CN112713292B - Hydrogen fuel cell membrane electrode assembly suitable for batch production and production process thereof - Google Patents
Hydrogen fuel cell membrane electrode assembly suitable for batch production and production process thereof Download PDFInfo
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- CN112713292B CN112713292B CN202011562859.3A CN202011562859A CN112713292B CN 112713292 B CN112713292 B CN 112713292B CN 202011562859 A CN202011562859 A CN 202011562859A CN 112713292 B CN112713292 B CN 112713292B
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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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
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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
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
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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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Abstract
The invention provides a hydrogen fuel cell membrane electrode assembly suitable for batch production and a processing technology thereof, wherein the hydrogen fuel cell membrane electrode assembly comprises a gas diffusion layer, a catalyst layer, a perfluorinated sulfonic acid resin membrane and a protective membrane frame; each side of the perfluorinated sulfonic acid resin film is sequentially and uniformly coated with a catalyst layer, a protective film frame and a gas diffusion layer; the inner edge of the protective film frame is 1-2mm closer to the center of the perfluorosulfonic acid resin film than the outer edge of the gas diffusion layer; the protective film frame is bonded to the perfluorinated sulfonic acid resin film through an adhesive; the gas diffusion layer is adhered to the protective film frame through an adhesive, and the coating width of the adhesive is less than 1mm and is 1-2mm away from the outer edge of the gas diffusion layer. By adopting the technical scheme of the invention, the mechanical strength and the service life of the membrane electrode assembly are ensured, and meanwhile, the membrane electrode assembly can realize batch automatic production.
Description
Technical Field
The invention relates to the field of proton exchange membrane fuel cells, in particular to a hydrogen fuel cell membrane electrode assembly suitable for batch production and a production process thereof.
Background
The hydrogen fuel cell is used as an energy conversion device, can convert the chemical reaction process between hydrogen and oxygen into electric energy for output, can generate a large amount of heat energy and water, and has the characteristic of environmental friendliness, which is more and more accepted and supported by the public.
When a Membrane Electrode Assembly (MEA) is used as a power generation unit of a fuel cell, an improper sealing structure not only affects the appearance and sealing performance of the MEA, but also causes a decrease in performance and life. The patent with publication number CN201060896Y discloses a composite membrane electrode of a proton exchange membrane fuel cell, and the membrane electrode sealing structure introduced in the patent enhances the mechanical strength of a membrane electrode due to the addition of a multilayer composite structure, but the structural characteristics of the membrane electrode sealing structure can only be manually manufactured, so that the product consistency of a membrane electrode assembly is poor, the yield is low, and automatic batch production cannot be realized.
In order to enhance the product consistency of a membrane electrode assembly (MEA for short) of a hydrogen fuel cell, improve the capacity of the MEA, and improve the yield, an MEA sealing structure suitable for mass production and a press-forming process scheme thereof need to be developed, so as to improve the capacity and the MEA production process, and improve the product consistency and reliability of the MEA.
Patent publication No. CN201060896Y discloses a composite membrane electrode for a proton exchange membrane fuel cell. Patent publication No. CN104577158A discloses a resin frame-equipped membrane-electrode assembly for a fuel cell.
Disclosure of Invention
According to the technical problems that the existing membrane electrode sealing structure products are poor in consistency and cannot be produced in batches and the like, the hydrogen fuel cell membrane electrode assembly suitable for batch production and the production process thereof are provided.
The technical means adopted by the invention are as follows:
a hydrogen fuel cell membrane electrode assembly suitable for batch production comprises a gas diffusion layer, a catalyst layer, a perfluorinated sulfonic acid resin film and a protective film frame; each side of the perfluorinated sulfonic acid resin film is sequentially and uniformly coated with a catalyst layer, a protective film frame and a gas diffusion layer; the inner edge of the protective film frame is 1-2mm closer to the center of the perfluorosulfonic acid resin film than the outer edge of the gas diffusion layer; the protective film frame is bonded to the perfluorinated sulfonic acid resin film through an adhesive; the gas diffusion layer is adhered to the protective film frame through an adhesive, and the coating width of the adhesive is less than 1mm and is 1-2mm away from the outer edge of the gas diffusion layer.
Further, the perfluorosulfonic acid resin film has a thickness of 8 to 25 μm, and the gas diffusion layer has a thickness of 150 to 300 μm.
Further, the protective film frame is made of a polytetrafluoroethylene film, a polyimide film, a polyethylene terephthalate film, a polyethylene naphthalate film or a polyether ether ketone film.
Further, the gas diffusion layer is the same size and is aligned with the catalyst layer on the side where it is located.
Further, the catalytic layers on both sides of the perfluorosulfonic acid resin membrane are uniform in size and aligned in position, and the catalytic layers are continuously or discontinuously coated on the perfluorosulfonic acid resin membrane.
