CN115188985A - Fuel cell integrated unit and fuel cell integrated unit manufacturing method - Google Patents
Fuel cell integrated unit and fuel cell integrated unit manufacturing method Download PDFInfo
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- CN115188985A CN115188985A CN202210915302.6A CN202210915302A CN115188985A CN 115188985 A CN115188985 A CN 115188985A CN 202210915302 A CN202210915302 A CN 202210915302A CN 115188985 A CN115188985 A CN 115188985A
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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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
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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
- H01M4/90—Selection of catalytic material
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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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
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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
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a fuel cell integrated unit and a manufacturing method thereof, wherein the fuel cell integrated unit comprises: the membrane electrode assembly comprises a membrane layer and a gas diffusion layer, wherein the gas diffusion layer is positioned on one surface of the membrane layer; the frame assembly comprises an inner frame and an outer frame, the inner side end of the inner frame exceeds the inner side end of the outer frame, and the inner side end is one end, facing the membrane electrode assembly, of the frame assembly; the edge area of the inner frame beyond the outer frame is an inner frame connecting part connected with the membrane electrode assembly, the first surface of the inner frame connecting part is contacted with one surface of the membrane layer, and the second surface of the inner frame connecting part is contacted with one surface of the gas diffusion layer facing the membrane layer; a gap is formed between the inner side end of the outer frame and the membrane electrode assembly. The invention provides a fuel cell integrated unit, which improves the production efficiency and the durability.
Description
Technical Field
The invention relates to the technical field of fuel cell processing and manufacturing equipment, in particular to a fuel cell integrated unit and a manufacturing method of the fuel cell integrated unit.
Background
A fuel cell is a device that directly converts chemical energy of fuel into electrical energy, and generally consists of a stack of dozens to hundreds of repeated Unit cells (Unit cells). One unit cell is composed of a pair of bipolar plates, a Membrane Electrode Assembly (MEA) sandwiched between the bipolar plates, and a resin frame located at the periphery of the Membrane Electrode Assembly.
The unit cell is divided into a central power generation region and a peripheral sealing region. In the central power generation area, fuel gas and oxidizing gas are respectively introduced into two sides of the membrane electrode to generate chemical reaction to generate electricity; sealing is performed in the peripheral sealing region so that leakage of fuel gas, oxidizing gas, and coolant from the respective cavities or blowby between the respective cavities does not occur.
At present, when the bipolar plate and the membrane electrode are integrally prepared, a molding sealing process or an adhesive sealing process is generally used, and glue dispensing and curing are carried out on a joint area of a frame and the membrane electrode, so that the manufacturing equipment and the process are complex, the time consumption of molding or glue dispensing and curing is long, and the production efficiency is low. In the current single cell integrated structure, a joint area of a membrane electrode and a peripheral resin frame exists, and the membrane electrode in the joint area is easy to generate stretching or stress concentration action in the process of cell assembly or long-term high-low temperature operation, so that the local gas transmittance of the membrane electrode is increased, and the durability is reduced.
Therefore, how to improve the production efficiency and durability is a problem to be solved urgently by those skilled in the art.
Disclosure of Invention
Accordingly, the present invention provides a fuel cell integrated unit to improve production efficiency and durability. The invention also provides a fuel cell integrated unit manufacturing method for manufacturing the fuel cell integrated unit.
In order to achieve the purpose, the invention provides the following technical scheme:
a fuel cell integrated unit comprising:
the membrane electrode assembly comprises a membrane layer and a gas diffusion layer, wherein the gas diffusion layer is positioned on one surface of the membrane layer;
the frame assembly comprises an inner frame and an outer frame, the inner side end of the inner frame exceeds the inner side end of the outer frame, and the inner side end is one end of the frame assembly facing the membrane electrode assembly; the edge area of the inner frame beyond the outer frame is an inner frame connecting part connected with the membrane electrode assembly, the first surface of the inner frame connecting part is contacted with one surface of the membrane layer, and the second surface of the inner frame connecting part is contacted with one surface of the gas diffusion layer facing the membrane layer; a gap is formed between the inner side end of the outer frame and the membrane electrode assembly.
