CN114883583B - High-stability high-temperature membrane electrode for fuel cell and preparation method thereof - Google Patents
High-stability high-temperature membrane electrode for fuel cell and preparation method thereof Download PDFInfo
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 155
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a high-stability high-temperature membrane electrode for a fuel cell and a preparation method thereof, wherein the high-temperature membrane electrode comprises a high-temperature polymer electrolyte membrane, a gas diffusion electrode and a membrane-electrode interface layer; wherein an interfacial layer composed of a mixture of one or more of a metal oxide having a nano particle diameter, a water-insoluble heteropolyacid salt, a pyrophosphate nanocarbon material, etc. is introduced between the high temperature polymer electrolyte membrane and the electrode; the interface layer can effectively slow down the migration rate of phosphoric acid from the high-temperature polymer electrolyte membrane into the catalytic layer, and improve the phosphoric acid retention capacity of the electrolyte membrane and the membrane electrode, thereby improving the working stability of the high-temperature membrane electrode; meanwhile, the interfacial layer can also improve the distribution of phosphoric acid in the catalytic layer and improve the output performance of the membrane electrode. The high-temperature polymer electrolyte membrane fuel cell has the advantages of excellent membrane electrode performance, good working stability and simple preparation method, and is suitable for industrial large-scale batch production.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a membrane electrode for a high-temperature polymer electrolyte membrane fuel cell and a preparation method thereof.
Background
The development of hydrogen energy promotes the transformation of global energy structures, the innovation of fuel cell technology accords with the low carbonization, electric and distributed development trend of global energy traffic, and is concerned by academic and industrial interest, and in particular, the polymer electrolyte membrane fuel cell technology is commercially applied to vehicle-mounted and aerospace power systems on a large scale.
Wherein, the high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) can simplify the water heat management system of the fuel cell stack and improve the tolerance to carbon monoxide (CO), sulfur dioxide (SO 2) and other impurity gases due to the higher operating temperature (120-180 ℃). When coupled with liquid fuel reformers such as methanol and formic acid, the fuel cell has the characteristics of no need of purification treatment of reformed gas, high heat efficiency and the like, and is an important development direction of polymer electrolyte membrane fuel cells. The core component of the HT-PEMFC is a high temperature membrane electrode (HT-MEA) assembled based on a phosphoric acid doped polymer electrolyte membrane. Phosphoric acid in the HT-MEA serves as a proton conductor of an electrolyte membrane on one hand, and transfers hydrogen protons generated by the anode to the cathode; on the other hand, part of phosphoric acid enters the catalytic layer to participate in constructing a solid-liquid-gas three-phase electrochemical reaction interface. However, the high phosphoric acid content and uneven phosphoric acid distribution in the catalytic layer easily cause blocking of the pore channels, and prevent the contact between the reaction gas and the platinum catalyst, resulting in a large local transmission resistance in the catalytic layer. Therefore, regulating the distribution of phosphoric acid in HT-MEA, especially the content and distribution in the catalytic layer, is critical for constructing HT-PEMFC with high performance and high stability.
During the membrane electrode assembly process, the assembled mechanical stress squeezes the polymer electrolyte membrane, causing phosphoric acid inside the membrane to overflow into the cracks of the catalytic layer and redistribute in the catalytic layer under the action of capillary force and phosphoric acid surface tension determined by the microporous structure and hydrophobicity of the catalytic layer. While the cell is running, the cell potential pulls the phosphate anions to migrate to the anode and the phosphoric acid loss with the product water and unreacted gases is also further promoted by the redistribution of phosphoric acid in the membrane electrode. The dynamic migration process of phosphoric acid in the membrane electrode can lead to the phosphoric acid in the electrolyte membrane to migrate into the catalytic layer in a large amount and continuously, and the catalytic reaction is easy to be causedThe layer is flooded by acid, so that the number of effective solid-liquid-gas electrochemical three-phase reaction interfaces is reduced, and the adsorption of phosphate anions on the surface of platinum seriously affects the operation stability of HT-PEMFC. Thus, to reduce the negative impact of phosphoric acid on the catalytic layer, a high catalyst platinum loading (typically at 1.0mg cm -2 Above), the cost of the HT-PEMFC is greatly increased, the requirement of practical large-scale application cannot be met, and the commercialization progress of the HT-PEMFC is seriously hindered.
Disclosure of Invention
In order to solve the problems, the invention proposes to construct an intermediate interface layer strategy with phosphoric acid interception capability between the polymer electrolyte membrane and the catalytic layer based on the distribution and migration mechanism of phosphoric acid in the membrane electrode and the influence of the content and distribution of phosphoric acid in the catalytic layer on the electrochemical active area of the membrane electrode, so as to regulate the rate of phosphoric acid entering the catalytic layer in the electrolyte membrane and the content and distribution of phosphoric acid in the catalytic layer, thereby achieving the purpose of improving the output performance and stability of HT-MEA.
The specific scheme is that the nano-coating is formed by one or more of metal oxide with nano particle size, water-insoluble heteropolyacid salt, pyrophosphatate nano carbon material and the like on the surface of the catalytic layer, and the migration speed of phosphoric acid to the catalytic layer is effectively slowed down by utilizing capillary condensation action of nano pore diameter formed by small-particle-size nano particles and strong chemical action of the nano material and phosphoric acid; and the porosity and thickness of the coating are regulated and controlled by regulating the particle size and the loading capacity of the nano particles so as to further regulate and control the phosphoric acid content in the catalytic layer. The material source of the interface layer is wide, the interface layer preparation method is simple and convenient, and the method is suitable for preparing the high-efficiency stable low-platinum HT-MEA with large scale and large size. Therefore, the high-temperature membrane electrode with the interface layer and the preparation method thereof disclosed by the invention are beneficial to improving the output performance and stability of the high-temperature membrane electrode, and can greatly promote the commercialization process of HT-PEMFC.
The membrane electrode prepared by the method not only can effectively regulate and control the content of phosphoric acid in the catalytic layer, improve the distribution of phosphoric acid in the catalytic layer and improve the utilization rate of a platinum catalyst, but also has good phosphoric acid retention capacity, and can slow down phosphoric acid in an electrolyte membraneLoss, thereby realizing low platinum loading of the high temperature polymer electrolyte membrane fuel cell<0.5mg cm -2 ) Lower high power output and stability. And the catalytic layer surface coating construction material has wide sources, the whole preparation method is simple, the interface layer thickness is adjustable, and the large-scale industrial production is very easy.
