CN114865029A - Proton exchange membrane fuel cell membrane electrode and preparation method thereof - Google Patents
Proton exchange membrane fuel cell membrane electrode and preparation method thereof Download PDFInfo
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- CN114865029A CN114865029A CN202210534425.5A CN202210534425A CN114865029A CN 114865029 A CN114865029 A CN 114865029A CN 202210534425 A CN202210534425 A CN 202210534425A CN 114865029 A CN114865029 A CN 114865029A
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- 239000012528 membrane Substances 0.000 title claims abstract description 99
- 239000000446 fuel Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 210000000170 cell membrane Anatomy 0.000 title claims description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 239000003792 electrolyte Substances 0.000 claims abstract description 42
- 238000009792 diffusion process Methods 0.000 claims abstract description 29
- 210000004027 cell Anatomy 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 11
- 238000007731 hot pressing Methods 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 150000003460 sulfonic acids Chemical class 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 238000007639 printing Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000007650 screen-printing Methods 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229920006267 polyester film Polymers 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000010923 batch production Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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]
-
- 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
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
- H01M4/8835—Screen printing
-
- 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
- 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
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention relates to the technical field of proton exchange membrane fuel cells, and particularly discloses a preparation method of a membrane electrode of a proton exchange membrane fuel cell. The invention realizes that the anode catalyst layer and the cathode catalyst layer are respectively attached to the anode diffusion layer and the electrolyte membrane by the screen printing technology, simplifies the operation difficulty, and has low equipment cost, small catalyst loss and flexible operation.
Description
Technical Field
The invention relates to the technical field of proton exchange membrane fuel cells, in particular to a membrane electrode of a proton exchange membrane fuel cell and a preparation method thereof.
Background
The proton exchange membrane fuel cell takes hydrogen as fuel and air as oxidant, and directly converts chemical energy in the fuel and the oxidant into electric energy through electrochemical reaction, is not limited by Carnot cycle, and has high energy conversion efficiency. Meanwhile, the reaction product is water, can be directly discharged and is environment-friendly. The proton exchange membrane fuel cell power generation system consists of a plurality of subsystems and parts. The membrane electrode is the core component and is the site of electrochemical reaction.
The membrane electrode is generally composed of an anode, an electrolyte membrane, and a cathode, wherein the electrolyte membrane is disposed between the anode and the cathode, and the three are in close contact. The anode is composed of an anode diffusion layer and an anode catalyst layer, the cathode is composed of a cathode diffusion layer and a cathode catalyst layer, the catalyst layer is arranged on one side close to the electrolyte membrane, the anode diffusion layer and the cathode diffusion layer are both composed of a carbon paper layer containing hydrophobic polytetrafluoroethylene and a porous layer, the thickness and the structure of the carbon paper layer of the cathode and the anode are the same, and the thickness and the structure of the porous layer can be the same or different.
Currently, diffusion layers have been formed into commercial products. The electrolyte membrane is also an immobilized commodity, and is a composite membrane compounded by perfluorinated sulfonic acid resin and a porous polytetrafluoroethylene membrane, wherein the porous polytetrafluoroethylene membrane is arranged in the middle, the perfluorinated sulfonic acid resin with certain thickness is arranged on the cathode surface and the anode surface, the resin penetrates through the porous membrane, the cathode resin membrane is thicker than the anode resin membrane, the cathode resin membrane has different specifications, and the thickness is about 8 micrometers and about 12 micrometers. The catalyst layer is composed of a catalyst and a perfluorosulfonic acid resin, and is usually applied to a diffusion layer (GDE) or an electrolyte membrane (CCM) by preparing the catalyst and a perfluorosulfonic acid resin solution into a uniform mixture in the form of ink.
At present, in order to reduce mass transfer resistance and reduce the thickness of a catalytic layer, the preparation method of the catalytic layer is mainly a CCM method, and the preparation method of the CCM is mainly a spraying method and a slit coating method. The spraying method has simple equipment and intermittent operation, is suitable for small-batch production, and has the problems of large catalyst waste and cost increase caused by spraying. The slit coating technology is suitable for large-scale operation, automatic operation and controllable quality. The problems exist that continuous production is needed, and a large amount of materials are wasted when the machine is stopped and started.
