍生物中的一种或多种。
更具体的，有机碳源与第二产物的质量比为0.1至3。
步骤S130的作用在于不破坏模板剂排列方式前提下与有机碳源混合。
S140：在真空或惰性气体的条件中对第三产物进行第一次热处理以获得第四产物。
具体而言，步骤S140中第一次热处理在真空或惰性气体的条件中进行，惰性气体包括氩气、氮气中的一种或两种。
更具体的，步骤S140中第一次热处理的升温速度的取值范围包括1℃/min至20℃/min，热处理温度的取值范围包括200℃至1000℃。
进一步可选的，第一次热处理的升温速度的取值范围包括5℃/min至10℃/min，热处理温度的取值范围包括500℃至700℃。
步骤S140的作用可将有机碳源碳化，得到特定孔、腔体结构，其中，孔的来源包括模板剂的造孔效果以及金属盐催化造孔，而碳源本身缩水碳化过程中产生孔或腔。第四产物为具有特定孔、腔体结构的碳粉。
步骤S140的作用可使模板剂与金属盐共同作用形成具有一定孔、腔结构的产物。
S150：对第四产物在酸洗液中进行洗涤并干燥以获得第五产物。
具体而言，酸洗液包括盐酸、硝酸、高氯酸、硫酸、醋酸、氢氟酸的一种或多种。
酸洗液的物质的量浓度的取值范围包括0.2mol/L至5mol/L，进一步可选的，酸洗液的物质的量浓度的取值范围包括0.5mol/L至2mol/L。
步骤S150的目的在于除去大部分的金属盐和模板剂。
S160：对第五产物进行第二次热处理以获得载体材料。
S160的目的在于部分孔会随石墨化过程封闭形成腔，部分腔体残留的金属盐与碳发生反应形成孔结构，同时金属会发生不同程度的催化石墨化作用，增加材料的石墨化程度。
具体而言，步骤S160主要包括如下步骤：
S161：对第五产物进行惰性氛围下高温热处理以获得中间产物。
具体的，惰性氛围气体包括氩气、氮气中的一种或两种。
步骤S161中高温热处理的升温速率的取值范围包括1℃/min至20℃/min，热处理温度的取值范围包括1000℃至2600℃。
进一步可选的，高温热处理的升温速率的取值范围包括5℃/min至10℃/min，热处理温度的取值范围包括1400℃至1900℃。
S162：对中间产物进行冷却处理。
具体的，冷却处理采用自然冷却至常温的方式。
S163：对冷却处理后的中间产物进行氧化性氛围下中温热处理，冷却后获得载体材料。
具体的，氧化性氛围气体包括二氧化碳、含氧氧化气氛(空气，水蒸气，氧气，臭氧等)、氨气中的一种或多种。
步骤S163中中温热处理的升温速率的取值范围包括1℃/min至20℃/min，热处理温度的取值范围包括150℃至500℃。
进一步可选的，中温热处理的升温速率的取值范围包括1℃/min至15℃/min，热处理温度的取值范围包括200℃至400℃。
采用以上步骤S160的热处理方案，控制载体材料410的孔特征值和腔特征值。
其中，高温热处理提高碳材料结晶程度，结晶程度越高，耐腐蚀能力增强，比表面积降低，碳材料会在高温状态下发生结构重整变化，表面类石墨微晶片层会在这个过程中进行聚合、重排，孔结构(孔径、孔容等)会在过程中发生变化，其中一部分孔会成为腔。同时高温还会使得一些金属盐逃逸出，造成新的孔、腔结构。
中温热处理对材料进行氧化改性处理，该工序会使材料固定碳含量降低，氧、氢、氮(根据合成条件)元素含量提升，对应基团含量提高以便于贵金属颗粒附着。并且还会使得孔结构连通性提高，部分腔结构转为孔结构。
第二方面，参照图3和图4所示，本申请实施例提供一种载体材料410，该载体材料410主要为催化层400中催化剂颗粒420(贵金属颗粒，比如Pt纳米颗粒)提供载体，该载体材料410为粉体材料。
具体而言，本申请的载体材料410的微观颗粒被构造为具有多个孔和多个腔，其中，孔与微观颗粒的外部连通，腔与微观颗粒的外部隔绝；将载体材料410的质量与孔的总体积的比值定义为孔特征值；将载体材料410的质量与腔的总体积的比值定义为腔特征值；其中，载体材料410的孔特值小于载体材料410的腔特征值。