The complete technical scheme of the invention comprises the following steps:
a high temperature polymer electrolyte membrane fuel cell membrane electrode, the high temperature polymer electrolyte membrane fuel cell membrane electrode at least comprises a high temperature polymer electrolyte membrane, a first gas diffusion electrode and a second gas diffusion electrode, the high temperature polymer electrolyte membrane is positioned between the first gas diffusion electrode and the second gas diffusion electrode,
a membrane-electrode interface layer is arranged between the high-temperature polymer electrolyte membrane and the catalytic layer of the first gas diffusion electrode and/or between the high-temperature polymer electrolyte membrane and the catalytic layer of the second gas diffusion electrode,
the membrane-electrode interface layer prevents or slows down the migration of phosphoric acid from the high temperature polymer electrolyte membrane to the catalytic layer of the gas diffusion electrode, and is composed of one or a mixture of more of silicon dioxide, montmorillonite, mica, metal oxide, water-insoluble heteropolyacid salt, pyrophosphates and nano carbon materials.
The particle size of the membrane-electrode interface layer material is 1 nm-500 nm; the metal oxide is one or more of aluminum oxide, titanium dioxide, tin dioxide, cerium oxide and zirconium oxide, the water-insoluble heteropolyacid salt is one or more of cesium phosphotungstate, ammonium phosphotungstate and cesium molybdenum tungstate, and the pyrophosphates are one or more of tin pyrophosphate, silicon pyrophosphate and zirconium pyrophosphate; the nano carbon material is one or more of carbon quantum dots, nano carbon spheres, graphene and carbon nanotubes.
The membrane-electrode interface layer material is a material capable of forming hydrogen bond with phosphoric acid, and the platinum loading capacity in the catalytic layer is 0.5mg/cm 2 。
The membrane-electrode interface layer material is nano SiO 2 The nano SiO 2 The particle size of the material is 25-30 nm smaller than that of the catalyst of the diffusion electrode catalytic layer; siO of the membrane-electrode interface layer 2 The loading is 0.05-0.2mg cm -2 The thickness of the interface layer is 3.2-9.4 μm;
the membrane-electrode interface layer is of a microporous structure, wherein the primary pore diameter of 0.01-0.1 mu m is not less than 65%, the secondary pore diameter of 0.1-1 mu m is not more than 12%, and the large pore diameter of more than 10 mu m is not more than 23%.
The preparation method of the membrane electrode of the high-temperature polymer electrolyte membrane fuel cell comprises the following steps:
(1) Preparation of gas diffusion electrode
Firstly, dispersing catalyst powder and polymer solution in a first solvent to prepare ink, shaking the prepared ink uniformly, then performing ultrasonic dispersion or high-speed homogenization until the ink has a certain viscosity, and covering the ink on carbon paper coated with a smoothening layer in an ultrasonic spraying, blade coating or screen printing mode; then heat treatment is carried out for a period of time in nitrogen atmosphere under a certain temperature condition to form a needed gas diffusion electrode;
(2) Construction of interface layer on surface of gas diffusion electrode
Dispersing nano powder for constructing an interface layer in a first solvent to prepare a uniformly dispersed suspension, coating the obtained suspension on the surface of a catalytic layer of the gas diffusion electrode obtained in at least one step (1), and carrying out heat treatment for a period of time in an air atmosphere at a certain temperature to fully volatilize the solvent in the interface layer to obtain the gas diffusion electrode containing the interface layer;
(3) Membrane electrode assembly
Placing a high-temperature polymer electrolyte membrane saturated by phosphoric acid doping between two gas diffusion electrodes, namely a first gas diffusion electrode and a second gas diffusion electrode, aligning the catalytic layer sides of the two gas diffusion electrodes towards the direction of the polymer electrolyte membrane, and hot-pressing for a period of time under certain temperature and pressure conditions by adopting a hot press to obtain a high-temperature membrane electrode containing an interface layer;
at least one of the first gas diffusion electrode and the second gas diffusion electrode is provided with an interface layer prepared by coating in the step (2).
The catalyst in the step (1) is platinum or a platinum-based alloy, and the polymer in the polymer solution is one or more of Polybenzimidazole (PBI), polyvinylpyrrolidone (PVP), polyarenylpiperidine (PAPs), polyarenylpyridine (PAPy), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), perfluorosulfonic acid resin (PFSI), phosphonated polymer resin (PPI) and Quaternized Anionic Polymer (QAPI); the first solvent is one or more of water, isopropanol, ethanol, methanol, N dimethylformamide, N dimethylacetamide and dimethyl sulfoxide.
The viscosity of the catalyst ink in the step (1) is 2-300 m.Pa.s; preferably, when the catalytic layer is prepared by adopting a doctor blade coating and screen printing mode, the viscosity of the ink is 100-300 m.Pa.s; the viscosity of the ink is 2-20 mPa.s when the catalytic layer is prepared by adopting an ultrasonic spraying mode.
The heat treatment temperature in the step (1) is 200-350 ℃; the heat treatment time is 10-60 minutes.
In the step (2), uniformly dispersed suspension is prepared by ultrasonic or ball milling and the like, the viscosity of the suspension is 2-300 m.Pa.s, and the suspension coating modes comprise spraying, knife coating, silk screen and the like. The viscosity of the suspension is selected according to the coating mode used for the interface layer: when the preparation modes of blade coating, screen printing and the like are adopted, the viscosity of the ink is preferably 100-300 m.Pa.s; when the preparation modes such as ultrasonic spraying are adopted, the viscosity of the ink is preferably 2-20 m.Pa.s.
The heat treatment temperature in the step (2) is 40-300 ℃; the heat treatment time is 10-120 minutes, the hot pressing temperature in the step (3) is room temperature-200 ℃, the hot pressing pressure is 0.1-5 MPa, and the hot pressing time is 2-10 minutes.
The invention has the advantages compared with the prior art that:
(1) The membrane electrode of the high-temperature polymer electrolyte membrane fuel cell prepared by the invention mainly comprises a gas diffusion electrode, an interface layer and a phosphoric acid doped polymer electrolyte membrane, and the prepared membrane electrode has excellent performance output and output stability.