Further, the adhesive is polypropylene, epoxy resin, EVA, silica gel or polyurethane adhesive.
Furthermore, the thickness of the protective film frame is 25-80 μm.
The invention also provides a production process of the membrane electrode assembly, which specifically comprises the following steps:
(1) Coating the catalyst slurry, namely uniformly coating the prepared catalyst slurry on two sides of a coiled perfluorosulfonic acid resin film by using slit coating equipment to form a catalytic layer, wherein the catalytic layer is continuously or discontinuously coated;
(2) Attaching a protective film frame to the perfluorinated sulfonic acid resin film coated with the catalytic layer, wherein one side of the protective film frame is coated with a bonding agent, the protective film frame is attached to two sides of the coiled perfluorinated sulfonic acid resin film coated with the catalytic layer on two sides by using rolling and pressing equipment, and the inner edge of the protective film frame 1 is 1-2mm closer to the center of the perfluorinated sulfonic acid resin film than the outer edge of the catalytic layer;
(3) Coating a binder around the outer edge of the gas diffusion layer, wherein the coating area of the binder is 1-2mm away from the outer edge of the gas diffusion layer; the adhesive is coated by transfer printing, dispensing, screen printing or spraying;
(4) Two gas diffusion layers are respectively bonded to two sides of a coiled perfluorosulfonic acid resin film with a protective film frame and a catalytic layer through adhesives to form a membrane electrode assembly.
Compared with the prior art, the invention has the following advantages:
the hydrogen fuel cell membrane electrode assembly suitable for batch production and the production process thereof provided by the invention can ensure the mechanical strength and the service life of the membrane electrode assembly, simultaneously realize batch automatic production of the membrane electrode assembly, improve the production efficiency and consistency of the membrane electrode and provide powerful support for industrialization.
Based on the reason, the invention can be widely popularized in the field of proton exchange membrane fuel cells.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic view of the membrane electrode assembly according to the present invention.
Fig. 2 is a schematic view of the structure of the clamp.
FIG. 3 is a schematic view of the catalytic layer coating process of the present invention.
Fig. 4 is a schematic diagram of the bonding process of the protective film frame according to the present invention.
Fig. 5 is a schematic diagram of the process of applying the adhesive to the outer edge of the gas diffusion layer according to the present invention.
Fig. 6 is a schematic view illustrating a bonding process of a gas diffusion layer according to the present invention.
Figure 7 is a schematic of a polarization curve for a membrane electrode assembly.
Fig. 8 is a HFR curve diagram of a membrane electrode assembly.
Fig. 9 is a schematic view of a hydrogen permeation current test curve of the membrane electrode assembly.
In the figure: 1. the device comprises a protective film frame, 2 parts of a perfluorinated sulfonic acid resin film, 3 parts of an anode gas diffusion layer, 4 parts of an anode catalytic layer, 5 parts of a cathode gas diffusion layer and 6 parts of a cathode catalytic layer; 7. a membrane electrode assembly; 8. a single cell cathode and anode end plate; 9. a single cell cathode and anode collector plate; 10. a cathode and anode graphite flow field plate; 11. an anode catalyst slurry coating head; 12. a cathode catalyst slurry coating head; 13. an upper compression roller; 14. a lower pressing roller; 15. gluing a needle head; 16. gluing a needle trajectory line; 17. and (6) gluing areas.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise. Meanwhile, it should be understood that the sizes of the respective portions shown in the drawings are not drawn in an actual proportional relationship for the convenience of description. Techniques, methods, and apparatus that are known by one of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate. Any specific values in all examples shown and discussed herein are to be construed as exemplary only and not as limiting. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
In the description of the present invention, it is to be understood that the directions or positional relationships indicated by the directional terms such as "front, rear, upper, lower, left, right", "lateral, vertical, horizontal" and "top, bottom", etc., are generally based on the directions or positional relationships shown in the drawings for the convenience of description and simplicity of description, and that these directional terms, unless otherwise specified, do not indicate and imply that the device or element so referred to must have a particular orientation or be constructed and operated in a particular orientation, and therefore should not be considered as limiting the scope of the invention: the terms "inner and outer" refer to the inner and outer relative to the profile of the respective component itself.
For ease of description, spatially relative terms such as "over 8230 \ 8230;,"' over 8230;, \8230; upper surface "," above ", etc. may be used herein to describe the spatial relationship of one device or feature to another device or feature as shown in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if a device in the figures is turned over, devices described as "above" or "on" other devices or configurations would then be oriented "below" or "under" the other devices or configurations. Thus, the exemplary terms "at 8230; \8230; above" may include both orientations "at 8230; \8230; above" and "at 8230; \8230; below". The device may be otherwise variously oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
It should be noted that the terms "first", "second", and the like are used to define the components, and are only used for convenience of distinguishing the corresponding components, and the terms have no special meanings unless otherwise stated, and therefore, the scope of the present invention should not be construed as being limited.