Disclosure of Invention
The invention aims to provide a membrane electrode of a proton exchange membrane fuel cell and a preparation method thereof, which are used for overcoming the problems in the preparation process of a membrane electrode catalyst layer in the prior art.
In order to solve the technical problem, the invention provides a preparation method of a membrane electrode of a proton exchange membrane fuel cell, which comprises the following steps:
s1, mixing a carbon-supported platinum catalyst with a perfluorinated sulfonic acid resin solution, and preparing a mixed emulsion by using isopropanol as a solvent;
s2, cutting the anode diffusion layer to a specified size, printing the mixed emulsion on the surface of a porous layer of the anode diffusion layer on a screen printer, and drying to finish the preparation of an anode catalyst layer;
s3, cutting the electrolyte membrane into a specified size, printing the mixed emulsion on the surface of the cathode surface of the electrolyte membrane on a screen printer, and drying to finish the preparation of the cathode catalyst layer;
and S4, contacting the anode surface of the electrolyte membrane with the surface of an anode catalyst layer of the anode diffusion layer, contacting the surface of a cathode catalyst layer of the electrolyte membrane with the surface of a porous layer of the cathode diffusion layer, and hot-pressing the anode surface, the cathode catalyst layer and the porous layer together on a hot press to form a membrane electrode.
Preferably, in step S1, the weight ratio of the carbon-supported platinum catalyst to the perfluorosulfonic acid resin solution is 3: 1.
preferably, in the step S1, the viscosity of the mixed emulsion is in the range of 30-80 cP.
Preferably, in the steps S2 and S3, the mesh of the screen printer is 80-100 mesh.
Preferably, in step S2, the thickness of the anode catalyst layer is 5 to 10 micrometers.
Preferably, in the steps S2 and S3, the drying temperature is 50-60 ℃ and the drying time is 3-5 minutes.
Preferably, in step S3, the cathode catalyst layer has a thickness of 15 to 25 μm.
Preferably, in step S4, the protective polyester support film on the anode surface of the electrolyte membrane is peeled off, and the anode surface of the electrolyte membrane is brought into contact with the surface of the anode catalyst layer of the anode diffusion layer.
Preferably, in the step S4, the hot pressing temperature of the hot press is 110 ℃ to 130 ℃, and the hot pressing pressure is 1.5 to 3 MPa.
The invention also provides a membrane electrode of the proton exchange membrane fuel cell, which is prepared by the preparation method of the membrane electrode of the proton exchange membrane fuel cell.
The proton exchange membrane fuel cell membrane electrode and the preparation method thereof of the invention provide a cathode catalyst layer and an anode catalyst layer which adopt different supporting methods according to different transfer speeds of hydrogen and oxygen in air and the characteristics of the current commercial membrane motor products, and realize that the anode catalyst layer and the cathode catalyst layer are respectively attached on the anode diffusion layer and the electrolyte membrane by a screen printing technology, thereby simplifying the operation difficulty, having low equipment cost, small catalyst loss and flexible operation.
Drawings
Fig. 1 is a schematic diagram of a method for preparing a membrane electrode of a proton exchange membrane fuel cell according to an embodiment of the present invention.
In the figure, 1: an anode diffusion layer; 2: an anode catalyst layer; 3: an electrolyte membrane; 4: a cathode catalyst layer; 5: and a cathode diffusion layer.
Detailed Description
The embodiments of the present invention will be described in further detail with reference to the drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
As shown in fig. 1, the preparation method of the membrane electrode of the proton exchange membrane fuel cell of the present embodiment includes the following steps:
s1, mixing a carbon-supported platinum catalyst with a perfluorinated sulfonic acid resin solution, wherein the carbon-supported platinum catalyst (Pt/C) and the perfluorinated sulfonic acid resin solution (Nafion solution) are mixed according to the ratio of Pt/C: nafion is 3: 1, and preparing a mixed emulsion with a certain viscosity by using isopropanol as a solvent, wherein the viscosity range is 30-80 cP.
