CN111564648B - Fuel cell membrane electrode assembly, preparation method and fuel cell - Google Patents
Fuel cell membrane electrode assembly, preparation method and fuel cell Download PDFInfo
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- CN111564648B CN111564648B CN202010322762.9A CN202010322762A CN111564648B CN 111564648 B CN111564648 B CN 111564648B CN 202010322762 A CN202010322762 A CN 202010322762A CN 111564648 B CN111564648 B CN 111564648B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention discloses a fuel cell membrane electrode assembly, which comprises a proton exchange membrane, wherein two sides of the proton exchange membrane are respectively provided with a moisturizing layer, the moisturizing layers are provided with avoiding regions corresponding to positions forming gas flow channels when the proton exchange membrane is assembled into a fuel cell, two sides of the proton exchange membrane and the avoiding regions filled in the moisturizing layers are respectively provided with a catalyst layer and a diffusion layer arranged outside the catalyst layer, and the hydrophilicity of the moisturizing layer, the catalyst layer and the diffusion layer is sequentially reduced. The diffusion layer and the catalyst layer in the membrane electrode assembly of the fuel cell are adjacently stacked, and the hydrophilicities of the moisture retention layer, the catalyst layer and the diffusion layer are sequentially reduced, so that the drainage capacity and the gas transportation capacity of the fuel cell are improved while the catalyst loading capacity is not reduced. The diffusion layer is thin and has low hydrophilicity, so that the diffusion layer is beneficial to the drainage process of the fuel cell and effectively prevents the flooding phenomenon.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a membrane electrode assembly of a fuel cell, a preparation method and the fuel cell.
Background
Proton exchange membrane fuel cells have gained wide attention in various fields due to their advantages of low operating temperature, high efficiency, large specific energy, no pollution, etc., and have been widely studied in the field of passenger vehicles. With the development of the fuel cell stack, the power requirement of the fuel cell stack is increased, and the membrane electrode assembly is one of the key points for determining the performance. Particularly under the working condition of high current density, the speed of reactants diffusing from the flow channel to the catalytic layer for reaction is limited by the mass transfer rate, so that the performance of the fuel cell is influenced.
The traditional proton exchange membrane fuel cell consists of a cathode plate and an anode plate, a diffusion layer, a catalyst layer and a proton exchange membrane, wherein the membrane electrode is formed by overlapping and pressing the diffusion layer, the catalyst layer, the proton exchange membrane, the catalyst layer and the diffusion layer in sequence layer by layer. The diffusion layer needs to bear the functions of transporting gas reactants and transporting reaction product water, and the bosses on the cathode plate and the anode plate have the effect of compressing the diffusion layer in the assembling process, so that the porosity of the diffusion layer is reduced, the conveying capacity of the diffusion layer is influenced, and the performance of the fuel cell is reduced.
For example, the invention disclosed in publication No. CN101271976A discloses a fuel cell capable of achieving high power generation efficiency in a polymer electrolyte fuel cell. Comprising: a membrane electrode assembly comprising: an electrolyte membrane, an anode catalyst layer and a cathode catalyst layer respectively arranged at both sides of the electrolyte membrane, and an anode gas diffusion layer and a cathode gas diffusion layer respectively arranged at the sides of the anode catalyst layer and the cathode catalyst layer opposite to the electrolyte membrane side; a cathode porous body provided on a side of the cathode gas diffusion layer opposite to the cathode catalyst layer side; and a cathode member provided on the side of the cathode porous body opposite to the cathode gas diffusion layer side and having a projection in contact with the cathode porous body, wherein pressure is applied to the cathode porous body by the cathode member so that the projection compresses the cathode porous body.
The invention with publication number CN101465434 discloses a fuel cell membrane electrode, which comprises: the proton exchange membrane comprises a proton exchange membrane and electrodes respectively arranged on two surfaces of the proton exchange membrane, wherein the electrodes consist of a gas diffusion layer and a catalyst layer, the gas diffusion layer comprises a carbon nano tube film structure, the carbon nano tube film structure comprises at least one carbon nano tube layer, and the carbon nano tubes in the carbon nano tube layer are arranged along the same direction in a preferred orientation mode. A preparation method of a fuel cell membrane electrode specifically comprises the following steps: providing a carbon nanotube array; drawing the carbon nanotube array to obtain at least one carbon nanotube film; preparing a gas diffusion layer by adopting the carbon nano tube film; forming a catalyst layer on the surface of the gas diffusion layer to obtain an electrode; and providing a proton exchange membrane, and respectively arranging the two electrodes on the two surfaces of the proton exchange membrane to obtain a fuel cell membrane electrode.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provide a fuel cell membrane electrode assembly with high gas transmission efficiency and strong water drainage capability.
