CN112909267A - MEA for proton exchange membrane fuel cell and preparation method thereof - Google Patents
MEA for proton exchange membrane fuel cell and preparation method thereof Download PDFInfo
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- CN112909267A CN112909267A CN202110156903.9A CN202110156903A CN112909267A CN 112909267 A CN112909267 A CN 112909267A CN 202110156903 A CN202110156903 A CN 202110156903A CN 112909267 A CN112909267 A CN 112909267A
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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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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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
- H01M4/8828—Coating with slurry or ink
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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
Abstract
The invention relates to an MEA for a proton exchange membrane fuel cell and a preparation method thereof, comprising an anode gas diffusion layer, a polymer exchange membrane and a cathode gas diffusion layer; the anode gas diffusion layer is coated with anode catalyst ink to prepare and form an anode gas diffusion electrode; one side of the polymer exchange membrane is coated with cathode catalyst ink to prepare a catalyst coating membrane coated with a cathode catalyst layer, and the other side of the polymer exchange membrane is attached to an anode gas diffusion electrode; and the cathode gas diffusion layer is attached to the cathode catalyst layer. In the process of preparing the MEA, the performance and the service life of the MEA are not influenced by the swelling of the membrane, and simultaneously, the dosage of the catalyst is reduced, and the performance of the MEA is improved.
Description
Technical Field
The invention belongs to the technical field of proton exchange membrane fuel cells, and particularly relates to an MEA (membrane electrode assembly) for a proton exchange membrane fuel cell and a preparation method thereof.
Background
A Membrane Electrode Assembly (MEA) is a core component of a Proton Exchange Membrane Fuel Cell (PEMFC), and provides a microchannel for heterogeneous material transfer and an electrochemical reaction site for the PEMFC. The current industrialization process of PEMFC still faces the problems of high cost, short service life and the like. The following two approaches are mainly used for improving the performance of the PEMFC and reducing the system cost: one is from the intrinsic activity of the catalyst, the use amount of the noble metal Pt is reduced by changing a carrier, preparing an alloy catalyst and the like, and the activity and the stability of the catalyst are improved. However, it is difficult to improve the performance of PEMFC completely in this way, because the electrochemical reaction process is also affected by many factors such as the three-phase interface and the mass transfer channels of electrons, protons, gas and water; and the other is from the angle of the structures of the membrane electrode and the catalyst layer, the performance of the PEMFC is improved by exploring a new membrane electrode preparation method and a new membrane electrode preparation process, and the mode has wide related factors, can coordinate the reaction process on the whole and improves the performance of the fuel cell.
The conventional MEA preparation method can be divided into two types according to the difference of cl (catalyst layer) support: one is CCS (catalyst coated substrate) method, which is to directly coat catalyst active components on GDL (gas diffusion layer), respectively prepare cathode GDE (gas diffusion electrode) and anode GDE (gas diffusion electrode) coated with catalyst layers, and then press two GDLs on two sides of PEM (polymer exchange membrane) by hot pressing method to obtain MEA; the other is ccm (catalyst coated membrane) method, which is to coat the catalyst active component on both sides of the PEM, and then attach the cathode and anode GDLs to cl (catalyst layer) on both sides respectively, and obtain the MEA by hot pressing.
The CCS method for preparing the MEA has the advantages that the preparation process is relatively simple and mature, the preparation process is beneficial to pore formation, and the PEM cannot deform due to membrane water absorption. The disadvantages are that the catalyst is easy to permeate into GDL in the preparation process, resulting in catalyst waste and lower catalyst utilization rate. In addition, the bonding force between CL and PEM is also generally poor and the interfacial resistance is large. Compared with the CCS method, the CCM method can effectively improve the utilization rate of the catalyst and greatly reduce the proton transfer resistance between the membrane and the CL, the PEM of the CCM method needs to contact with a solvent, and a pure proton exchange membrane is easy to swell, so that the catalyst layer is not uniform, and the CCM method is not suitable for large-scale mass production.
The PEM does not need to contact with a solvent in the CCM preparation process by a transfer method, so that the problems of membrane 'water absorption', expansion, wrinkling and the like are effectively avoided, and the method becomes one of reliable methods for improving the performance of the CCM type MEA. However, there is also a problem that the transfer of the catalytic layer is incomplete.