S2, cutting the anode diffusion layer to a specified size, printing the mixed emulsion on the surface of the porous layer of the anode diffusion layer on a screen printer, drying the mesh of the screen printer to 80-100 meshes at the drying temperature of 50-60 ℃ for 3-5 minutes, printing the catalyst layer once or for multiple times according to different catalyst loading amounts and finishing the preparation of the anode catalyst layer, wherein the thickness of the catalyst layer can be 5-10 micrometers according to different catalyst loading amounts.
S3, at present, a layer of protective supporting polyester film is arranged on the anode surface of the commercial electrolyte membrane, the electrolyte membrane is cut into a specified size, the cathode surface of the electrolyte membrane faces to the direction of a screen printing machine, the surface of the polymer protective supporting polyester film faces to the table top of the screen printing machine, the protective supporting polyester film on the anode surface of the electrolyte membrane can play a supporting role, the electrolyte membrane can be subjected to screen printing on the screen printing machine, if the protective supporting polyester film is not arranged, the electrolyte membrane cannot be subjected to screen printing by using the screen printing machine due to thinness, the electrolyte membrane is fixed, the mixed emulsion is printed on the surface of the cathode surface of the electrolyte membrane on the screen printing machine, the grid of the screen printing machine is 80-100 meshes, drying is carried out, the drying temperature is 50-60 ℃, the drying time is 3-5 minutes, the thickness of the catalyst layer can be 15-25 micrometers according to different catalyst loading amounts, the cathode catalyst layer can be printed once or for multiple times according to the requirement of catalyst loading capacity, and the preparation of the cathode catalyst layer is completed.
S4, peeling off the protective supporting polyester film on the anode surface of the electrolyte membrane, contacting the anode surface of the electrolyte membrane with the surface of the anode catalyst layer of the anode diffusion layer, contacting the surface of the cathode catalyst layer of the electrolyte membrane with the surface of the porous layer of the cathode diffusion layer, and hot-pressing the three together on a hot press, wherein the hot press temperature of the hot press is 110-130 ℃, and the hot press pressure is 1.5-3MPa, so that a membrane electrode is formed.
The membrane electrode of the pem fuel cell in this embodiment is made by the method as described in the claim, and as shown in fig. 1, it includes: an anode diffusion layer 1, an anode catalytic layer 2, an electrolyte membrane 3, a cathode catalytic layer 4, and a cathode diffusion layer 5.
The proton exchange membrane fuel cell membrane electrode and the preparation method thereof of the invention provide a cathode catalyst layer and an anode catalyst layer which adopt different supporting methods according to different transfer speeds of hydrogen and oxygen in air and the characteristics of the current commercial membrane motor products, and realize that the anode catalyst layer and the cathode catalyst layer are respectively attached on a diffusion layer and an electrolyte membrane by a screen printing technology, thereby simplifying the operation difficulty, having low equipment cost, small catalyst loss and flexible operation.
Because the cathode catalyst layer is thicker than the anode catalyst layer, the electrolyte layer on the cathode side of the electrolyte membrane is also thicker than the electrolyte layer on the anode side, the cathode directly coats the catalyst on the electrolyte membrane to ensure that the cathode diffusion layer is firmly combined with the catalyst, and meanwhile, the transfer resistance of the electrochemical reaction is mainly concentrated on the cathode, so that the catalyst layer is more favorably prepared on the electrolyte membrane; the anode catalytic layer is thin, the electrolyte layer of the electrolyte membrane is also thin, and the catalytic layer is attached to the diffusion layer, so that the catalytic layer is more favorable for being combined with the electrolyte.
Since the hydrogen gas has a much higher transport rate than oxygen and pure hydrogen is present on the anode side and air containing about 20% oxygen is present on the cathode side. A suitable reduction in the anode transfer rate does not affect the overall electrochemical reaction. The cathode and anode catalyst layers are prepared in different modes mainly by considering the characteristics of the cathode and anode reaction and the structure of the electrolyte membrane, so that the preparation process is simplified to the greatest extent on the premise of not influencing the performance of the battery, the operation is easy, the equipment investment is low, and the size of the membrane electrode is flexibly changed.