Optionally, in the above fuel cell integrated unit, the membrane layer includes two membrane layer portions and two catalytic layers, where the two catalytic layers are an anode catalytic layer and a cathode catalytic layer, and the anode catalytic layer and the cathode catalytic layer are respectively disposed on two side surfaces of the membrane layer;
the number of the gas diffusion layers is two, and the two gas diffusion layers are respectively an anode gas diffusion layer and a cathode gas diffusion layer;
the anode gas diffusion layer is positioned on one surface, back to the membrane layer part, of the anode catalyst layer, and the cathode gas diffusion layer is positioned on one surface, back to the membrane layer part, of the cathode catalyst layer.
Optionally, in the above fuel cell integrated unit, the number of the frame assemblies is two, and the frame assemblies are respectively a first frame assembly and a second frame assembly;
the first frame assembly comprises a first inner frame and a first outer frame, and the second frame assembly comprises a second inner frame and a second outer frame;
wherein, the first and the second end of the pipe are connected with each other,
the inner side end of the first inner frame exceeds the inner side end of the first outer frame, and the inner side end is one end, facing the membrane electrode assembly, of the frame assembly; the edge area of the first inner frame beyond the first outer frame is a first inner frame connecting part connected with the membrane electrode assembly, and a gap is formed between the inner side end of the first outer frame and the membrane electrode assembly;
and/or the inner side end of the second inner frame exceeds the inner side end of the second outer frame, and the inner side end is one end of the frame assembly facing the membrane electrode assembly; the edge area of the second inner frame beyond the second outer frame is a second inner frame connecting part connected with the membrane electrode assembly, and a gap is formed between the inner side end of the second outer frame and the membrane electrode assembly.
Optionally, in the above fuel cell integrated unit, the frame assembly includes a first inner frame, a second inner frame, and a second outer frame, which are arranged in sequence;
the inner ends of the first inner frame and the second inner frame exceed the inner end of the second outer frame, and the inner end is one end of the frame assembly facing the membrane electrode assembly;
the edge area of the first inner frame beyond the second outer frame is a first inner frame connecting part connected with the membrane electrode assembly, and a gap is formed between the inner side end of the second outer frame and the membrane electrode assembly;
the edge area of the second inner frame beyond the second outer frame is a second inner frame connecting part connected with the membrane electrode assembly, and a gap is formed between the inner side end of the second outer frame and the membrane electrode assembly.
Optionally, in the above fuel cell integrated unit, the frame assembly includes a first outer frame, a second inner frame, and a second outer frame, which are arranged in sequence;
the inner side end of the second inner frame exceeds the inner side ends of the first outer frame and the second outer frame, and the inner side end is one end of the frame assembly facing the membrane electrode assembly; the edge area of the second inner frame beyond the first outer frame and the second outer frame is a second inner frame connecting part connected with the membrane electrode assembly;
and a gap is reserved between the inner ends of the first outer frame and the second outer frame and the membrane electrode assembly.
Optionally, in the above fuel cell integrated unit, the frame assembly further includes an adhesive film layer disposed on one surface of the inner frame and the outer frame facing the film layer;
the inner frame and the outer frame are resin frames.
Optionally, in the above fuel cell integrated unit, the membrane electrode assembly is disposed between an anode plate of the fuel cell integrated unit and a cathode plate of the fuel cell integrated unit;
one side of the frame component, which faces the anode plate, is connected with the anode plate through an anode plate adhesive layer, and one side of the frame component, which faces the cathode plate, is connected with the cathode plate through a cathode plate adhesive layer.
Optionally, in the above fuel cell integrated unit, the anode plate and the cathode plate are metal plates, graphite-resin composite material plates, or conductive plastic plates;
and/or the surfaces of the anode plate and the cathode plate are provided with conductive coatings;
and/or the surfaces of the anode plate and the cathode plate are provided with primer layers for increasing the bonding strength of the anode plate and the cathode plate with adhesive layers.
Optionally, in the above fuel cell integrated unit, the fuel cell integrated unit is a proton exchange membrane fuel cell, and the membrane layer is a proton exchange membrane;
or, the fuel cell integrated unit is a solid electrolyte membrane fuel cell, and the membrane layer is a solid electrolyte membrane.