Disclosure of Invention
The invention aims to solve the technical problem of providing an MEA for a proton exchange membrane fuel cell and a preparation method thereof aiming at the defects of the background art, in the process of preparing the MEA, the performance and the service life of the MEA are not influenced by the swelling of a membrane, the dosage of a catalyst is reduced, and the performance of the MEA is improved.
The invention adopts the following technical scheme for solving the technical problems:
an MEA for a proton exchange membrane fuel cell comprising an anode gas diffusion layer, a polymer exchange membrane and a cathode gas diffusion layer;
the anode gas diffusion layer is coated with anode catalyst ink to prepare and form an anode gas diffusion electrode;
one side of the polymer exchange membrane is coated with cathode catalyst ink to prepare a catalyst coating membrane coated with a cathode catalyst layer, and the other side of the polymer exchange membrane is attached to an anode gas diffusion electrode;
and the cathode gas diffusion layer is attached to the cathode catalyst layer.
Further, the anode catalyst ink is formed by mixing and dispersing an anode catalyst and a resin solution.
Furthermore, the cathode catalyst ink is formed by mixing and dispersing a cathode catalyst and a resin solution.
Furthermore, the polymer exchange membrane and the anode gas diffusion electrode are attached by hot pressing.
A preparation method of MEA for proton exchange membrane fuel cell comprises the following steps:
s1, preparation of anode gas diffusion electrode:
s1a, mixing and dispersing an anode catalyst and a resin solution to form anode catalyst ink;
s1b, coating anode catalyst ink on an anode gas diffusion layer by adopting a spraying, silk-screen, brush coating, blade coating or slit coating mode, and drying to form an anode catalyst layer, thereby finally obtaining an anode gas diffusion electrode;
s2, preparation of catalyst coated membrane:
s2a, mixing and dispersing the cathode catalyst and the resin solution to form cathode catalyst ink;
s2b, coating the cathode catalyst ink on one surface of the polymer exchange membrane with the protective film on one surface to form a cathode catalyst layer by adopting a spraying, silk-screen, brush coating, blade coating or slit coating mode to obtain a catalyst coating film coated with the cathode catalyst layer;
s3, preparing a membrane electrode:
tearing off the protective film of the polymer exchange membrane, then adhering one surface which is not coated with the cathode catalyst layer with the anode catalyst layer of the anode gas diffusion electrode, and then hot-pressing in a hot-pressing device; directly attaching the cathode gas diffusion layer and the cathode catalyst layer after hot pressing to form a five-in-one membrane electrode; the loading capacity of the anode Pt is between 0.01mg/cm2 and 0.1mg/cm2, and the loading capacity of the cathode Pt is between 0.05mg/cm2 and 0.5mg/cm 2.
Compared with the prior art, the invention adopting the technical scheme has the following technical effects:
1. in the process of preparing the MEA, the performance and the service life of the MEA are not influenced by the swelling of the membrane; (ii) a
2. In the process of preparing the MEA, because a new CCM and MEA preparation process is adopted, the process is suitable for large-scale production; (ii) a
3. The method for preparing the MEA by combining the anode GDE and the cathode CCM is introduced in the preparation process, the advantages of the anode GDE and the cathode CCM are combined, the catalyst consumption is reduced, and the performance of the MEA is improved.
Drawings
FIG. 1 is a flow chart of the preparation of anode GDE;
FIG. 2 is a flow chart of catalyst coating film preparation;
FIG. 3 is a flow chart of a five-in-one MEA preparation process.
In the figure, 1, anode catalyst; 2. a resin solution; 3. an anode catalyst ink; 4. an anode gas diffusion layer; 5. an anode catalyst layer; 6. an anode gas diffusion electrode; 7. a cathode catalyst; 8. a resin solution; 9. a cathode catalyst ink; 10. a polymer exchange membrane; 11. a cathode catalyst layer; 12. a catalyst coating film; 13. a four-in-one membrane electrode; 14. a cathode gas diffusion layer; 15. a five-in-one membrane electrode.