作为可选方案，载体材料410至少由碳材料构成。
碳材料的传质能力与孔的大小和种类有关，通常孔径在2nm及以上时，传质过程中能与外界连通空间更容易持续稳定发生反应且能及时将生成的水排开，保证反应的持续进行，这些空间被称为孔，包括交联孔、通孔和盲孔。这些孔的表面积可以通过气体吸附法进行检测分析。
除了这些孔之外，载体材料410的微观颗粒中可能还有一些封闭空间，这些孔的孔径较小(≤2nm)或是与外表面不相通而导致流体不能渗入，在采用气体吸附法和压汞法等测定方法无法有效测出这些空间，在工况下很难作为持续稳定的电化学反应发生场所。
因此，本申请的载体材料的微观颗粒中的孔，当孔径小于等于2nm时，流体已经很难进入，因此，也可以将孔径小于等于2nm的孔也划归为本申请中所定义的腔。也即本申请中所称的“与载体材料410的微观颗粒外部隔绝”是以流体不能有效流入作为标准的，也即本申请中所称的“与载体材料410的微观颗粒外部隔绝”的“腔”既包含完全不与载体材料410的微观颗粒外部连通的封闭空间，也包含这些虽然与载体材料410的微观颗粒外部连通但是孔径小于等于2nm的孔(非封闭空间)。
具有较大孔特征值的碳材料在高电流密度工况下，极大改善传质能力，降低传质阻力，合适的孔结构会延缓催化剂水淹及气体扩散孔道被堵塞现象，此外高腔特征值的载体材料410在启停等工况下表现出更高的载体材料410耐久性。
这种优化了孔与腔的多孔碳材料同样可能应用于其他涉及传质传荷过程的领域，比如锂电池、钠离子电池、药物搭载等。
在一些实施例中，载体材料410的孔特征值与腔特征值的比值的取值范围包括0.005至0.045。
在一些实施例中，载体材料410的孔特征值与腔特征值的比值的取值范围包括0.0102至0.0163，更具体包括0.014至0.015，或者0.0145至0.0148。
在一些实施例中，载体材料410的孔特征值与腔特征值的比值的取值范围包括0.0232至0.0384，更具体包括0.020至0.030，或者0.025至0.028。
在一些实施例中，载体材料410的孔特征值与腔特征值的比值的取值范围包括0.0090至0.0180，更具体包括0.012至0.013，或者0.0125至0.0129。
在一些实施例中，载体材料410的孔特征值的取值范围可以为0.250g/cm3至0.450g/cm3。
在一些实施例中，载体材料410的孔特征值的取值范围可以为0.260g/cm3至0.350g/cm3。
在一些实施例中，载体材料410的腔特征值的取值范围可以为10.00g/cm3至50.00g/cm3。
在一些实施例中，载体材料410的腔特征值的取值范围可以为20.00g/cm3至40.00g/cm3。
在一些实施例中，载体材料410的孔特征值的取值范围可以为0.256g/cm3 至0.298g/cm3；同时，载体材料410的腔特征值的取值范围可以为18.306g/cm3至24.902g/cm3。
在一些实施例中，载体材料410的孔特征值的取值范围可以为0.375g/cm3至0.418g/cm3；同时，载体材料410的腔特征值的取值范围可以为10.897g/cm3至16.105g/cm3。
在一些实施例中，载体材料410的孔特征值的取值范围可以为0.260g/cm3至0.350g/cm3；同时，载体材料410的腔特征值的取值范围可以为19.306g/cm3至30.026g/cm3。
在一些实施例中，载体材料410的孔特征值的取值可以为0.284、0.319或者0.399。
在一些实施例中，载体材料410的腔特征值的取值可以为14.298、19.306或者24.902。