A fuel cell membrane electrode assembly comprises a proton exchange membrane, wherein a moisturizing layer is respectively arranged on two sides of the proton exchange membrane, an avoiding area is arranged at a position where a gas flow channel is formed when the proton exchange membrane is assembled into a fuel cell, a catalysis layer and a diffusion layer are respectively arranged on two sides of the proton exchange membrane and filled in the avoiding area of the moisturizing layer, and the hydrophilicity of the moisturizing layer, the catalysis layer and the diffusion layer is sequentially reduced.
Preferably, the material of the moisture-keeping layer is carbon cloth, carbon paper, carbon felt or foam carbon.
Preferably, the diffusion layer is formed by adding a hydrophobic agent to the corresponding position of the moisture retention layer. The diffusion layer is obtained by directly adding the hydrophobic agent on the substrate material serving as the moisturizing layer, and the preparation method is simple and convenient.
The hydrophobic agent is at least one of polytetrafluoroethylene, polyvinylidene fluoride, fluorinated ethylene copolymer and fluorinated ethylene propylene. The hydrophobing agent can be added in a spraying mode, the position where the hydrophobing agent is not required to be sprayed is shielded by using the baffle plate, the position where the hydrophobing agent is required to be sprayed is reserved, and spraying operation can be conveniently carried out. After spraying the hydrophobic agent, the hydrophobic agent is attached to the corresponding position of the substrate material serving as the moisture retention layer through a baking-sintering process to prepare the diffusion layer with the hydrophobicity of the designated area.
The catalyst component used in the catalytic layer may be of a type commonly used in the art, and preferably, the catalyst component in the catalytic layer is at least one of platinum, gold, iridium, palladium, ruthenium, and osmium. In general, a platinum-based catalyst is used in a large amount.
The hydrophilic contact angle of the moisture retention layer is 75-80 degrees, the hydrophilic contact angle of the diffusion layer is 115-120 degrees, and the hydrophilic contact angle of the catalyst layer is 95-100 degrees.
The invention also provides a preparation method of the fuel cell membrane electrode assembly, which comprises the following steps:
(1) taking a first material as a moisture retention layer, adding a hydrophobic agent to a position on the first material for forming a diffusion layer, and enabling the hydrophobic agent to be attached to the first material to form the diffusion layer;
(2) processing a first material for forming a diffusion layer at a position corresponding to the diffusion layer to form a catalyst layer, or taking a second material as a proton exchange membrane, and processing positions of a cathode surface and an anode surface on the second material corresponding to the catalyst layer to form catalyst layers of a cathode and an anode respectively;
(3) and respectively laminating two first materials processed with a diffusion layer and a catalyst layer on two sides of a cathode and an anode of a second material, or respectively laminating two first materials processed with the diffusion layer on two sides of the cathode and the anode of the second material processed with the catalyst layer, wherein the diffusion layer corresponds to the catalyst layer, and hot-press molding to obtain the fuel cell membrane electrode assembly.
When the catalyst is sprayed, the spraying thickness of the anode end is 0.006-0.008 mm, and the spraying thickness of the cathode end is 0.01-0.012 mm.
The catalytic layer and the diffusion layer are correspondingly stacked, after hot pressing, the total thickness of the catalytic layer and the diffusion layer is equal to the thickness of the moisture retention layer, the thickness of the diffusion layer is relatively thin, the gas transportation capability of the diffusion layer is improved, and the performance attenuation of the fuel cell caused by concentration polarization is favorably improved.
The invention also provides a fuel cell of the fuel cell membrane electrode assembly.
Preferably, the two sides of the fuel cell membrane electrode assembly are respectively provided with a cathode plate and an anode plate, a gas flow channel is arranged on the interface of the electrode plate and the fuel cell membrane electrode assembly, and the gas flow channel is arranged on one side of the electrode plate and one side of the fuel cell membrane electrode assembly or is formed by combining part of the electrode plate and part of the fuel cell membrane electrode assembly.