Detailed Description
The technical scheme of the invention is further explained in detail by combining the attached drawings:
the invention provides an MEA for a proton exchange membrane fuel cell, which comprises an anode gas diffusion layer 4(GDL), a polymer exchange membrane 10(PEM) and a cathode gas diffusion layer 14 (GDL);
an anode gas diffusion electrode 6(GDE) is prepared by coating anode catalyst ink on the anode gas diffusion layer 4 (GDL);
one side of the polymer exchange membrane 10(PEM) is coated with cathode catalyst ink to prepare a catalyst coated membrane 12(CCM) coated with a cathode catalyst layer 11(CL), and the other side is attached to an anode gas diffusion electrode 6 (GDE);
the cathode gas diffusion layer 14(GDL) and the cathode catalyst layer 11(CL) are bonded.
Further, the anode catalyst ink is formed by mixing and dispersing the anode catalyst 1 and the resin solution 2.
Further, the cathode catalyst ink is formed by mixing and dispersing the cathode catalyst 7 and the resin solution 8.
Further, the polymer exchange membrane 10(PEM) and the anode gas diffusion electrode 6(GDE) are attached by hot pressing.
The invention also provides a preparation method of MEA for proton exchange membrane fuel cell, which comprises the following steps:
s1, preparation of anode gas diffusion electrode 6 (GDE):
s1a, mixing and dispersing an anode catalyst 1 and a resin solution 2 to form anode catalyst ink;
s1b, coating anode catalyst ink on an anode gas diffusion layer 4(GDL) by adopting a spraying, silk-screen, brush-coating, blade-coating or slit coating mode, and drying to form an anode catalyst layer 5(CL), and finally obtaining an anode gas diffusion electrode 6(GDE), wherein the loading capacity of anode Pt is 0.01mg/cm2-0.1mg/cm 2;
s2, preparation of catalyst coated membrane 12 (CCM):
s2a, mixing and dispersing the cathode catalyst 7 and the resin solution 8 to form cathode catalyst ink;
s2b, coating cathode catalyst ink on one side of a polymer exchange membrane 10(PEM) with a protective membrane on one side to form a cathode catalyst layer 11(CL) by adopting a spraying, silk-screen, brush-coating, blade-coating or slit coating mode to obtain a catalyst coated membrane 12(CCM) coated with the cathode catalyst layer 11(CL), wherein the loading amount of cathode Pt is 0.05mg/cm2-0.5mg/cm 2;
s3, Membrane Electrode (MEA) preparation:
tearing off the protective film of the polymer exchange membrane 10(PEM), then adhering the surface which is not coated with the cathode catalyst layer 11(CL) to the anode catalyst layer 5 of the anode gas diffusion electrode 6(GDE), and then hot-pressing in a hot-pressing device to form an anode-supported four-in-one membrane electrode 13 (MEA); after hot pressing, the cathode gas diffusion layer 14(GDL) and the cathode catalyst layer 11(CL) are directly bonded to form a five-in-one membrane electrode 15 (MEA).
The specific embodiment is as follows:
example 1:
1. weighing 1.1 g of 50% Pt/C catalyst (TKK company) in a 50ml beaker, adding 15ml of deionized water, and stirring for dispersion; weighing 3ml of isopropanol and 11ml of 5% mass percent Nafion solution, uniformly mixing, and fully performing ultrasonic dispersion to form ink, wherein the ultrasonic time is about 30min, the standing time is 5min, and the standing temperature is 35 ℃ C.
2. The 29BC GDL of SGL was removed in an area of 5 × 5cm 2.
3. Coating the catalyst ink on the surface of the microporous layer of P29BC, drying the microporous layer with the area size of 5 × 5cm2, and obtaining the catalyst ink shown in figure 1.
4. The nafion211 membrane was removed with an area of 10 x 10cm2 and catalyst ink was sprayed on one side of the nafion211 membrane with an area size of 5 x 5cm2 as shown in fig. 2.
5. Placing PTFE on the GDL coated with the catalyst layer and the non-catalyst surface of the membrane coated with the catalyst 211 in sequence on the side far away from the proton exchange membrane, pressurizing the superposed material to obtain CCM (catalyst coated membrane), and hot-pressing for 3min, as shown in figure 3.
6. Dispensing the CCM, and pasting the CCM with a GDL (with a microporous layer on one side near the catalyst layer) to obtain a Membrane Electrode Assembly (MEA) as shown in fig. 3.
Example 2:
1. weighing 1 g of 60% Pt/C catalyst (Xinwan Town Wanfeng company, England) and placing the Pt/C catalyst into a 50ml beaker, adding 15ml of deionized water, and stirring and dispersing; measuring 1ml of isopropanol, 11ml of 5% mass percent Nafion solution and 10mg of PEG, uniformly mixing, and fully performing ultrasonic dispersion to form ink, wherein the ultrasonic time is about 20min, standing for 2min, and the standing temperature is 35 oC.