The present invention also provides a fuel cell integrated unit manufacturing method for preparing the fuel cell integrated unit as described in any one of the above, including:
preparing a component, namely preparing a membrane layer, a gas diffusion layer, a frame assembly, an anode plate and a cathode plate;
the anode plate adhesive layer is attached to the anode plate, and the cathode plate adhesive layer is attached to the cathode plate;
and (3) hot-pressing, namely stacking the film layer, the gas diffusion layer, the inner frame of the frame assembly, the outer frame of the frame assembly, the anode plate and the cathode plate in sequence and performing hot-pressing operation.
Optionally, in the method for manufacturing an integrated unit of a fuel cell, before the step of hot pressing, the method further includes the steps of: the frame component is used for carrying out corona treatment or plasma treatment on the surface attached to the anode plate adhesive layer and/or the cathode plate adhesive layer.
Optionally, in the method for manufacturing a fuel cell integrated unit, the step of attaching the adhesive layer includes: and pressurizing or heating the anode plate adhesive layer and the anode plate, and pressurizing or heating the cathode plate adhesive layer and the cathode plate.
Optionally, in the above method for manufacturing a fuel cell integrated unit, in the step of hot pressing, the membrane layer, the gas diffusion layer, the inner frame of the frame assembly, the outer frame of the frame assembly, the anode plate and the cathode plate are formed by one-step hot pressing;
or, in the step of hot-pressing, the film layer, the gas diffusion layer, the inner frame of the frame assembly, the outer frame of the frame assembly, the anode plate and the cathode plate are formed by hot-pressing for multiple times, and the hot-pressing components are different in any two hot-pressing operation processes.
According to the fuel cell integrated unit provided by the invention, the first surface of the inner frame connecting part is contacted with one surface of the membrane layer, and the second surface of the inner frame connecting part is contacted with one surface of the gas diffusion layer facing the membrane layer, so that the inner frame connecting part is clamped between the catalyst layer and the gas diffusion layer in the processing process of the fuel cell integrated unit, the connection between the inner frame and the membrane electrode assembly can be realized through hot press molding, the glue dispensing and curing are not required to be carried out in the joint area of the membrane electrode assembly and the frame assembly, the manufacturing process is simplified, and the production efficiency is improved. And a gap is formed between the inner side end of the outer frame and the membrane electrode assembly, so that a multi-layer frame staggered bonding structure is realized, the inner frame is connected with the membrane layer which effectively protects a gap area (the area between the inner side end of the outer frame and the membrane electrode assembly), the membrane layer in the gap area is prevented from being damaged due to local stretching or stress concentration, the membrane electrode at the gap between the frame assembly (the outer frame) and the gas diffusion layer is protected from being easily damaged due to stretching, and the durability of the membrane electrode assembly is improved.
Since the above-described fuel cell integrated unit manufacturing method is used to prepare any of the above-described fuel cell integrated units, the above-described fuel cell integrated unit manufacturing method has the same technical effects as the above-described fuel cell integrated unit, and will not be described in detail herein.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is an exploded schematic view of a fuel cell integrated unit according to an embodiment of the present invention;
fig. 2 is a schematic view of a first structure of a fuel cell integrated unit according to an embodiment of the present invention;
fig. 3 is a schematic diagram of a second structure of a fuel cell integrated unit according to an embodiment of the present invention;
fig. 4 is a schematic view of a third structure of a fuel cell integrated unit provided by an embodiment of the invention;
fig. 5 is a fourth structural schematic diagram of a fuel cell integrated unit provided in an embodiment of the present invention;
fig. 6 is a schematic diagram of a fifth structure of a fuel cell integrated unit according to an embodiment of the present invention;
fig. 7 is a schematic flow chart of a method for manufacturing a fuel cell integrated unit according to an embodiment of the present invention;
FIG. 8 is a schematic view of the assembly process of the membrane electrode assembly in the integrated unit of the fuel cell according to the embodiment of the present invention;
fig. 9 is a front view of an inner frame and an outer frame of a fuel cell integrated unit according to an embodiment of the present invention;
fig. 10 is a cross-sectional view of an inner frame and an outer frame of a fuel cell integrated unit according to an embodiment of the present invention;
fig. 11 is a flow chart illustrating a process of bonding an adhesive layer and a plate in a fuel cell integrated unit according to an embodiment of the present invention;
fig. 12 is a schematic flow chart of a one-step hot press forming of a fuel cell integrated unit manufacturing method according to an embodiment of the present invention;
fig. 13 is a schematic view showing a first flow of secondary hot press molding of the method for manufacturing a fuel cell integrated unit according to the embodiment of the present invention;
fig. 14 is a schematic flow chart of the secondary hot press molding of the method for manufacturing the fuel cell integrated unit according to the embodiment of the present invention.