(2) The intermediate interface layer of the membrane electrode of the high-temperature polymer electrolyte membrane fuel cell prepared by the invention is mainly nano material or has good interaction force with phosphoric acid, so that the retention capacity of phosphoric acid in the electrolyte membrane can be improved, the migration rate of phosphoric acid into a catalytic layer can be slowed down, and the even distribution of phosphoric acid in the catalytic layer can be promoted, thereby simultaneously realizing the high output performance and high durability of the high-temperature polymer electrolyte membrane fuel cell.
(3) The preparation method is simple, the nano material interface layer is directly constructed between the polymer electrolyte membrane and the gas diffusion electrode, and the content and the distribution of the phosphoric acid in the catalytic layer can be regulated by the material type, the particle size and the thickness of the interface layer, so that the output performance of the battery can be regulated and controlled, and the stability of the performance output can be ensured. The cost of raw materials is low, the loading capacity can be accurately controlled, and the method is very suitable for large-scale preparation.
Drawings
Fig. 1 is a schematic diagram of a membrane electrode assembly structure and a conventional membrane electrode structure according to the present invention, wherein a is a single interfacial layer membrane electrode assembly according to the present invention, b is a double interfacial layer membrane electrode assembly according to the present invention, and c is a conventional membrane electrode.
FIG. 2 shows the cell performance at 160℃of the high temperature membrane electrodes prepared in comparative example 1 and examples 2, 4, and 6.
FIG. 3 shows the time dependence of the internal resistance of the membrane electrode of the gas diffusion electrodes prepared in comparative example 1 and example 6 of the present invention under the humidifying condition of 80 ℃.
In the figure, a 1-gas diffusion layer; 2-a catalytic layer; 3-interfacial layer; 4-phosphoric acid doped polymer electrolyte membrane.
Detailed Description
The following detailed description of the embodiments of the present invention, such as the designed mutual positions and connection relationships between the parts, the roles and working principles of the parts, the manufacturing process and the operation and use method, etc., is provided to help those skilled in the art to more fully, accurately and deeply understand the inventive concept and technical scheme of the present invention.
The invention discloses a high-temperature polymer electrolyte membrane fuel cell membrane electrode (hereinafter referred to as a high-temperature membrane electrode) and a preparation method thereof. The high-temperature membrane electrode disclosed by the invention comprises a high-temperature polymer electrolyte membrane, a gas diffusion electrode and a membrane-electrode interface layer; the interface layer is introduced between the high-temperature polymer electrolyte membrane and the electrode and is composed of one or a mixture of a plurality of metal oxides, water-insoluble heteropolyacid salts, pyrophosphates nano carbon materials and the like, the material sources are wide, the preparation method of the interface layer is simple, and the interface layer is suitable for industrial large-scale batch production; the interface layer can effectively slow down the migration rate of phosphoric acid from the high-temperature polymer electrolyte membrane into the catalytic layer, and improve the phosphoric acid retention capacity of the electrolyte membrane and the membrane electrode, thereby improving the working stability of the high-temperature membrane electrode; meanwhile, the interfacial layer can also improve the distribution of phosphoric acid in the catalytic layer and improve the output performance of the membrane electrode.
The preparation method mainly comprises three steps of preparation of a gas diffusion electrode, construction of an interface layer and assembly of a membrane electrode, wherein a membrane electrode structure schematic diagram is shown in figure 1, and the preparation method specifically comprises the following steps:
(1) Preparation of gas diffusion electrode
First, platinum catalyst powder and a polymer solution are dispersed in water or an organic solvent (such as isopropanol, ethanol, methanol, N dimethylformamide, N dimethylacetamide, dimethyl sulfoxide) to form a catalyst ink, and the mass ratio is generally 1:1000-1:50. And then treating the prepared ink in an ultrasonic vibrator or a high-speed homogenizer for a period of time until the ink reaches a certain viscosity, wherein the viscosity of the ink is usually 2-300 mPa s. And then the gas diffusion layer 1 is covered by ultrasonic spraying, knife coating or screen printing.
And carrying out heat treatment on the prepared gas diffusion layer with the catalytic layer 2 for 1-100 min under the high temperature condition of 320-400 ℃ in a nitrogen atmosphere, and obtaining the required gas diffusion electrode after the solvent is completely volatilized and the binder is thermally molded.
(2) Construction of interfacial layer
The nano carbon material (such as nano carbon sphere, flake carbon material, carbon quantity)Sub-dots) or hydrophilic inorganic nanomaterials (e.g. SiO 2 ，Al 2 O 3 ，SnO 2 ，TiO 2 Montmorillonite, silicate, etc.) in water or an organic solvent (e.g., methanol, ethanol, isopropanol) to obtain a dispersion having a concentration of 0.1 to 10 wt%.
And (3) uniformly dispersing the obtained dispersion liquid by ultrasonic, coating the surface of the catalytic layer prepared in the step (1) by ultrasonic spraying or knife coating, and drying at 60-200 ℃ (corresponding adjustment is carried out according to different selected solvents and drying temperatures) until the solvents are completely volatilized, thus obtaining the gas diffusion electrode with the coating.
(3) Membrane electrode assembly
And placing the phosphoric acid doped polymer electrolyte membrane 4 soaked in the phosphoric acid solution between the two prepared gas diffusion electrodes, aligning the catalytic layer sides of the two gas diffusion electrodes towards the direction of the polymer electrolyte membrane, and hot-pressing for 1-10 minutes by adopting a hot press under the conditions of a certain room temperature to 200 ℃ and a pressure of 0.1-5 MPa to obtain the high-temperature membrane electrode containing the interface layer 3.
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The platinum-based catalyst is a catalyst with the platinum content of 60wt%, the preparation mode of the gas diffusion electrode is a spraying mode, the interface layer material is graphene, the membrane electrode assembly mode is a gas diffusion electrode with interface layers at both sides of the cathode and the anode, and the preparation and assembly processes are as follows:
(1) 60wt% Pt/C catalyst and PTFE emulsion were dispersed in ethanol (25 mL) at a mass ratio of 1:400. Ultrasonic dispersion was carried out in an ultrasonic cleaner for 6 hours to obtain a uniformly dispersed suspension.