More preferably, the width of the gas channel is not greater than the width of the avoiding area; the width of the gas flow channel is 0.6-5 mm. The structure characteristic of the application can be suitable for a wide flow channel, the processing of the flow channel on the polar plate is convenient, and the processing cost is reduced.
The diffusion layer and the catalyst layer in the membrane electrode assembly of the fuel cell are adjacently stacked, and the hydrophilicities of the moisture retention layer, the catalyst layer and the diffusion layer are sequentially reduced, so that the drainage capacity and the gas transportation capacity of the fuel cell are improved while the catalyst loading capacity is not reduced. The diffusion layer is thin and has low hydrophilicity, so that the diffusion layer is beneficial to the drainage process of the fuel cell and effectively prevents the flooding phenomenon.
When the device works under a low current density, moisture is taken away by reactant gas, and the moisture in the moisture retention layer diffuses to the proton exchange membrane and the catalyst layer, so that the performance of the battery is improved; when the catalyst layer works under high current density, a large amount of water is generated on the surface of the catalyst layer, the moisture retention layer can absorb enough water, and the diffusion layer can discharge excessive water to prevent from blocking the porous gaps of the diffusion layer and the catalyst layer.
Drawings
Fig. 1 is a schematic view of a positional relationship structure of a moisture retention layer, a catalyst layer, a diffusion layer, and a gas flow channel.
Fig. 2 is a schematic structural view of a membrane electrode assembly of a fuel cell according to the present invention.
Detailed Description
Example 1
As shown in fig. 1 and 2, a fuel cell membrane electrode assembly 50 includes a membrane electrode assembly 30 and a respective electrode plate 05 disposed on both sides of the membrane electrode assembly 30, wherein a gas flow channel 04 is disposed at an interface between the electrode plate 05 and the membrane electrode assembly 30, and an anode and a cathode are disposed on both sides of the membrane electrode assembly 30.
The membrane electrode assembly 30 comprises a proton exchange membrane 06, a moisture retention layer 01 is respectively arranged on two sides of the proton exchange membrane 06, the moisture retention layer 01 is provided with an avoidance area corresponding to a position where a gas flow passage 04 is formed when the proton exchange membrane is assembled into a fuel cell, a catalyst layer 02 is respectively arranged on two sides of the proton exchange membrane 06 and filled in the avoidance area of the moisture retention layer 01, and a diffusion layer 03 is arranged on the outer side of the catalyst layer 02, and the hydrophilicity of the moisture retention layer 01, the catalyst layer 02 and the diffusion layer 03 is sequentially reduced. The hydrophilic contact angle of the moisture retention layer is 75-80 degrees, the hydrophilic contact angle of the diffusion layer is 115-120 degrees, and the hydrophilic contact angle of the catalyst layer is 95-100 degrees.
The material of the moisture-keeping layer 01 is carbon cloth, carbon paper, carbon felt or foam carbon. The diffusion layer 03 is formed by adding a hydrophobic agent to the corresponding position of the moisture retention layer 01. The diffusion layer 03 is obtained by directly adding a hydrophobizing agent to the base material serving as the moisturizing layer 01, and the preparation method is simple and convenient. The hydrophobic agent used can be at least one of polytetrafluoroethylene, polyvinylidene fluoride, fluorinated ethylene copolymer and fluorinated ethylene propylene. The hydrophobing agent can be added in a spraying mode, the position where the hydrophobing agent is not required to be sprayed is shielded by using the baffle plate, the position where the hydrophobing agent is required to be sprayed is reserved, and spraying operation can be conveniently carried out. After the water repellent agent is sprayed, the water repellent agent is attached to the corresponding position of the substrate material serving as the moisture retention layer 01 through a baking-sintering process, and the diffusion layer 03 with the hydrophobicity of the designated area is manufactured.
The catalyst component used in the catalytic layer 02 may be of a type commonly used in the art, for example, the catalyst component is at least one of platinum, gold, iridium, palladium, ruthenium, and osmium. In general, a platinum-based catalyst is used in a large amount.