Detailed Description
The invention discloses a fuel cell integrated unit for improving production efficiency and durability. The invention also provides a fuel cell integrated unit manufacturing method for manufacturing the fuel cell integrated unit.
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 of the embodiments. 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.
As shown in fig. 1 to 14, an embodiment of the present invention provides a fuel cell integrated unit, including a membrane electrode assembly 10 and a frame assembly 30, where the membrane electrode assembly 10 includes a membrane layer 14 and a gas diffusion layer 13, and the gas diffusion layer 13 is located on one side of the membrane layer 14; the frame assembly 30 comprises an inner frame and an outer frame, the inner side end of the inner frame exceeds the inner side end of the outer frame, and the inner side end is one end of the frame assembly 30 facing the membrane electrode assembly 10; the edge region of the inner frame beyond the outer frame is connected to the inner frame connected to the membrane electrode assembly 10. Wherein, a first surface of the inner frame connecting part is in contact with one surface of the membrane layer 14, and a second surface of the inner frame connecting part is in contact with one surface of the gas diffusion layer 13 facing the membrane layer 14; a gap is provided between the inner end of the outer frame and the membrane electrode assembly 10.
In the fuel cell integrated unit provided by the embodiment of the invention, because the first surface of the inner frame connecting part is in contact with one surface of the membrane layer 14, and the second surface of the inner frame connecting part is in contact with one surface of the gas diffusion layer 13 facing the membrane layer 14, in the processing process of the fuel cell integrated unit, the inner frame connecting part is clamped between the catalyst layer 12 and the gas diffusion layer 13, the connection between the inner frame and the membrane electrode assembly 10 can be realized through hot press molding, the glue dispensing and curing are not required to be carried out in the joint area of the membrane electrode assembly 10 and the frame assembly 30, the manufacturing process is simplified, and the production efficiency is improved. Moreover, a gap is formed between the inner end of the outer frame and the membrane electrode assembly 10, so that a multi-layer frame staggered bonding structure is realized, the inner frame is connected with the membrane layer 14 which effectively protects a gap area (an area between the inner end of the outer frame and the membrane electrode assembly 10), the membrane layer 14 in the gap area is prevented from being damaged due to local stretching or stress concentration, the membrane electrode at the gap between the frame assembly 30 (the outer frame) and the gas diffusion layer 13 is protected from being easily stretched and damaged, and the durability of the membrane electrode assembly 10 is improved.
Specifically, the membrane layer 14 includes a membrane layer portion 11 and two catalytic layers 12, the catalytic layers 12 are two and are respectively an anode catalytic layer 12A and a cathode catalytic layer 12C, and the anode catalytic layer 12A and the cathode catalytic layer 12C are respectively disposed on two side surfaces of the membrane layer portion 11; the number of the gas diffusion layers 13 is two and is an anode gas diffusion layer 13A and a cathode gas diffusion layer 13C, respectively; the anode gas diffusion layer 13A is located on the side of the anode catalyst layer 12A facing away from the membrane portion 11, and the cathode gas diffusion layer 13C is located on the side of the cathode catalyst layer 12C facing away from the membrane portion 11.
As shown in fig. 1 and 2, in the first embodiment, the number of the frame components 30 is two, and the frame components are a first frame component and a second frame component respectively; the first frame assembly includes a first inner frame 31 and a first outer frame 33, and the second frame assembly includes a second inner frame 35 and a second outer frame 37.
The inner end of the first inner frame 31 exceeds the inner end of the first outer frame 33, and the inner end is the end of the frame assembly 30 facing the membrane electrode assembly 10; the edge area of the first inner frame 31 beyond the first outer frame 33 is a first inner frame 31 connecting part connected with the membrane electrode assembly 10, and a gap is formed between the inner end of the first outer frame 33 and the membrane electrode assembly 10. The inner end of the second inner frame 35 exceeds the inner end of the second outer frame 37, and the inner end is the end of the frame assembly 30 facing the membrane electrode assembly 10; the edge region of the second inner frame 35 beyond the second outer frame 37 is a second inner frame connecting portion connected to the membrane electrode assembly 10, and a gap is provided between the inner end of the second outer frame 37 and the membrane electrode assembly 10.