(2) And filling the uniformly dispersed suspension into a syringe, regulating the injection speed, ultrasonic power and the operation speed of a spray head, uniformly spraying the obtained ink on the gas diffusion electrode through ultrasonic spraying equipment, and drying at the temperature of 60 ℃ on a heating table to obtain the gas diffusion electrode which is not subjected to heat treatment.
(3) Placing the untreated gas diffusion electrode obtained in the step (2) into a tube furnace, regulating the gas atmosphere of the furnace to be nitrogen or argon, carrying out heat treatment at the temperature of 350 ℃ for 40 minutes, and taking out after the treatment to obtain the required gas diffusion electrode, wherein the platinum loading amount is 0.5mg/cm 2 。
(4) Graphene is dispersed in ethanol (20 mL) with a mass ratio of 1:2000. Ultrasonic treatment was carried out in an ultrasonic cleaner for 1 hour to obtain a uniformly dispersed suspension.
(5) Filling the uniformly dispersed graphene suspension obtained in the step (4) into an injector, then adjusting the injection speed, the ultrasonic power and the operation speed of a spray head, spraying the graphene suspension on the surface of a catalytic layer of a gas diffusion electrode through ultrasonic spraying equipment, and drying at the temperature of 70 ℃ on a heating table to obtain the graphene-loaded material with 0.05mg/cm 2 And a gas diffusion electrode of the interface layer.
(6) The polymer electrolyte membrane immersed in 85wt% phosphoric acid solution at room temperature for 24 hours was erased from the surface phosphoric acid, and placed between the two gas diffusion electrodes with interface layers prepared in (5), to assemble a membrane electrode.
Example 2
The platinum-based catalyst is a catalyst with the platinum content of 60wt%, the preparation mode of the gas diffusion electrode is a spraying mode, the interface layer material is XC-72 carbon sphere powder, the membrane electrode assembly mode is that the cathode side is the gas diffusion electrode with the interface layer, and the anode side is the conventional gas diffusion electrode, and the preparation process is as follows:
(1) 60wt% Pt/C catalyst and PTFE emulsion were dispersed in isopropyl alcohol (25 mL) at a mass ratio of 1:500. Ultrasonic treatment was carried out in an ultrasonic cleaner for 30 minutes to obtain a uniformly dispersed suspension.
(2) And filling the uniformly dispersed suspension into a syringe, regulating the injection speed, ultrasonic power and the operation speed of a spray head, uniformly spraying the obtained ink on the gas diffusion electrode through ultrasonic spraying equipment, and drying at the temperature of 70 ℃ on a heating table to obtain the gas diffusion electrode which is not subjected to heat treatment.
(3) And (3) putting the untreated gas diffusion electrode obtained in the step (2) into a tube furnace, regulating the gas atmosphere of the furnace to be nitrogen or argon, carrying out heat treatment at 360 ℃ for 30mins, and taking out after the heat treatment to obtain the required gas diffusion electrode, wherein the platinum loading amount is 0.5mg/cm < 2 >.
(4) XC-72 carbon sphere powder was dispersed in isopropyl alcohol (25 mL) at a mass ratio of 1:2000. Ultrasonic treatment was carried out in an ultrasonic cleaner for 30 minutes to obtain a uniformly dispersed suspension.
(5) Filling the suspension of the XC-72 carbon sphere powder obtained in the step (4) in a syringe, regulating the injection speed, ultrasonic power and the operation speed of a spray head, spraying the obtained XC-72 suspension on the surface of a catalytic layer of a gas diffusion electrode through an ultrasonic spraying device, and drying at a temperature of 70 ℃ on a heating table to obtain the catalyst with the XC-72 carbon sphere loading of 0.05mg/cm 2 And a gas diffusion electrode of the interface layer.
(6) The polymer electrolyte membrane immersed in 85wt% phosphoric acid solution at room temperature for 24 hours was erased from the surface phosphoric acid, and placed between the gas diffusion electrode with an interface layer prepared in (5) and a conventional gas diffusion electrode, wherein the gas diffusion electrode with an interface layer was used as a cathode, and a membrane electrode was assembled.
Example 3
The platinum-based catalyst is a catalyst with the platinum content of 40wt%, the preparation mode of the gas diffusion electrode is a spraying mode, and the interface layer material is Al 2 O 3 The nano powder is assembled by using a membrane electrode in a way that an anode side is a gas diffusion electrode with an interface layer and a cathode side is a conventional gas diffusion electrode, and the preparation process is as follows:
(1) 40wt% Pt/C catalyst and perfluorosulfonic acid membrane were dispersed in ethanol (30 mL) at a mass ratio of 1:500. Ultrasonic treatment was carried out in an ultrasonic cleaner for 6 hours to obtain a uniformly dispersed suspension.
(2) And filling the uniformly dispersed suspension into a syringe, regulating the injection speed, ultrasonic power and the operation speed of a spray head, uniformly spraying the obtained ink on the gas diffusion electrode through ultrasonic spraying equipment, and drying at the temperature of 70 ℃ on a heating table to obtain the gas diffusion electrode which is not subjected to heat treatment.
(3) And (3) putting the untreated gas diffusion electrode obtained in the step (2) into a tube furnace, regulating the gas atmosphere of the furnace to be nitrogen or argon, carrying out heat treatment at 120 ℃ for 30min, and taking out after the treatment to obtain the required gas diffusion electrode, wherein the platinum loading amount is 0.5mg/cm < 2 >.
(4) Al is added with 2 O 3 The nano powder is dispersed in isopropanol (25 mL), and the mass ratio of the nano powder to the isopropanol is 1:2500. Ultrasonic treatment was carried out in an ultrasonic cleaner for 30 minutes to obtain a uniformly dispersed suspension.
(5) The Al obtained in (4) was reacted with 2 O 3 The suspension of evenly dispersed nano powder is filled in a syringe, then the injection speed and ultrasonic power and the operation speed of a spray head are regulated, and the obtained Al is sprayed by ultrasonic spraying equipment 2 O 3 Spraying the suspension onto the surface of the catalytic layer of the gas diffusion electrode, and oven drying at 50deg.C to obtain a product containing Al 2 O 3 The loading was 0.2mg/cm 2 And a gas diffusion electrode of the interface layer.