在一些实施例中，载体材料410的比表面积的取值范围可以为400m2/g至1500m2/g。作为更进一步的选择，载体材料410的比表面积的取值范围可以为500m2/g至1100m2/g。
在一些实施例中，载体材料410的粒径的取值范围可以为100nm至2μm。作为更进一步的选择，载体材料410的粒径的取值范围可以为200nm至800nm。
在一些实施例中，载体材料410的压实密度的取值范围可以为0.05g/mL至0.80g/mL。作为更进一步的选择，载体材料410的压实密度的取值范围可以为0.10g/mL至0.50g/mL。
在一些实施例中，载体材料410的电导率的取值范围可以为6.4S/cm至26.5S/cm。
在一些实施例中，载体材料410的固定碳含量的取值范围可以为84.5％至97.2％。
为定量表示碳材料中有利于发生传质反应孔的结构特征，本申请设定孔特征值ρA作为可表示载体材料中可稳定发生传质反应孔含量的特征值，设定腔特征值ρIr作为可表示载体材料中不可稳定发生传质反应腔含量的特征值；其推导公式如下：


公式1中：ρId指理想单晶石墨的理论真密度(为2.266g/cm3)，m指理想单晶石墨的质量，VId指质量为m理想单晶石墨的体积。
公式2中：ρT指载体材料的真密度，m指载体材料的质量，VId指质量为m理想单晶石墨的体积，VIr指质量为m载体材料的腔体积。
公式3中：ρC指载体材料的压实密度，m指载体材料的质量，VId指质量为m理想单晶石墨的体积，VA指质量为m载体材料的孔体积，VIr指质量为m载体材料的腔体积。
其中对于特定孔结构的载体材料如公式4、5所示。

则孔特征值ρA、腔特征值ρIr特征值如公式6、7所示。

以上介绍了本申请中孔特征值和腔特征值的计算公式，所以通过指载体材料的真密度ρT、指载体材料的压实密度ρC和理想单晶石墨的理论真密度ρId即可以计算得出本申请中的孔特征值和腔特征值。
第三方面，参照图5所示，本申请实施例提供一种利用上述载体材料制备催化层的方法，包括如下步骤：
S210：取定量贵金属前驱体溶解于有机溶剂中，在剧烈搅拌下加定量的载体材料410，密封搅拌均匀后、干燥后得到第六产物。
具体而言，S210中有机溶剂包括乙醇、异丙醇、乙二醇、正丁醇中的一种或多种。
步骤S210中贵金属前驱体包括氯铂酸、氯铂酸钾、氯亚铂酸钾、二氯化铂、四氯化铂、二氯四氨合铂、二(乙酰丙酮)铂中的一种或多种。
步骤S210中的贵金属前驱体的物质的量浓度范围包括0.1mol/L至5mol/L，进一步可选的范围包括1mol/L至2mol/L。
S210中剧烈搅拌的转速为300-1000rpm/min。
S220：取第六产物，在特定浓度H2与惰性气体混合气体氛围下进行加热还原，得到特定贵金属含量的碳粉(第七产物)。
具体而言，S220中特定浓度H2可以为H2与Ar或H2与N2的任意比值混合气。
步骤S220中加热还原的升温速度的取值范围包括1℃/min至20℃/min，进一步可选的取值范围5℃/min至10℃/min；加热还原的温度范围200℃至900℃，进一步可选的取值范围300℃至400℃。
S230：取定量第七产物，经酸洗液洗涤、干燥得到含铂的催化剂。
具体而言，S230中酸洗液包括硝酸、高氯酸、醋酸中的一种或多种。
S230中酸洗液的物质的量浓度范围包括0.2mol/L至5mol/L，进一步可选的范围包括0.5mol/L至2mol/L。
可以理解的是，燃料电池催化层400的传质能力与碳材料孔的大小、种类有关，传质过程中与外界连通的空腔和孔道内持续稳定发生反应且能及时将生成的水排开，保证反应的持续进行。经高温处理的有机生物质前驱体受热分解碳化，在模板剂的作用下产生相应孔结构，并在金属盐的催化下，表面类石墨微晶片层分子进行聚合、重排，规整度和有序度不断提高而趋向石墨化，最终形成具有一定石墨化程度的多孔碳结构。