The unit battery 100 is mainly composed of four parts: a membrane electrode assembly 10, a pair of bipolar plates 20 sandwiching the membrane electrode assembly 10, a frame assembly 30 between the bipolar plates 20 and joined to the outer periphery of the membrane electrode assembly 10, and an adhesive layer 40 for bonding the bipolar plates 20 and the frame assembly 30.
The mea 10 includes a membrane layer 14 (including a membrane layer portion 11 and a catalyst layer 12) and a gas diffusion layer 13. The catalyst layer 12 includes an anode catalyst layer 12A and a cathode catalyst layer 12C, and the gas diffusion layer 13 includes an anode gas diffusion layer 13A and a cathode gas diffusion layer 13C.
The bipolar plate 20 includes an anode plate 21 and a cathode plate 22, a fuel gas flow path 24 and an anode plate coolant flow path 28 are distributed on the anode plate 21, and an oxidizing gas flow path 23 and a cathode plate coolant flow path 29 are distributed on the cathode plate 22. The frame assembly 30 includes an inner frame 30A and an outer frame 30B, and is specifically subdivided into a first inner frame resin layer (a first inner frame 31), a first inner frame adhesive film 32, a first outer frame resin layer (a first outer frame 33), a first outer frame adhesive film 34, a second inner frame resin layer (a second inner frame 35), a second inner frame adhesive film 36, a second outer frame resin layer (a second outer frame 37) and a second outer frame adhesive film 38, wherein the frame assembly 30 is provided with a fuel gas inlet flow path 15A, a fuel gas outlet flow path 15B, an oxidizing gas inlet flow path 16A and an oxidizing gas outlet flow path 16B. The adhesive layer 40 includes an anode plate adhesive layer 41 and a cathode plate adhesive layer 42. The unit cell 100 has three inlets and outlets, i.e., a fuel gas inlet 25A, a fuel gas outlet 25B, an oxidizing gas inlet 27A, an oxidizing gas outlet 27B, a coolant inlet 26A, and a coolant outlet 26B, respectively.
The Membrane electrode assembly 10 is abbreviated as MEA, the gas diffusion layer is abbreviated as GDL, and the Membrane layer portion 11 and the Catalyst layer 12 together form a Membrane layer 14 (Catalyst Coated Membrane, abbreviated as CCM).
Specifically, in the process of manufacturing the fuel cell integrated unit provided in the first embodiment, a component is prepared, wherein the component to be prepared includes: the cathode plate comprises an anode plate 21, a cathode plate 22, a first inner frame 31, a first outer frame 33, a second inner frame 35, a second outer frame 37, a membrane part 11 (proton exchange membrane) 11, an anode catalyst layer 12A, a cathode catalyst layer 12C, an anode gas diffusion layer 13A, a cathode gas diffusion layer 13C, an anode plate adhesive layer 41 and a cathode plate adhesive layer 42.
After that, an adhesive layer is attached, and in order to improve the connection strength of the adhesive layer, it is preferable to attach the anode plate adhesive layer 41 to the anode plate 21 and the cathode plate adhesive layer 42 to the cathode plate 22. The polar plate has better strength, smoothness and thermal stability, can be matched with mounting equipment such as a clamp, a tool and the like, and is pressed under higher pressure or higher heating temperature, so that the bonding position of the adhesive layer and the polar plate is uniformly pressed, bubbles between the adhesive layer and the polar plate can be better discharged, and the bonding strength of the adhesive layer and the polar plate is improved; in addition, the smoothness of the attachment of the pole plate and the adhesive layer is improved, the pole plate is not easy to warp, the generation of internal stress is avoided, and the connection reliability is improved.