Example 1
As shown in fig. 1, the present invention provides a hydrogen fuel cell membrane electrode assembly suitable for mass production, which includes a gas diffusion layer, a catalyst layer, a perfluorosulfonic acid resin membrane 2, and a protective membrane frame 1; each side of the perfluorinated sulfonic acid resin membrane 2 is sequentially and uniformly coated with a catalytic layer, a protective membrane frame and a gas diffusion layer;
in the present embodiment, the catalytic layers include an anode catalytic layer 4 and a cathode catalytic layer 6, and the gas diffusion layers include an anode gas diffusion layer 3 and a cathode gas diffusion layer 5;
the inner edge of the protective film frame 1 is 1-2mm closer to the center of the perfluorosulfonic acid resin film 2 than the outer edge of the gas diffusion layer; the protective film 1 frame is bonded to the perfluorosulfonic acid resin film 2 through an adhesive; the gas diffusion layer is adhered to the protective film frame 1 through an adhesive, and the coating width of the adhesive is less than 1mm and is 1-2mm away from the outer edge of the gas diffusion layer.
The protective film frame 1 has the protective effect on the perfluorinated sulfonic acid resin film 2 and the sealing effect of isolating the gas of the cathode and the anode, and the membrane electrode assembly can effectively protect the perfluorinated sulfonic acid resin film, improves the durability of the membrane electrode and is easy to realize automatic batch manufacturing.
Further, the thickness of the perfluorosulfonic acid resin film 2 is 8 to 25 μm, and the thickness of the gas diffusion layer is 150 to 300 μm.
Further, the protective film frame 1 is made of a teflon film, a polyimide film, a polyethylene terephthalate film, a polyethylene naphthalate film or a polyetheretherketone film, or other common commercial materials.
Further, the gas diffusion layer is the same size and is aligned with the catalyst layer on the side where it is located.
Further, the catalytic layers on both sides of the perfluorosulfonic acid resin membrane 2 are uniform in size and aligned in position, and the catalytic layers are continuously or intermittently coated on the perfluorosulfonic acid resin membrane 2.
Furthermore, the adhesive is polypropylene, epoxy resin, EVA, silica gel or polyurethane adhesive, or other common commercial materials.
Further, the thickness of the protective film frame 1 is 25-80 μm.
Further, the perfluorosulfonic acid resin film 2 employs Gore
Perfluorosulfonic acid resin film, using Toray gas diffusion layers, all common commercial materials.
The invention also provides a batch production process of the membrane electrode assembly, which specifically comprises the following steps:
(1) As shown in fig. 3, catalyst slurry coating, namely uniformly coating the prepared catalyst slurry on two sides of a roll of perfluorosulfonic acid resin film 2 by using a slit coating device (comprising an anode catalyst slurry coating head 11 and a cathode catalyst slurry coating head 12) to form a catalytic layer, wherein the catalytic layer can be continuously or discontinuously coated;
(2) As shown in fig. 4, a protective film frame 1 is attached to a perfluorosulfonic acid resin film 2 coated with a catalytic layer, one side of the protective film frame 1 is coated with an adhesive, the protective film frame 1 is attached to two sides of the perfluorosulfonic acid resin film 2 coated with the catalytic layer on two sides of a roll by using a rolling and pressing device (comprising an upper press roller 13 and a lower press roller 14), and the inner edge of the protective film frame 1 is 1-2mm closer to the center of the perfluorosulfonic acid resin film 2 than the outer edge of the catalytic layer;
(3) As shown in fig. 5, the adhesive is coated around the outer edge of the gas diffusion layer, and the coated area of the adhesive is 1-2mm from the outer edge of the gas diffusion layer; the adhesive can be applied by transferring, dispensing, screen printing or spraying, for example, the adhesive can be applied by the glue applying needle 15 along a predetermined line of the glue applying needle in the glue applying region 17 of the gas diffusion layer;
(4) As shown in fig. 6, two gas diffusion layers are respectively bonded to both sides of a rolled perfluorosulfonic acid resin film 2 with a protective film frame 1 and a catalytic layer by an adhesive to form a membrane electrode assembly, and the gas diffusion layers are the same in size and aligned in position with the catalyst layers on the sides where the gas diffusion layers are located.