Example 2
(1) And manufacturing a spraying baffle according to the flow channel pattern on the bipolar plate drawing, wherein the baffle is provided with a layer of holes cut at the position corresponding to the flow channel of the bipolar plate. Preparing a piece of 0.1mm thick Nippon Dongli carbon paper (as a moisturizing layer, the contact angle is 75-80 degrees), paving the paper on a negative pressure platform, and placing a spraying baffle on the negative pressure platform. The polytetrafluoroethylene resin is sprayed on the carbon paper in a spraying mode, and then the hydrophobic agent is attached to the carbon paper through a baking-sintering process to prepare a diffusion layer with the hydrophobicity of a specified area, wherein the hydrophobic contact angle of the diffusion layer is 115-plus-120 degrees.
(2) 1g of platinum-carbon catalyst, 30g of n-propanol, 20g of water and 3g of 50% PTFE resin emulsion are taken, and the catalyst slurry is prepared by ultrasonic oscillation, stirring and other modes. Cutting according to the requirements of a drawing to prepare a perfluorosulfonic acid proton exchange membrane, flatly laying the perfluorosulfonic acid proton exchange membrane on a heating table, and then spraying a catalyst in a specified area (corresponding to a hydrophobic area of a diffusion layer) according to the requirements, wherein the spraying thickness of an anode surface is 0.008mm, and the spraying thickness of a cathode surface is 0.012mm, so that a membrane electrode (CCM) with a contact angle of 95-100 degrees is prepared.
(3) And laminating the prepared membrane electrode and the diffusion layer on a heating plate correspondingly according to the requirements of a drawing, and putting the membrane electrode and the diffusion layer into a hot press for hot press molding to obtain the membrane electrode assembly, namely the membrane electrode assembly of the fuel cell.
Example 3
(1) And manufacturing a spraying baffle according to the flow channel pattern on the bipolar plate drawing, wherein the baffle is provided with a layer of holes cut at the position corresponding to the flow channel of the bipolar plate. Preparing a piece of 0.1mm thick Nippon Dongli carbon paper (as a moisturizing layer, the contact angle is 75-80 degrees), paving the paper on a negative pressure platform, and placing a spraying baffle on the paper. The polytetrafluoroethylene resin is sprayed on the carbon paper in a spraying mode, and then the hydrophobic agent is attached to the carbon paper through a baking-sintering process to prepare a diffusion layer with the hydrophobicity of a specified area, wherein the hydrophobic contact angle of the diffusion layer is 115-plus-120 degrees.
(2) 1g of platinum-carbon catalyst, 30g of n-propanol, 20g of water and 3g of 50% PTFE resin emulsion are taken, and the catalyst slurry is prepared by ultrasonic oscillation, stirring and other modes. And flatly spreading the diffusion layer on a heating table, and then spraying a catalyst on the hydrophobic region of the diffusion layer as required, wherein the spraying thickness of the anode end diffusion layer is 0.006mm, and the spraying thickness of the cathode end diffusion layer is 0.01mm, so that a diffusion layer electrode (GDE) with a contact angle of 95-100 degrees is prepared.
(3) And laminating the prepared diffusion layer electrode and the proton exchange membrane on a heating plate according to the requirements of a drawing, and putting the heating plate into a hot press for hot press molding to obtain the membrane electrode assembly, namely the membrane electrode assembly of the fuel cell.
Claims (7)
1. A fuel cell membrane electrode assembly comprises a proton exchange membrane, and is characterized in that two sides of the proton exchange membrane are respectively provided with a moisture retention layer, the moisture retention layers are provided with avoidance areas corresponding to positions forming gas flow channels when the proton exchange membrane is assembled into a fuel cell, two sides of the proton exchange membrane and the avoidance areas filled in the moisture retention layers are respectively provided with a catalyst layer and a diffusion layer arranged outside the catalyst layer, the hydrophilicity of the moisture retention layers, the catalyst layers and the diffusion layer is sequentially reduced,
the material of the moisture-keeping layer is carbon cloth, carbon paper, carbon felt or foam carbon,
the diffusion layer is formed by adding a hydrophobic agent into the corresponding position of the moisture retention layer,
the hydrophilic contact angle of the moisture retention layer is 75-80 degrees, the hydrophilic contact angle of the diffusion layer is 115-120 degrees, and the hydrophilic contact angle of the catalyst layer is 95-100 degrees.