具体而言，以孔特征值ρA作为可表示载体材料中可稳定发生传质反应孔含量的特征值，孔特征值ρA越小，载体材料可稳定发生传质反应的能力越强，由催化层400反应产生的水更容易排出，进而降低反应发生场所被水淹而抑制氧的进入的风险。
除了这些孔之外，载体材料410中还有一些与外表面不相通，且流体不能渗入的腔，这些腔在电化学反应初期不直接影响催化层400性能，也无法通过气体吸附法进行检测分析，但在启动停止等高电位工况下，这些腔的存在会加剧载体材料的腐蚀。
具体而言，以腔特征值ρIr作为可表示该结构的特征参数，用来评估与外表面不相通，且流体不能渗入的腔的状况，腔特征值ρIr越大，腔结构越少，对应耐腐蚀的高石墨化组分越多，在启动停止等高电位工况下载体材料具有更强的耐腐蚀性能。
第四方面，上述的载体材料在燃料电池的膜电极中的应用，使得膜电极具有优异的传质能力。
本申请的有益效果在于：提供了一种通过控制孔特征值和腔特征值以改善由载体材料构成的膜电极的传质阻力的载体材料及其制备方法。
以下结合具体实施例对本申请的技术方案进行进一步的说明。
实施例1
(1)取碳量子点分散于10mg/mL硝酸铁的异丙醇混合溶液中，室温下密封搅拌，得到10wt.％的模板剂混合液(第一产物)；其中，硝酸铁的异丙醇混合溶液中水和异丙醇的体积比的比值为0.5。
(2)取第一产物，在-40℃低温真空干燥得到模板剂金属盐混合物(第二产物)。
(3)在第二产物中加入重油，室温下密封搅拌获得第三产物；其中，重油与第二产物的质量比的比值为0.1。
(4)在氮气的条件中，对第三产物进行第一次热处理，采用合肥科晶的KSL-1700L箱式炉，第一次热处理的升温速率1℃/min，温度为200℃，冷却取出后获得第四产物。
(5)将第四产物加入0.2mol/L盐酸溶液中进行酸洗、纯化，过滤及干燥获得碳粉(第五产物)。
(6)将第五产物在氩气氛围下进行第二次热处理(高温热处理)，设备选用弗拉德石墨化炉，高温热处理的升温速率为10℃/min，温度为1600℃，自然冷却至常温，然后在二氧化碳氛围下进行中温热处理，中温热处理的升温速率为10℃/min，温度为200℃，冷却后得到载体材料，将本实施例的载体材料定义为C1。
(7)将载体材料在500rpm/min转速下加到1mol/L氯铂酸的乙醇溶液中，密封搅拌均匀并干燥后获得第六产物。
(8)将第六产物在H2(20％Ar)气体氛围下进行加热还原获得第七产物，设备采用郑州博纳的管式炉，加热还原的升温速率为5℃/min，温度为200℃。
(9)将第七产物在1mol/L盐酸溶液中酸洗、纯化，过滤及干燥得到含铂的催化剂，将本实施例的含铂催化剂定义为C1-cat。
实施例2-10
实施例2-10与实施例1的区别之处在于(1)中所得到的模板剂混合液(第一产物)的质量浓度不同。
表1实施例2-10中模板剂混合液(第一产物)的质量浓度
实施例11-19
实施例11-19与实施例1的区别之处在于(1)中硝酸铁的异丙醇混合溶液的浓度不同。
表2硝酸铁的异丙醇混合溶液的浓度

以下对本申请的测试方法进行说明。
1)碳材料比表面积的测试方法：
在恒温低温下，采用ASAP2460麦克比表测试仪，测定不同相对压力时的气体在固体表面的吸附量后，基于布朗诺尔-埃特-泰勒吸附理论及其公式(BET公式)求得试样单分子层吸附量，从而计算出材料的比表面积SA。
2)孔特征值与腔特征值的测试方法：
随机获取载体材料，通过Pentapyctm5200e真密度测试仪测得ρT，通过GeoPyc-1365麦克振实密度测试仪测得ρC(压力与膜电极制备压力相同为1MPa)，由公式6、7及理想单晶石墨的理论真密度ρId(为2.266g/cm3)，得到碳材料孔特征值ρA、腔特征值ρIr。
3)载体材料粒度的测试方法：