Finally, the components are sequentially stacked on the hot press assembly according to a certain stacking sequence and position, wherein the stacking sequence sequentially comprises the anode plate 21, the anode plate adhesive layer 41 attached to the anode plate 21, the first outer frame 33, the anode gas diffusion layer 13A separated from the first outer frame 33, the first inner frame 31 (contacting with a partial region of the anode gas diffusion layer 13A and the first outer frame 33), the anode catalyst layer 12A (contacting with a partial region of the first inner frame 31 and the anode gas diffusion layer 13A), the membrane layer part 11 (contacting with a partial region of the first inner frame 31 and the anode catalyst layer 12A), the cathode catalyst layer 12C (contacting with the membrane layer part 11), the second inner frame 35 (contacting with a partial region of the cathode catalyst layer 12C, a partial region of the membrane layer part 11 and a partial region of the first inner frame 31), the second outer frame 37, the cathode gas diffusion layer 13C separated from the second outer frame 37, and the cathode adhesive layer 42 and 22 attached to the cathode plate 22. And then, carrying out hot-pressing processing at a certain temperature and pressure by using a hot-pressing tool and a hot press to complete the manufacture of the single battery. Preferably, the hot pressing temperature is generally not more than 140 ℃ and the pressure is generally not more than 4MPa.
The anode catalyst layer 12A and the cathode catalyst layer 12C may be separately manufactured or may be formed by coating on the film layer portion 11. In this embodiment, the anode catalyst layer 12A and the cathode catalyst layer 12C are preferably formed by coating on the membrane layer portion 11. That is, a catalyst slurry is prepared, and then the catalyst slurry is applied to both side surfaces of the membrane layer portion 11 to form the anode catalyst layer 12A and the cathode catalyst layer 12C, respectively, thereby completing the operation of preparing the membrane layer 14.
The edges of the anode catalyst layer 12A and the cathode catalyst layer 12C may be aligned or not aligned (misaligned), which depends on the actual requirement, and are not described in detail herein and are within the protection scope.
The gas diffusion layer 13 is made of a material having air permeability and an electron conduction function, and may be specifically made of carbon paper, a porous graphite material, a foamed metal, a metal mesh, or the like.
An anode gas diffusion layer 13A and a cathode gas diffusion layer 13C are respectively attached to both sides of the membrane layer 14, the anode gas diffusion layer 13A is in contact with the anode catalyst layer 12A, and the cathode gas diffusion layer 13C is in contact with the cathode catalyst layer 12C, together constituting the membrane electrode assembly 10. Similarly, the edges of the anode gas diffusion layer 13A and the cathode gas diffusion layer 13C may be aligned or not aligned (misaligned), depending on the actual requirements, and are not described in detail herein and are within the scope of protection.
Specifically, the frame assembly 30 includes two inner frames and two outer frames, i.e., a first inner frame 31, a first outer frame 33, a second inner frame 35, and a second outer frame 37. Preferably, each layer of the frame has an adhesive film layer, that is, the frame and the adhesive film layer corresponding to the frame form an assembly. That is, one side of the first inner frame 31 facing the film 14 has a first inner frame glue film 32, one side of the first outer frame 33 facing the film 14 has a first outer frame glue film 34, one side of the second inner frame 35 facing the film 14 has a second inner frame glue film 36, and one side of the second outer frame 37 facing the film 14 has a second outer frame glue film 38.
It can be understood that the adhesive film layer can be coated on the frame, so that the frame and the adhesive film layer form a frame material with a composite structure, and the inner frame and the outer frame are obtained after the frame material is blanked.
Preferably, the first inner frame 31, the first outer frame 33, the second inner frame 35 and the second outer frame 37 are preferably resin frame layers, the material of which may be an insulating resin material such as PEN, PET, polypropylene (PP), epoxy resin, phenolic resin, etc., and the material of the adhesive film layer may be an acrylate, epoxy resin, phenolic resin, modified polyolefin adhesive material, etc.
As shown in fig. 9, in particular, the edge region (inner frame connecting portion) of the inner frame 30A beyond the outer frame 30B may be formed in a frame blanking operation. That is, the protruding width (the length of the inner frame 30A beyond the edge area of the outer frame 30B) is T1 or T2, the edge of the gas diffusion layer 13 is located between the inner edge 30A of the inner frame and the inner edge of the outer frame 30B, and the protruding inner frame 30A protects the film layer 14 at the gap between the frame and the gas diffusion layer 13 from being easily broken.
In fig. 10, the inner frame 30A includes a first inner frame 31 and a first inner frame glue film 32 facing one side of the film 14, and the outer frame 30B includes a first outer frame 33 and a first outer frame glue film 34 facing one side of the film 11.
The surface of the inner frame adhesive film, which is attached to the proton exchange membrane, is called a first surface of the inner frame, and the surface of the opposite inner frame resin layer is called a second surface of the inner frame; the surface of the outer frame adhesive film, which is attached to the inner frame, is called the first surface of the outer frame, and the surface of the opposite resin layer of the outer frame is called the second surface of the outer frame.