2. The 29BC GDL of SGL was removed in an area of 5 × 5cm 2.
3. Spraying catalyst ink on the surface of the microporous layer of P29BC, drying the microporous layer with the area size of 5 × 5cm2, and obtaining the product shown in figure 1.
4. The nafion112 membrane was removed at 10 x 10cm2 area and catalyst ink was drawn down on one side of the nafion112 membrane at 5 x 5cm2 area size as shown in figure 2.
5. Placing PTFE on the GDL coated with the catalyst layer and the non-catalyst surface of the membrane coated with the catalyst 112 in sequence on the side far away from the proton exchange membrane, pressurizing the laminated material to obtain CCM (catalyst coated membrane), and hot-pressing for 3min, as shown in figure 3.
6. Dispensing the CCM, and pasting the CCM with a GDL (with a microporous layer on one side near the catalyst layer) to obtain a Membrane Electrode Assembly (MEA) as shown in fig. 3.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modifications made on the basis of the technical scheme according to the technical idea of the present invention fall within the protection scope of the present invention. While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (5)
1. An MEA for a proton exchange membrane fuel cell, comprising: comprises an anode gas diffusion layer, a polymer exchange membrane and a cathode gas diffusion layer;
the anode gas diffusion layer is coated with anode catalyst ink to prepare and form an anode gas diffusion electrode;
one side of the polymer exchange membrane is coated with cathode catalyst ink to prepare a catalyst coating membrane coated with a cathode catalyst layer, and the other side of the polymer exchange membrane is attached to an anode gas diffusion electrode;
and the cathode gas diffusion layer is attached to the cathode catalyst layer.
2. The MEA for a proton exchange membrane fuel cell according to claim 1, wherein: the anode catalyst ink is formed by mixing and dispersing an anode catalyst and a resin solution.
3. The MEA for a proton exchange membrane fuel cell according to claim 1, wherein: the cathode catalyst ink is formed by mixing and dispersing a cathode catalyst and a resin solution.
4. The MEA for a proton exchange membrane fuel cell according to claim 1, wherein: and the polymer exchange membrane is attached to the anode gas diffusion electrode by hot pressing.
5. The method of claim 1, wherein the MEA is prepared by: the method comprises the following steps:
s1, preparation of anode gas diffusion electrode:
s1a, mixing and dispersing an anode catalyst and a resin solution to form anode catalyst ink;
s1b, coating anode catalyst ink on an anode gas diffusion layer by adopting a spraying, silk-screen, brush coating, blade coating or slit coating mode, and drying to form an anode catalyst layer, thereby finally obtaining an anode gas diffusion electrode;
s2, preparation of catalyst coated membrane:
s2a, mixing and dispersing the cathode catalyst and the resin solution to form cathode catalyst ink;
s2b, coating the cathode catalyst ink on one surface of the polymer exchange membrane with the protective film on one surface to form a cathode catalyst layer by adopting a spraying, silk-screen, brush coating, blade coating or slit coating mode to obtain a catalyst coating film coated with the cathode catalyst layer;
s3, preparing a membrane electrode:
tearing off the protective film of the polymer exchange membrane, then adhering one surface which is not coated with the cathode catalyst layer with the anode catalyst layer of the anode gas diffusion electrode, and then hot-pressing in a hot-pressing device; directly attaching the cathode gas diffusion layer and the cathode catalyst layer after hot pressing to form a five-in-one membrane electrode; the loading capacity of the anode Pt is between 0.01mg/cm2 and 0.1mg/cm2, and the loading capacity of the cathode Pt is between 0.05mg/cm2 and 0.5mg/cm 2.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113991128A (en) * | 2021-10-27 | 2022-01-28 | 中汽创智科技有限公司 | Method and equipment for mass production of membrane electrode assembly |
| CN114792811A (en) * | 2022-06-27 | 2022-07-26 | 浙江高成绿能科技有限公司 | Fuel cell membrane electrode and preparation method thereof |
| CN114865029A (en) * | 2022-05-17 | 2022-08-05 | 上海安池科技有限公司 | Proton exchange membrane fuel cell membrane electrode and preparation method thereof |
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