(6) The polymer electrolyte membrane immersed in 85wt% phosphoric acid solution at room temperature for 24 hours was erased from the surface phosphoric acid, and placed between the gas diffusion electrode with an interface layer prepared in (5) and a conventional gas diffusion electrode, wherein the gas diffusion electrode with an interface layer was used as an anode, and a membrane electrode was assembled.
Example 4
The platinum-based catalyst is a catalyst with the platinum content of 60wt%, the preparation mode of the gas diffusion electrode is a spraying mode, and the interface layer material is SiO with the diameter of 100nm 2 The nano powder is assembled by a membrane electrode in a way that a cathode side is a gas diffusion electrode with an interface layer and an anode side is a conventional gas diffusion electrode, and the preparation process is as follows:
(1) 60wt% Pt/C catalyst and polyvinylidene fluoride were dispersed in N, N dimethylformamide (25 mL) at a mass ratio of 1:20. Homogenizing in a high-speed homogenizer for 40 minutes to obtain a uniform catalyst slurry.
(2) And placing the obtained catalyst slurry on a flat plate, then adjusting the scraping speed and the scraping height, uniformly scraping the obtained ink on the gas diffusion electrode through a scraping device, and drying at the temperature of 90 ℃ on a heating table to obtain the gas diffusion electrode which is not subjected to heat treatment.
(3) Placing the untreated gas diffusion electrode obtained in the step (2) into a tube furnace, regulating the gas atmosphere of the furnace to be nitrogen or argon, carrying out heat treatment at 180 ℃ for 40min, and taking out after the treatment to obtain the required gas diffusion electrode with a platinum loading of 0.5mg/cm 2 。
(4) Will be 100nm SiO 2 The nano powder is dispersed in ethanol (20 mL) with the mass ratio of the nano powder to the ethanol being 1:2000. Ultrasonic treatment was carried out in an ultrasonic cleaner for 40mins to obtain a uniformly dispersed suspension.
(5) The 100nm SiO obtained in (4) was reacted with 2 Filling the suspension with evenly dispersed nano powder into a syringe, then adjusting the injection speed, ultrasonic power and the operation speed of a spray head, and using ultrasonic spraying equipment to obtain 100-150 nm SiO 2 Spraying the suspension onto the surface of the catalytic layer of the gas diffusion electrode, and oven drying at 70deg.C to obtain SiO-containing powder 2 The loading was 0.1mg/cm 2 And a gas diffusion electrode of the interface layer.
(6) The polymer electrolyte membrane immersed in 85wt% phosphoric acid solution at room temperature for 24 hours was erased from the surface phosphoric acid, and placed between the gas diffusion electrode with an interface layer prepared in (5) and a conventional gas diffusion electrode, wherein the gas diffusion electrode with an interface layer was used as a cathode, and a membrane electrode was assembled.
Example 5
The platinum-based catalyst is a catalyst with the platinum content of 40wt%, the preparation mode of the gas diffusion electrode is a screen printing mode, and the interface layer material is TiO 2 The nanometer powder and the membrane electrode are assembled in a gas diffusion electrode with interface layers at both sides of a cathode and an anode, and the preparation process is as follows:
(1) 40wt% Pt/C catalyst and polybenzimidazole were dispersed in N, N dimethylacetamide (30 mL) at a mass ratio of 1:15. Homogenizing in a high-speed homogenizer for 30 minutes, to obtain a uniform catalyst slurry.
(2) And placing the obtained catalyst slurry on a flat plate, then adjusting the doctor-blading speed and the screen height of screen printing, uniformly doctor-coating the obtained ink on a gas diffusion electrode through doctor-blading equipment, and drying at the temperature of 90 ℃ on a heating table to obtain the gas diffusion electrode without heat treatment.
(3) Placing the untreated gas diffusion electrode obtained in the step (2) into a tube furnace, regulating the gas atmosphere of the furnace to be nitrogen or argon, carrying out heat treatment at the temperature of 200 ℃ for 20min, and taking out after the treatment to obtain the required gas diffusion electrode, wherein the platinum loading amount is 0.5mg/cm 2 。
(4) TiO is mixed with 2 The nano powder is dispersed in ethanol (20 mL) with the mass ratio of the nano powder to the ethanol being 1:1800. Ultrasonic treatment was carried out in an ultrasonic cleaner for 20mins to obtain a uniformly dispersed suspension.
(5) The TiO obtained in (4) is reacted with 2 The suspension of evenly dispersed nano powder is filled in a syringe, then the injection speed and ultrasonic power and the operation speed of a spray head are regulated, and the obtained TiO is sprayed by ultrasonic spraying equipment 2 Spraying the suspension onto the surface of the catalytic layer of the gas diffusion electrode, and drying at 70deg.C to obtain the final product with TiO 2 The loading was 0.1mg/cm 2 And a gas diffusion electrode of the interface layer.
(6) The polymer electrolyte membrane immersed in 85wt% phosphoric acid solution at room temperature for 24 hours was erased from the surface phosphoric acid, and placed between the two gas diffusion electrodes with interface layers prepared in (5), to assemble a membrane electrode.
Example 6
The platinum-based catalyst is a catalyst with the platinum content of 60wt%, the preparation mode of the gas diffusion electrode is a spraying mode, and the interface layer material is SiO with the diameter of 10-20nm 2 The nano powder is assembled by a membrane electrode in a way that a cathode side is a gas diffusion electrode with an interface layer and an anode side is a conventional gas diffusion electrode, and the preparation process is as follows:
(1) 60wt% Pt/C catalyst and PTFE emulsion were dispersed in ethanol (25 mL) at a mass ratio of 1:400. Ultrasonic treatment was carried out in an ultrasonic cleaner for 3 hours to obtain a uniformly dispersed suspension.
(2) And filling the uniformly dispersed suspension into a syringe, regulating the injection speed, ultrasonic power and the operation speed of a spray head, uniformly spraying the obtained ink on the gas diffusion electrode through ultrasonic spraying equipment, and drying at the temperature of 60 ℃ on a heating table to obtain the gas diffusion electrode which is not subjected to heat treatment.