The following performance tests were performed in comparison with the membrane electrode assembly described herein, using a conventional membrane electrode assembly as a comparative example:
(1) Testing the electrical property of the membrane electrode assembly, namely testing the polarization curve and the properties of HFR and E-IR free of the membrane electrode assembly by using a clamp battery clamp commonly used in the industry, wherein the used battery clamp is shown in figure 2 and comprises a membrane electrode assembly 7, a single cell cathode and anode end plate 8, a single cell cathode and anode current collecting plate 9 and a cathode and anode graphite flow field plate 10; the test results are shown in fig. 7 and 8; fig. 7 shows that the basic performance of the membrane electrode is not affected by the structure of the present application. Fig. 8 shows that the structure of the present application has no effect on the high-frequency impedance of the membrane electrode.
(2) And (3) accelerated life verification, namely performing a mechanochemical accelerated durability test on the membrane electrode assembly, and periodically performing a hydrogen permeation current test, wherein the data of the hydrogen permeation current test are shown in figure 9, and the result shows that the membrane electrode assembly can protect the perfluorinated sulfonic acid resin membrane, and compared with a comparative example, the service life and the reliability of the membrane cannot be reduced.
Compared with the existing products, the membrane electrode assembly and the processing method thereof are easier to realize mechanical operation and are suitable for batch production, and meanwhile, the new structure does not influence the performance and durability of the products as shown in figures 7-9.
The membrane electrode assembly structure can ensure the mechanical strength and the service life, simultaneously realize the batch automatic production of the membrane electrode assembly, improve the production efficiency and consistency of the membrane electrode and provide powerful support for industrialization.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. A hydrogen fuel cell membrane electrode assembly suitable for batch production comprises a gas diffusion layer, a catalyst layer and a perfluorinated sulfonic acid resin membrane, and is characterized by also comprising a protective membrane frame;
each side of the perfluorinated sulfonic acid resin film is sequentially and uniformly coated with a catalyst layer, a protective film frame and a gas diffusion layer; the inner edge of the protective film frame is 1-2mm closer to the center of the perfluorosulfonic acid resin film than the outer edge of the gas diffusion layer;
the protective film frame is bonded to the perfluorinated sulfonic acid resin film through a bonding agent;
the gas diffusion layer is adhered to the protective film frame through an adhesive, the coating width of the adhesive is less than 1mm, and the distance between the coating width and the outer edge of the gas diffusion layer is 1-2mm; the thickness of the perfluorinated sulfonic acid resin film is 8-25 mu m, and the thickness of the gas diffusion layer is 150-300 mu m; the thickness of the protective film frame is 25 to 80 mu m;
the production process of the membrane electrode assembly specifically comprises the following steps:
(1) Coating catalyst slurry, namely uniformly coating the prepared catalyst slurry on two sides of a coiled perfluorosulfonic acid resin film by using slit coating equipment to form a catalytic layer, wherein the catalytic layer is continuously or discontinuously coated;
(2) Attaching the protective film frame to the perfluorinated sulfonic acid resin film coated with the catalytic layer, wherein one side of the protective film frame is coated with a binder, the protective film frame is attached to two sides of the coiled perfluorinated sulfonic acid resin film coated with the catalytic layer, and the inner edge of the protective film frame is 1-2mm closer to the center of the perfluorinated sulfonic acid resin film than the outer edge of the catalytic layer;
(3) Coating a binder around the outer edge of the gas diffusion layer, wherein the coating area of the binder is 1-2mm away from the outer edge of the gas diffusion layer; the adhesive is coated by transfer printing, dispensing, screen printing or spraying;
(4) Two gas diffusion layers are respectively bonded to two sides of a coiled perfluorinated sulfonic acid resin film with a protective film frame and a catalytic layer through a bonding agent to form a membrane electrode assembly.
2. The hydrogen fuel cell membrane electrode assembly suitable for mass production according to claim 1, wherein the protective film frame is made of a polytetrafluoroethylene film, a polyimide film, a polyethylene terephthalate film, a polyethylene naphthalate film, or a polyetheretherketone film.
3. The hydrogen fuel cell membrane electrode assembly according to claim 1, wherein the gas diffusion layer is the same size and is aligned with the catalytic layer on the side where the gas diffusion layer is located.
4. The hydrogen fuel cell membrane electrode assembly suitable for mass production according to claim 1, wherein the catalytic layers on both sides of the perfluorosulfonic acid resin membrane are uniform in size and aligned in position, and the catalytic layers are continuously or intermittently applied to the perfluorosulfonic acid resin membrane.
5. The hydrogen fuel cell membrane electrode assembly suitable for mass production according to claim 1, wherein the adhesive is a polypropylene-based, epoxy-based, EVA-based, silica-gel-based, or polyurethane-based adhesive.
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| CN114420984B (en) * | 2021-12-22 | 2024-09-03 | 新源动力股份有限公司 | Manufacturing method of fuel cell membrane electrode assembly |
| CN114824352A (en) * | 2022-05-05 | 2022-07-29 | 上海安池科技有限公司 | Method for manufacturing fuel cell membrane electrode with protection frame and membrane electrode |
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