The embodiments of the present invention have been presented for purposes of illustration and description, and are not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
Claims (10)
1. A preparation method of a membrane electrode of a proton exchange membrane fuel cell is characterized by comprising the following steps:
s1, mixing a carbon-supported platinum catalyst with a perfluorinated sulfonic acid resin solution, and preparing a mixed emulsion by using isopropanol as a solvent;
s2, cutting the anode diffusion layer to a specified size, printing the mixed emulsion on the surface of a porous layer of the anode diffusion layer on a screen printer, and drying to finish the preparation of an anode catalyst layer;
s3, cutting the electrolyte membrane into a specified size, printing the mixed emulsion on the surface of the cathode surface of the electrolyte membrane on a screen printer, and drying to finish the preparation of the cathode catalyst layer;
and S4, contacting the anode surface of the electrolyte membrane with the surface of an anode catalyst layer of the anode diffusion layer, contacting the surface of a cathode catalyst layer of the electrolyte membrane with the surface of a porous layer of the cathode diffusion layer, and hot-pressing the anode surface, the cathode catalyst layer and the porous layer together on a hot press to form a membrane electrode.
2. The method for preparing a membrane electrode assembly for a proton exchange membrane fuel cell according to claim 1, wherein in step S1, the weight ratio of the carbon-supported platinum catalyst to the perfluorinated sulfonic acid resin solution is 3: 1.
3. the method for preparing a membrane electrode assembly for a proton exchange membrane fuel cell according to claim 1, wherein the viscosity of the mixed emulsion in step S1 is in the range of 30-80 cP.
4. The method for preparing a membrane electrode assembly for a proton exchange membrane fuel cell according to claim 1, wherein the mesh size of the screen printer is 80-100 mesh in steps S2 and S3.
5. The method for preparing a membrane electrode assembly for a proton exchange membrane fuel cell according to claim 1, wherein in step S2, the thickness of the anode catalyst layer is 5 to 10 μm.
6. The method for preparing a membrane electrode assembly for a proton exchange membrane fuel cell according to claim 1, wherein the drying temperature is 50-60 ℃ and the drying time is 3-5 minutes in steps S2 and S3.
7. The method for preparing a membrane electrode assembly for a proton exchange membrane fuel cell according to claim 1, wherein in step S3, the thickness of the cathode catalyst layer is 15 to 25 μm.
8. The method for preparing a membrane electrode assembly for a proton exchange membrane fuel cell according to claim 1, wherein in step S4, the protective polyester support film on the anode surface of the electrolyte membrane is peeled off, and then the anode surface of the electrolyte membrane is brought into contact with the surface of the anode catalyst layer of the anode diffusion layer.
9. The method for preparing a membrane electrode assembly for a proton exchange membrane fuel cell according to claim 1, wherein in step S4, the hot pressing temperature of the hot press is 110-130 ℃, and the hot pressing pressure is 1.5-3 MPa.
10. A proton exchange membrane fuel cell membrane electrode made by the method of making a proton exchange membrane fuel cell membrane electrode of any of claims 1-9.
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| CN202210534425.5A CN114865029A (en) | 2022-05-17 | 2022-05-17 | Proton exchange membrane fuel cell membrane electrode and preparation method thereof |
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| CN202210534425.5A CN114865029A (en) | 2022-05-17 | 2022-05-17 | Proton exchange membrane fuel cell membrane electrode and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1853296A (en) * | 2003-06-04 | 2006-10-25 | 乌米科雷股份两合公司 | Membrane-electrode unit for direct methanol fuel cells and method for the production thereof |
| CN112909267A (en) * | 2021-02-04 | 2021-06-04 | 南京壹元新能源科技有限公司 | MEA for proton exchange membrane fuel cell and preparation method thereof |
| CN113328106A (en) * | 2021-06-02 | 2021-08-31 | 永安行科技股份有限公司 | Fuel cell membrane electrode and preparation method and application thereof |
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- 2022-05-17 CN CN202210534425.5A patent/CN114865029A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1853296A (en) * | 2003-06-04 | 2006-10-25 | 乌米科雷股份两合公司 | Membrane-electrode unit for direct methanol fuel cells and method for the production thereof |
| CN112909267A (en) * | 2021-02-04 | 2021-06-04 | 南京壹元新能源科技有限公司 | MEA for proton exchange membrane fuel cell and preparation method thereof |
| CN113328106A (en) * | 2021-06-02 | 2021-08-31 | 永安行科技股份有限公司 | Fuel cell membrane electrode and preparation method and application thereof |
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