(3) Placing the untreated gas diffusion electrode obtained in the step (2) into a tube furnace, regulating the gas atmosphere of the furnace to be nitrogen or argon, carrying out heat treatment at the temperature of 350 ℃ for 40min, and taking out after the treatment to obtain the required gas diffusion electrode, wherein the platinum loading amount is 0.5mg/cm 2 。
(4) SiO of 10-20nm 2 The nano powder is dispersed in ethanol (20 mL) with the mass ratio of the nano powder to the ethanol being 1:2000. Ultrasonic treatment was carried out in an ultrasonic cleaner for 40mins to obtain a uniformly dispersed suspension.
(5) 100nm SiO obtained in (4) was reacted with 2 The suspension of evenly dispersed nano powder is filled in a syringe, then the injection speed and ultrasonic power and the operation speed of a spray head are regulated, and the obtained 20nm SiO is sprayed by ultrasonic spraying equipment 2 Spraying the suspension onto the surface of the catalytic layer of the gas diffusion electrode, and oven drying at 70deg.C to obtain SiO-containing powder 2 The loading was 0.1mg/cm 2 And a gas diffusion electrode of the interface layer.
(6) The polymer electrolyte membrane immersed in 85wt% phosphoric acid solution at room temperature for 24 hours was erased from the surface phosphoric acid, and placed between the gas diffusion electrode with an interface layer prepared in (5) and a conventional gas diffusion electrode, wherein the gas diffusion electrode with an interface layer was used as a cathode, and a membrane electrode was assembled.
Example 7
The platinum-based catalyst is a catalyst with the platinum content of 40wt%, the preparation mode of the gas diffusion electrode is a knife coating mode, and the interface layer material is SiO with the diameter of 10-20nm 2 Nanometer powder and membrane electrode assembly mode is cathodeThe gas diffusion electrode with interface layer is arranged on the side, the conventional gas diffusion electrode is arranged on the anode side, and the preparation process is as follows:
(1) 40wt% Pt/C catalyst and polytetrafluoroethylene were dispersed in ethanol (50 mL) at a mass ratio of 1:20. Homogenizing in a high-speed homogenizer for 60 minutes to obtain a uniform catalyst slurry.
(2) And placing the obtained catalyst slurry on a flat plate, then adjusting the scraping speed and the scraping height, uniformly scraping the obtained ink on the gas diffusion electrode through a scraping device, and drying at the temperature of 60 ℃ on a heating table to obtain the gas diffusion electrode which is not subjected to heat treatment.
(3) Placing the untreated gas diffusion electrode obtained in the step (2) into a tube furnace, regulating the gas atmosphere of the furnace to be nitrogen or argon, carrying out heat treatment at 370 ℃ for 150mins, and taking out after the treatment to obtain the required gas diffusion electrode with a platinum loading of 0.5mg/cm 2 。
(4) SiO with average grain diameter of 15nm 2 The nano powder is dispersed in isopropanol (20 mL), and the mass ratio of the nano powder to the isopropanol is 1:2000. Ultrasonic treatment was carried out in an ultrasonic cleaner for 30 minutes to obtain a uniformly dispersed suspension.
(5) The SiO obtained in (4) was reacted with 2 The suspension of evenly dispersed nano powder is filled in a syringe, then the injection speed and ultrasonic power and the operation speed of a spray head are regulated, and the obtained SiO is sprayed by ultrasonic spraying equipment 2 Spraying the suspension onto the surface of the catalytic layer of the gas diffusion electrode, and oven drying at 50deg.C to obtain SiO-containing material 2 The loading was 0.2mg/cm 2 And a gas diffusion electrode of the interface layer.
(6) The polymer electrolyte membrane immersed in 85wt% phosphoric acid solution at room temperature for 24 hours was erased from the surface phosphoric acid, and placed between the gas diffusion electrode with an interface layer prepared in (5) and a conventional gas diffusion electrode, wherein the gas diffusion electrode with an interface layer was used as a cathode, and a membrane electrode was assembled.
Example 8
The platinum-based catalyst is a catalyst with the platinum content of 40wt%, the preparation mode of the gas diffusion electrode is a knife coating mode, the interface layer material is cesium phosphotungstate nano powder with the diameter of 20nm, the membrane electrode assembly mode is that the anode side is the gas diffusion electrode with the interface layer, and the cathode side is the conventional gas diffusion electrode, and the preparation process is as follows:
(1) 40wt% Pt/C catalyst and polytetrafluoroethylene were dispersed in ethanol (50 mL) at a mass ratio of 1:20. Homogenizing in a high-speed homogenizer for 30 minutes, to obtain a uniform catalyst slurry.
(2) And placing the obtained catalyst slurry on a flat plate, then adjusting the scraping speed and the scraping height, uniformly scraping the obtained ink on the gas diffusion electrode through a scraping device, and drying at the temperature of 60 ℃ on a heating table to obtain the gas diffusion electrode which is not subjected to heat treatment.
(3) Placing the untreated gas diffusion electrode obtained in the step (2) into a tube furnace, regulating the gas atmosphere of the furnace to be nitrogen or argon, carrying out heat treatment at the temperature of 370 ℃ for 150 minutes, and taking out after the treatment to obtain the required gas diffusion electrode, wherein the platinum loading amount is 0.5mg/cm 2 。
(4) Cesium phosphotungstate nano-powder is dispersed in isopropanol (20 mL), and the mass ratio of the cesium phosphotungstate nano-powder to the isopropanol is 1:20. Homogenizing in a high-speed homogenizer for 40mins to obtain uniform slurry.
(5) Placing cesium phosphotungstate slurry obtained in the step (4) on a flat plate, regulating the scraping speed and the scraping height, uniformly scraping the obtained ink on a gas diffusion electrode through a scraping device, and drying at a temperature of 60 ℃ on a heating table to obtain the cesium phosphotungstate with a cesium phosphotungstate loading of 0.2mg/cm 2 And a gas diffusion electrode of the interface layer.
(6) The polymer electrolyte membrane immersed in 85wt% phosphoric acid solution at room temperature for 24 hours was erased from the surface phosphoric acid, and placed between the gas diffusion electrode with an interface layer prepared in (5) and a conventional gas diffusion electrode, wherein the gas diffusion electrode with an interface layer was used as an anode, and a membrane electrode was assembled.