通过马尔文3000激光粒度仪测试载体材料的粒度。颗粒在各个方向产生的散射光强度分布取决于颗粒的尺寸，大颗粒为小散射角，小颗粒为大散射角，从而利用激光衍射的散射光强度分布得到颗粒的粒径分布。
4)催化剂铂含量的测试方法：
通过将定量催化剂样品加入王水消解，过滤、定容，由ICP光谱仪测试元素含量ICP-Pt。
5)催化剂电化学活性面积及保持率的测试方法：
通过三电极系统测试载体材料所制备的催化剂性能，称取定量催化剂并依次加入5％Nafion溶液、去离子水及异丙醇。超声使浆液混合均匀。按照电极表面催化剂担载量为20ug/cm2～50ug/cm2，取分散好的浆液分别均匀地加到圆盘电极表面，干燥后作为工作电极。将工作电极、参比电极和对电极置于电解池中，组成三电极体系。其中，参比电极为RHE可逆氢电极，对电极为大面积Pt片，电解质为饱和的0.1M HClO4溶液。
测试循环伏安曲线。先以20mV/s的扫描速度对催化剂进行活化，直至氢脱附峰面积不再增加时，以20mV/s的速度扫描10圈，电位扫描范围为1.0V～1.5VvsRHE。选取稳定后的循环伏安曲线，对其氢脱附峰(0.05V～0.4VvsRHE)进行积分，得到面积S，按公式8计算电化学活性面积ECSA：
公式8中：ECSA指电化学活性面积，单位为平方米每克(m/g)，S指氢脱附区的积分面积，单位为安伏(A*V)，C指光滑Pt表面吸附氢氧化吸附电量常数，取0.21豪库仑每平方厘米(0.21mC/cm2)，V指扫描速度，单位为毫伏每秒(mV/s)，M指电极上Pt的质量，单位为克(g)。
在1.0V～1.5VvsRHE范围内循环10000Cycles，并记录工作电极循环伏安法测试前后电化学活性面积保持率。
6)催化层质量传输阻抗的测试方法：
通过电池测试台架测试碳材料制备催化层单电池性能，所用膜电极阳极催化剂载量0.2mg/cm2，阴极催化剂载量0.4mg/cm2。经过充分活化后，阻抗测试在电池运行温度80℃，湿度100RH％，电池背压150kPa/150kPa的条件下进行，接入负载使电流达到2A/cm2，在电流控制模式下，施加10％的扰动电流，频率为10000Hz～0.5Hz。
参照图6所示，EIS测试所得到的奈奎斯特图通过图6所示的等效电路进行拟合，通过有限的Warburg阻抗元件对质量传输阻抗进行表征。
SA、固定碳、电导率、孔特征值、腔特征值、理想密度、真密度和压实密度的检测结果如表3所示。
ICP-Pt、ECSA、ECSA保持率以及质量传输阻抗的检测结果如表4所示。
表3

表4
结合实施例1-19和表3-4的检测结果可知，载体材料孔的来源包括模板剂的造孔以及金属盐的催化造孔，本申请实施例主要改变模板剂混合液的质量浓度以及金属盐混合溶液的浓度，二者共同作用对造孔/造腔均起作用，所获得的载体材料的孔特征值为0.15-0.52g/cm3，腔特征值约为7-60g/cm3，所能达到的ICP-Pt为46.2-49.2wt.％，ECSA为66.7-96.2g/cm3，ECSA保持率为62.54-83.84％，质量传输阻抗为0.553-1.1312A/cm2@Ω.cm2，根据所需要达到的ECSA保持率以及质量传输阻抗，筛选适应本申请的孔特征值与腔特征值，从而实现采用孔特征值与腔特征值代表膜电极的传质能力。
结合实施例6和实施例9以及表4的检测结果可知，实施例6的比表面积为1459.56m2/g，ECSA为79.1m2/g，ECSA保持率为62.54％，质量传输阻抗为1.131Ω.cm2@2A/cm2；实施例9的比表面积为1502.91m2/g，ECSA为89.5m2/g，ECSA保持率为83.84％，质量传输阻抗为0.637Ω.cm2@2A/cm2；实施例6和实施例9属于具有相近比表面积的载体材料，但二者的ECSA保持率与质量传输阻抗差异明显，表明载体材料构成的膜电极的传质差异较大。