The frame member 30 is subjected to corona treatment or plasma treatment on the surface to be bonded to the anode plate adhesive layer 41 and/or the cathode plate adhesive layer 42. The corona treatment or the plasma treatment is to pretreat the surface of the frame material by using a corona treatment machine or a plasma treatment machine so as to change the molecular structure and the roughness of the surface of the material and improve the adhesive force of the surface of the material. With the above arrangement, the surface wetting tension after the treatment needs to be 30N/mm or more.
As shown in fig. 11, the upper surface and the lower surface of the adhesive layer are covered with release films, which are respectively designated as a first release film 44 and a second release film 46, the release films can protect the adhesive layer, and release agents, which are respectively designated as a first release agent 43 and a second release agent 45, exist between the release films and the adhesive layer. The peeling strength of the first release agent is lower than that of the second release agent 45, when the adhesive layer is attached to the polar plate, the first release film 44 and the first release agent 43 are peeled off and removed firstly, and the first surface of the adhesive layer is attached to the polar plate.
In the manufacturing process, in order to ensure the reliability of the bonding, the adhesive layer can be pressed on the polar plate through modes of clamp pressing, rolling or hot pressing and the like under higher pressure or higher heating temperature, so that bubbles on a bonding interface in the bonding process can be discharged more conveniently, and the bonding strength and the flatness can be ensured. And then, after the first surface is attached to the polar plate, removing the second release film 46 and the second release agent 45 to obtain the polar plate attached with the adhesive layer. In the laminating process, the second release film 46 can prevent the adhesive layer from being bonded with the pressing fixture or the tool. The temperature, pressure and duration of the first surface of the adhesive layer and the pole plate are related to the materials on the two sides.
Preferably, in the operation process of adhering the adhesive layer, the temperature is between room temperature and 50 ℃, the pressure is 4MPa, and too high temperature may cause the cooling process of the pressurization and/or heating process to be too long, so that the viscosity of the second release agent 45 and the adhesive layer 40 changes, and the adhesive layer 40 has a relatively obvious thickness change.
The thickness of the adhesive layer 40 is generally 10-100 um, and the material of the adhesive layer 40 may be the same as or different from the material of the adhesive film layer. The adhesive layer 40 may be a single layer structure of a single material or a multi-layer structure of a plurality of materials.
As shown in fig. 12, stacking of components of the unit cells is performed in the following relative order and placement position.
The stacking sequence is as follows: placing the anode plate 21 and the anode plate adhesive layer 41 attached to the anode plate 21 on a hot-pressing tool to form a first layer stacking structure L1; the first outer frame 33 (having the first outer frame adhesive film layer 34) and the anode gas diffusion layer 13A are separated from each other to form a second stacked structure L2; the first inner frame 31 (having the first inner frame glue film layer 32) forms a third layer stacking structure L3; a membrane layer 14 composed of the anode catalyst layer 12A, the membrane layer 11 and the cathode catalyst layer 12C forms a fourth stacked structure L4; the second inner frame 35 (having the second inner frame glue film layer 36) forms a fifth layer stacking structure L5; the second outer frame 37 (having the second outer frame glue film layer 38) and the cathode gas diffusion layer 13C are separated from each other to form a sixth stacked structure L6; the cathode plate adhesive layer 42 attached to the cathode plate 22 and the cathode plate 22 form a seventh stacked structure L7. And then, carrying out primary hot-press forming on the hot press by using a hot-press tool to manufacture the single battery. Wherein, the seven-layer stacking structure can be stacked from L1 to L7 or from L7 to L1.
Specifically, the hot pressing temperature of the hot press is generally not more than 140 ℃, and the pressure is generally not more than 4MPa.
As shown in FIG. 3, in the second embodiment, the number of the frame members 30 is two and is respectively the first frame member and the second frame member; the first frame assembly includes a first inner frame 31 and a first outer frame 33, and the second frame assembly includes a second inner frame 35 and a second outer frame 37.