Comparative example 1
The platinum-based catalyst is a catalyst with the platinum content of 60wt%, the preparation mode of the gas diffusion electrode is a spraying mode, the membrane electrode assembly mode is that the cathode side is a conventional gas diffusion electrode, and the preparation process is as follows:
(1) 60wt% Pt/C catalyst and PTFE emulsion were dispersed in isopropyl alcohol (25 mL) at a mass ratio of 1:500. Ultrasonic treatment was carried out in an ultrasonic cleaner for 6 hours to obtain a uniformly dispersed suspension.
(2) And filling the uniformly dispersed suspension into a syringe, regulating the injection speed, ultrasonic power and the operation speed of a spray head, uniformly spraying the obtained ink on the gas diffusion electrode through ultrasonic spraying equipment, and drying at the temperature of 60 ℃ on a heating table to obtain the gas diffusion electrode which is not subjected to heat treatment.
(3) And (3) putting the untreated gas diffusion electrode obtained in the step (2) into a tube furnace, regulating the gas atmosphere of the furnace to be nitrogen or argon, carrying out heat treatment at the temperature of 360 ℃ for 30mins, and taking out after the treatment, thus obtaining the required gas diffusion electrode.
(4) The polymer electrolyte membrane after being immersed in 85wt% phosphoric acid solution at room temperature for 24 hours was erased from the surface phosphoric acid and placed between the conventional gas diffusion electrodes prepared in (3), to assemble a membrane electrode.
In the embodiment, the relation between the material particle size of the interface layer, the thickness of the formed interface layer, the nano material loading, the morphology of the micropore structure and the like and the migration speed of phosphoric acid to the catalytic layer is researched, and the related parameters in the case of adopting silicon dioxide as the interface layer material are specifically optimized, so that the effect of better preventing the migration of phosphoric acid to the catalytic layer is achieved, the adopted nano SiO 2 The particle size is about 25 to 30nm smaller than that of the catalyst of the diffusion electrode catalyst layer, and in the present embodiment, the nano particle size of the Pt/C catalyst of the catalyst layer is about 45nm, so that the cost in the production process and the remarkable effect of preventing the migration of phosphoric acid are comprehensively considered, and the SiO used is selected 2 The particle size is most preferably 10-20 nm.
At the same time by different SiO 2 The research on the influence of the coating amount on the surface morphology shows that the internal pore structure of the uncovered front electrode catalytic layer is relatively loose, and the large pores among the catalyst agglomerates are more. Within a certain loading range, with SiO 2 Increased coating capacity, cracks on the electrode surface are formed by SiO 2 The pore diameter is gradually reduced, and the space size provided for phosphoric acid accumulation is also reduced, so that the electrolyte membrane can be effectively prevented from leaking out of phosphoric acid caused by extrusion of assembly stress, and the amount of phosphoric acid migrating to the catalytic layer. Through analysis of different pore diameter contents, the SiO is adopted 2 The loading is 0.05-0.2mg cm -2 The thickness of the interface layer is 3.2-9.4 μm; and when the percentage of primary pore diameter of 0.01-0.1 μm in the interface layer is not less than 65%, the percentage of secondary pore diameter of 0.1-1 μm is not more than 12%, and the percentage of large pore diameter of more than 10 μm is not more than 23%, the SiO can be prepared under the condition of reducing cost and preparation difficulty 2 The interface layer has a pore diameter structure which is denser and uniform than that of the catalytic layer, and the agglomerated particles are finer, so that the migration of phosphoric acid to the catalytic layer is effectively prevented even under the condition of low Pt loading and thinner catalytic layer thickness; preventing the occurrence of acid flooding due to the invasion of phosphoric acid from the electrolyte membrane.
As can be seen from fig. 2, the membrane electrode (example 2, example 4 and example 6) prepared according to the present invention has higher performance output compared with the high temperature polymer electrolyte membrane fuel cell assembled with the membrane electrode (comparative example 1), and still shows comparable performance (comparable voltage and power density) even at a larger current density, which means that by constructing an interface layer between the gas diffusion electrode and the polymer electrolyte membrane and optimizing the type of the interface layer material, the material particle size and the interface layer thickness, the migration rate of phosphoric acid in the electrolyte membrane into the catalyst layer is advantageously slowed down, thereby improving the three-phase interface transmission in the catalyst layer and improving the output performance of the high temperature polymer electrolyte membrane fuel cell. The interface layer material in the embodiment 2 adopts XC-72 carbon spheres, and the size of the interface layer material is similar to that of a platinum catalyst; in example 4, the interface layer material was 50 to 70nm of SiO 2 The nano-sphere particles are slightly larger than the size of the platinum catalyst carbon carrier; in example 6, the interface layer material was 10 to 20nm of SiO 2 The size of the nano-sphere particles is far lower than that of the platinum catalyst carbon carrier. Due to SiO 2 There is a strong interaction with phosphoric acid(silicon phosphoric acid can be generated at 160 ℃), the particle size of the interface layer is smaller than that of the catalyst carrier carbon particles, the pore size of the formed interface layer is obviously smaller than that of the catalyst layer, the speed of phosphoric acid in the polymer electrolyte membrane entering the catalyst layer can be obviously slowed down, and meanwhile, the phosphoric acid can enter the catalyst layer more uniformly, so that the phosphoric acid distribution of the catalyst layer is improved, and more effective electrochemical reaction interfaces are constructed. FIG. 3 is a graph showing the ohmic resistance of the high temperature polymer electrolyte membrane fuel cell assembled in example 6 and comparative example 1 with time under the condition that 80 ℃ at 100RH% nitrogen is introduced into the cathode, and it can be seen that the surface of the catalyst layer is structured with SiO 2 After the nano coating, the ohmic resistance of the membrane electrode changes less along with time, and the stability is obviously improved.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent structural changes made to the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A high temperature polymer electrolyte membrane fuel cell membrane electrode comprising at least a high temperature polymer electrolyte membrane, a first gas diffusion electrode, a second gas diffusion electrode, the high temperature polymer electrolyte membrane being located between the first gas diffusion electrode and the second gas diffusion electrode, characterized in that,
the high-temperature polymer electrolyte membrane is a phosphoric acid doped polymer electrolyte membrane;
a membrane-electrode interface layer is arranged between the high-temperature polymer electrolyte membrane and the catalytic layer of the first gas diffusion electrode and/or between the high-temperature polymer electrolyte membrane and the catalytic layer of the second gas diffusion electrode, the membrane-electrode interface layer is made of a material capable of forming hydrogen bonding with phosphoric acid, and the platinum loading capacity in the catalytic layer is less than 0.5mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The pore diameter of the membrane-electrode interface layer is smaller than that of the catalytic layer;
the membrane-electrode interface layer prevents or slows down the migration of phosphoric acid from the high temperature polymer electrolyte membrane to the catalytic layer of the gas diffusion electrode, and is composed of one or a mixture of more of silicon dioxide, montmorillonite, mica, metal oxide, water-insoluble heteropolyacid salt, pyrophosphate and nano carbon material.