2. The fuel cell membrane electrode assembly according to claim 1 wherein said hydrophobic agent is at least one of polytetrafluoroethylene, polyvinylidene fluoride, and polyfluoroethylene propylene.
3. The fuel cell membrane electrode assembly according to claim 1 wherein the catalyst component in the catalytic layer is at least one of platinum, gold, iridium, palladium, ruthenium, and osmium.
4. A method of making a fuel cell membrane electrode assembly according to any one of claims 1 to 3, comprising the steps of:
(1) taking a first material as a moisture retention layer, adding a hydrophobic agent to a position on the first material for forming a diffusion layer, and enabling the hydrophobic agent to be attached to the first material to form the diffusion layer;
(2) processing a first material for forming a diffusion layer at a position corresponding to the diffusion layer to form a catalyst layer, or taking a second material as a proton exchange membrane, and processing positions of a cathode surface and an anode surface on the second material corresponding to the catalyst layer to form catalyst layers of a cathode and an anode respectively;
(3) and respectively laminating two first materials processed with a diffusion layer and a catalyst layer on two sides of a cathode and an anode of a second material, or respectively laminating two first materials processed with the diffusion layer on two sides of the cathode and the anode of the second material processed with the catalyst layer, wherein the diffusion layer corresponds to the catalyst layer, and hot-press molding to obtain the fuel cell membrane electrode assembly.
5. A fuel cell comprising a fuel cell membrane electrode assembly according to any one of claims 1 to 3.
6. The fuel cell according to claim 5, wherein the fuel cell membrane electrode assembly has a cathode plate and an anode plate on both sides thereof, and a gas flow channel is provided at the interface between the cathode plate and the fuel cell membrane electrode assembly and the gas flow channel is provided at one side of the cathode plate and the anode plate, at one side of the fuel cell membrane electrode assembly, or formed by combining the cathode plate and the anode plate with a part of the fuel cell membrane electrode assembly.
7. The fuel cell according to claim 6, wherein the width of the gas flow channel is not greater than the width of the bypass region; the width of the gas flow channel is 0.6-5 mm.
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| CN112952166B (en) * | 2021-02-24 | 2021-10-15 | 上海捷氢科技有限公司 | Membrane electrode and battery with wetting function and high mass transfer |
| CN113506888B (en) * | 2021-09-07 | 2021-11-30 | 爱德曼氢能源装备有限公司 | Fuel cell polar plate structure and electric pile |
| CN115483411A (en) * | 2022-09-20 | 2022-12-16 | 中国科学院宁波材料技术与工程研究所 | Fuel cell unit, fuel cell, power generation system, and power consumption device |
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| JP2003197203A (en) * | 2001-12-28 | 2003-07-11 | Nissan Motor Co Ltd | Fuel cell |
| CN1976763A (en) * | 2004-04-14 | 2007-06-06 | 通用汽车公司 | Device of diffusion media with pattern |
| CN110350207A (en) * | 2019-06-18 | 2019-10-18 | 武汉理工大学 | Fuel cell carbon paper fixture and the preparation method that hydrophobicity carbon paper is prepared using the fixture |
| CN110676468A (en) * | 2019-08-30 | 2020-01-10 | 天津大学 | Method for processing hydrophobic property of cathode gas diffusion layer material in proton exchange membrane fuel cell |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003197203A (en) * | 2001-12-28 | 2003-07-11 | Nissan Motor Co Ltd | Fuel cell |
| CN1976763A (en) * | 2004-04-14 | 2007-06-06 | 通用汽车公司 | Device of diffusion media with pattern |
| CN110350207A (en) * | 2019-06-18 | 2019-10-18 | 武汉理工大学 | Fuel cell carbon paper fixture and the preparation method that hydrophobicity carbon paper is prepared using the fixture |
| CN110676468A (en) * | 2019-08-30 | 2020-01-10 | 天津大学 | Method for processing hydrophobic property of cathode gas diffusion layer material in proton exchange membrane fuel cell |
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Application publication date: 20200821 Assignee: Zhejiang Tianneng Hydrogen Energy Technology Co.,Ltd. Assignor: TIANNENG BATTERY GROUP Co.,Ltd. Contract record no.: X2022330000396 Denomination of invention: A fuel cell membrane electrode assembly, preparation method and fuel cell Granted publication date: 20210921 License type: Common License Record date: 20220810 |
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