结合在同一金属盐条件下，改变模板剂混合液的浓度，所制备的载体材料有助于在模板上附着更均匀的金属盐，以便在第一次热处理过程中能够与碳源充分接触，形成一定的模板剂相连或相近的孔或腔体。若模板剂混合液的质量浓度过大，则可能导致金属盐在模板上分散不够均匀，则无法实现上述造孔过程。如果金属盐不经过模板剂直接作用于碳源上，则会产生大量不连通的微孔及腔体。
在相同浓度模板剂的条件下，改变金属盐混合溶液的浓度，可实现在第二次热处理过程中，金属盐可起到催化石墨化作用，有助于提高传质过程的稳定性；另外残留的金属盐还可起到造孔剂的作用，将一些细小的微孔打通形成孔，降低腔结构比例，增大了腔特征值，便于提高石墨化程度，应用在启动停止等高电位工况下，该载体材料具有更强的耐腐蚀性。
结合实施例1-19、表4及图7的检测结果可知，本申请所制备的载体材料的孔特征值与质量传输阻抗存在一定的规律，随着孔特征值的增加，在趋势上质量传输阻抗同步增加，但是在变化过程中会存在突变值，因此对孔特征值做进一步的筛选，孔特征值在0.25-0.45g/cm3之间，可获得具有较高的质量传输阻抗的载体材料，膜电极的传质能力良好。而孔特征值超过0.45g/cm3时，质量传输阻抗急剧上升，导致膜电极极化曲线上电流密度迅速下降，进而导致膜电极功率密度降低；而当孔特征值小于0.25g/cm3时，质量传输阻抗变化不够明显。
结合实施例1-19、表4及图8的检测结果可知，本申请所制备的载体材料的腔特征值与ECSA保持率存在一定的规律，随着腔特征值的增加，在趋势上ECSA保持率先增加后逐渐降低，因此腔特征值的优选范围为10-50g/cm3。
综上所述，膜电极的传质能力与碳材料孔的大小、种类有关，传质过程中与外界连通的空腔和孔道内持续稳定发生反应且能及时将生成的水排开，保证反应的持续进行。经高温处理的有机生物质前驱体受热分解碳化，在模板剂的作用下产生相应孔结构，并在金属盐的催化下，表面类石墨微晶片层分子进行聚合、重排，规整度和有序度不断提高而趋向石墨化，最终形成具有一定石墨化程度的多孔碳结构，使得膜电极的传质能力较优异。
以上对本申请实施例所提供的载体材料及其制备方法进行了详细介绍，本文中应用了具体个例对本申请的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本申请的方法及其核心思想；同时，对于本领域的技术人员，依据本申请的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本申请的限制。

Claims (12)

  1. 一种载体材料的制备方法，包括如下步骤：
    将模板剂分散于金属盐混合溶液中以获得特定浓度的第一产物；
    对所述第一产物进行低温真空干燥以获得第二产物；
    将有机碳源与所述第二产物混合以获得第三产物；
    在真空或惰性气体的条件中对所述第三产物进行第一次热处理以获得第四产物；
    对所述第四产物在酸洗液中进行洗涤并干燥以获得第五产物；
    对所述第五产物进行第二次热处理以获得所述载体材料；
    其中，所述载体材料的微观颗粒被构造为具有多个孔和多个腔，其中，所述孔与所述微观颗粒的外部连通，所述腔与所述微观颗粒的外部隔绝；
    将所述载体材料的质量与所述孔的总体积的比值定义为孔特征值；将所述载体材料的质量与所述腔的总体积的比值定义为腔特征值；所述载体材料的孔特值小于所述载体材料的腔特征值。
  2. 如权利要求1所述的载体材料的制备方法，其中，
    所述载体材料的孔特征值的取值范围包括0.250g/cm3至0.450g/cm3；和/或所述载体材料的腔特征值的取值范围包括10.00g/cm3至50.00g/cm3。
  3. 如权利要求1所述的载体材料的制备方法，其中，
    所述模板剂包括碳量子点、纳米氧化铝、纳米氧化硅、纳米氧化镁、纳米氧化钙、纳米碳酸钙中的一种或多种；