2. The high temperature polymer electrolyte membrane fuel cell membrane electrode according to claim 1, wherein the particle size of the membrane-electrode interface layer material is 1 nm-500 nm; the metal oxide is one or more of aluminum oxide, titanium dioxide, tin dioxide, cerium oxide and zirconium oxide, the water-insoluble heteropolyacid salt is one or more of cesium phosphotungstate, ammonium phosphotungstate and cesium molybdenum tungstate, and the pyrophosphate is one or more of tin pyrophosphate, silicon pyrophosphate and zirconium pyrophosphate; the nano carbon material is one or more of carbon quantum dots, nano carbon spheres, graphene and carbon nanotubes.
3. The high temperature polymer electrolyte membrane fuel cell membrane electrode according to claim 2, wherein the membrane-electrode interfacial layer material is nano SiO 2 The nano SiO 2 The particle size of the material is 25-30 nm smaller than that of the catalyst of the diffusion electrode catalytic layer; siO of the membrane-electrode interface layer 2 The loading is 0.05-0.2mg cm -2 The thickness of the interface layer is 3.2-9.4 μm;
the membrane-electrode interface layer is of a microporous structure, wherein the primary pore diameter of 0.01-0.1 mu m is not less than 65%, the secondary pore diameter of 0.1-1 mu m is not more than 12%, and the large pore diameter of more than 10 mu m is not more than 23%.
4. A method for producing a membrane electrode for a high temperature polymer electrolyte membrane fuel cell according to any one of claims 1 to 3, comprising the steps of:
(1) Preparation of gas diffusion electrode
Firstly, dispersing catalyst powder and polymer solution in a first solvent to prepare ink, shaking the prepared ink uniformly, then performing ultrasonic dispersion or high-speed homogenization until the ink has a certain viscosity, and covering the ink on carbon paper coated with a smoothening layer in an ultrasonic spraying, blade coating or screen printing mode; then heat treatment is carried out for a period of time in nitrogen atmosphere under a certain temperature condition to form a needed gas diffusion electrode;
(2) Construction of interface layer on surface of gas diffusion electrode
Dispersing nano powder for constructing an interface layer in a first solvent to prepare a uniformly dispersed suspension, coating the obtained suspension on the surface of a catalytic layer of the gas diffusion electrode obtained in at least one step (1), and carrying out heat treatment for a period of time in an air atmosphere at a certain temperature to fully volatilize the solvent in the interface layer to obtain the gas diffusion electrode containing the interface layer;
(3) Membrane electrode assembly
Placing a phosphoric acid doped saturated high-temperature polymer electrolyte membrane between two gas diffusion electrodes, namely a first gas diffusion electrode and a second gas diffusion electrode, aligning the catalytic layer sides of the two gas diffusion electrodes towards the direction of the polymer electrolyte membrane, and hot-pressing for a period of time under certain temperature and pressure conditions by adopting a hot press to obtain a high-temperature membrane electrode containing an interface layer;
at least one of the first gas diffusion electrode and the second gas diffusion electrode is provided with an interface layer prepared by coating in the step (2).
5. The method for producing a membrane electrode for a high temperature polymer electrolyte membrane fuel cell according to claim 4, wherein the catalyst in step (1) is platinum or a platinum-based alloy, and the polymer in the polymer solution is one or more of polybenzimidazole, polyvinylpyrrolidone, polyarylene piperidine, polyarylene pyridine, polytetrafluoroethylene, polyvinylidene fluoride, perfluorosulfonic acid resin, phosphonated polymer resin, and quaternized anionic polymer; the first solvent is one or more of water, isopropanol, ethanol, methanol, N dimethylformamide, N dimethylacetamide and dimethyl sulfoxide.
6. The method for producing a membrane electrode for a high temperature polymer electrolyte membrane fuel cell according to claim 4, wherein the viscosity of the catalyst ink in the step (1) is 2 to 300 m.pa.s.
7. The method for preparing a membrane electrode of a high temperature polymer electrolyte membrane fuel cell according to claim 6, wherein the viscosity of the ink is 100-300 m.pa.s when the catalyst layer is prepared by doctor blade coating or screen printing; when the ultrasonic spraying mode is adopted to prepare the catalytic layer, the viscosity of the ink is 2-20 m.Pa.s.
8. The method for producing a membrane electrode for a high temperature polymer electrolyte membrane fuel cell according to claim 4, wherein the heat treatment temperature in step (1) is 200 to 350 ℃; the heat treatment time is 10-60 minutes.
9. The method for preparing a membrane electrode of a high temperature polymer electrolyte membrane fuel cell according to claim 4, wherein in the step (2), a uniformly dispersed suspension is prepared by ultrasonic or ball milling, the viscosity of the suspension is 2-300 m.Pa.s, and the suspension coating method comprises spraying, knife coating, coating and silk screen method; the viscosity of the suspension is selected according to the coating mode used for the interface layer: when a doctor-blading and screen printing preparation mode is adopted, the viscosity of the ink is 100-300 m.Pa.s; when the ultrasonic spraying preparation mode is adopted, the viscosity of the ink is 2-20 m.Pa.s.
10. The method for producing a membrane electrode for a high temperature polymer electrolyte membrane fuel cell according to claim 4, wherein the heat treatment temperature in step (2) is 40 to 300 ℃; the heat treatment time is 10-120 minutes, and the hot pressing temperature in the step (3) is room temperature-200 ℃ o And C, the hot pressing pressure is 0.1-5 MPa, and the hot pressing time is 2-10 minutes.
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