    所述金属盐混合溶液中金属盐包括硝酸铁、硝酸铬、硝酸钴、硝酸镍、硝酸锌、硝酸镁、氯化铁、氯化钴、氯化镍、氯化锌、氯化镁、硫酸铁、硫酸铁、硫酸铁、硫酸锌、硫酸镁的一种或多种；
    所述金属盐混合溶液中混合溶剂包括异丙醇、乙二醇、正丁醇、N-甲基吡咯烷酮、乙醇中的一种或多种与蒸馏水的混合物；
    所述金属盐混合溶液的溶液浓度范围包括10mg/mL至100mg/mL，所述特定浓度的第一产物的浓度范围包括10wt.％至50wt.％。
  4. 如权利要求1所述的载体材料的制备方法，其中，
    所述有机碳源包括沥青、糖、重油、脂肪酸、聚乙烯醇、聚酰胺、环氧树脂、酚醛树脂、有机盐及其衍生物中的一种或多种；
    将所述有机碳源与所述第二产物混合以获得第三产物中，所述有机碳源与所述第二产物的质量比的取值范围包括0.1至3。
  5. 如权利要求1所述的载体材料的制备方法，其中，
    所述在真空或惰性气体的条件中对所述第三产物进行第一次热处理以获得第四产物中，所述第一次热处理的升温速度的取值范围包括1℃/min至20℃/min，热处理温度的取值范围包括200℃至1000℃。
  6. 如权利要求1所述的载体材料的制备方法，其中，
    所述酸洗液包括盐酸、硝酸、高氯酸、硫酸、醋酸、氢氟酸的一种或多种；
    所述酸洗液的物质的量浓度的取值范围包括0.2mol/L至5mol/L。
  7. 如权利要求1至6中任意一项所述的载体材料的制备方法，其中，
    对所述第五产物进行第二次热处理以获得所述载体材料，包括如下步骤：
    对所述第五产物进行惰性氛围下高温热处理以获得中间产物；
    对所述中间产物进行冷却处理；
    对冷却处理后的中间产物进行氧化性氛围下中温热处理以获得所述载体材料；
    其中，所述高温热处理的升温速率的取值范围包括1℃/min至15℃/min，热处理温度的取值范围包括1000℃至3000℃；所述中温热处理的升温速率的取值范围包括1℃/min至15℃/min，热处理温度的取值范围包括100℃至600℃。
  8. 一种载体材料，所述载体材料的微观颗粒被构造为具有多个孔和多个腔，其中，所述孔与所述微观颗粒的外部连通，所述腔与所述微观颗粒的外部隔绝；
    其中，
    将所述载体材料的质量与所述孔的总体积的比值定义为孔特征值；
    将所述载体材料的质量与所述腔的总体积的比值定义为腔特征值；
    其中，所述载体材料的孔特值小于所述载体材料的腔特征值。
  9. 如权利要求8所述的载体材料，其中，
    所述载体材料的孔特征值的取值范围包括0.250g/cm3至0.450g/cm3；和/或所述载体材料的腔特征值的取值范围包括10.00g/cm3至50.00g/cm3。
  10. 如权利要求8所述的载体材料，其中，
    所述载体材料的比表面积的取值范围包括400m2/g至1500m2/g；
    和/或所述载体材料的粒径的取值范围包括100nm至2μm；
    和/或所述载体材料的压实密度的取值范围包括0.05g/mL至0.80g/mL；
    所述载体的电导率的取值范围包括6.4S/cm至26.5S/cm；
    所述载体的固定碳含量的取值范围包括84.5％至97.2％。
  11. 一种燃料电池，包括权利要求8至10任意一项所述的载体材料。
  12. 如权利要求8-10任意一项所述的载体材料在燃料电池的膜电极中的应用。
PCT/CN2024/108259 2023-09-28 2024-07-29 载体材料及其制备方法 Pending WO2024251306A1 (zh)

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