Wherein, the inner end of the first inner frame 31 is flush with the inner end of the first outer frame 33, and the inner end is the end of the frame assembly 30 facing the membrane electrode assembly 10; the inner end of the second inner frame 35 exceeds the inner end of the second outer frame 37, and the inner end is the end of the frame assembly 30 facing the membrane electrode assembly 10; the edge region of the second inner frame 35 beyond the second outer frame 37 is a second inner frame connecting portion connected to the membrane electrode assembly 10, and a gap is provided between the inner end of the second outer frame 37 and the membrane electrode assembly 10.
That is, in the processing process, the second inner frame connecting portion of the second inner frame 35 is only required to be attached between the cathode catalyst layer 12C and the cathode gas diffusion layer 13C, and the connection between the membrane electrode assembly 10 and the frame assembly 30 can be completed by hot pressing.
In the third embodiment, as shown in fig. 4, the frame assembly 30 includes a first inner frame 31, a second inner frame 35 and a second outer frame 37 arranged in sequence. The inner ends of the first inner frame 31 and the second inner frame 35 exceed the inner end of the second outer frame 37, and the inner ends are the ends of the frame assemblies 30 facing the membrane electrode assembly 10; the edge area of the first inner frame 31 beyond the second outer frame 37 is a first inner frame 31 connecting part connected with the membrane electrode assembly 10, and a gap is formed between the inner end of the second outer frame 37 and the membrane electrode assembly 10; the edge area of the second inner frame 35 beyond the second outer frame 37 is a second inner frame 35 connecting part connected with the membrane electrode assembly 10, and a gap is formed between the inner end of the second outer frame 37 and the membrane electrode assembly 10.
In the present embodiment, the first inner frame 31 is located between the film layer 14 and the anode gas diffusion layer 13A. Of course, it is also possible to have the first inner frame 31 between the film layer 14 and the cathode gas diffusion layer 13C. That is, the bezel assembly shown in fig. 4 is formed by symmetrically inverting the vertical direction.
Of course, during the processing, the hot pressing of the membrane electrode assembly 10 may be completed first, and then the membrane electrode assembly 10 is connected to the frame assembly 30, and then the stack and the second hot pressing are performed on the polar plate.
As shown in fig. 5, in the fourth embodiment, the frame assembly 30 includes a first outer frame 33, a second inner frame 35 and a second outer frame 37 arranged in sequence; the inner end of the second inner frame 35 exceeds the inner ends of the first outer frame 33 and the second outer frame 37, and the inner end is the end of the frame assembly 30 facing the membrane electrode assembly 10; the edge area of the second inner frame 35 beyond the first outer frame 33 and the second outer frame 37 is a second inner frame 35 connecting part connected with the membrane electrode assembly 10; a gap is formed between the inner ends of the first and second outer frames 33 and 37 and the membrane electrode assembly 10.
In the present embodiment, the second inner frame 35 is located between the film layer 14 and the cathode gas diffusion layer 13C. Of course, it is also possible to have the second inner frame 35 between the film layer 14 and the anode gas diffusion layer 13A. That is, the bezel assembly shown in fig. 5 is formed by symmetrically inverting the vertical direction.
Through the arrangement, the frame assembly is asymmetrically arranged. The second inner frame 35 overlaps the gas diffusion layer 13.
It is understood that, in the third and fourth embodiments, since the frame assembly 30 is asymmetrically arranged, the thicknesses (the vertical dimensions in the drawings) of the components in the frame assembly 30 can be adjusted in order to fit the membrane electrode assembly 10.
In a fifth embodiment, as shown in fig. 6, the plates are graphite plates.
In the first to fourth embodiments, the electrode plate may be a metal electrode plate, a graphite electrode plate, or an electrode plate made of other materials, such as a graphite-resin composite electrode plate or a conductive plastic electrode plate.
Preferably, the surfaces of the anode plate 21 and the cathode plate 22 have a conductive coating to ensure the conductive effect.
The surfaces of the anode plate 21 and the cathode plate 22 are provided with primer layers for increasing the bonding strength with the adhesive layers.
In this embodiment, the fuel cell integrated unit is a proton exchange membrane fuel cell, and the membrane layer 14 is a proton exchange membrane. Of course, it is also possible to make the fuel cell integrated unit a solid electrolyte membrane fuel cell, and the membrane layer 14 a solid electrolyte membrane.
As shown in fig. 7, an embodiment of the present invention further provides a fuel cell integrated unit manufacturing method for preparing any one of the fuel cell integrated units described above, including:
s1: preparing a component, namely preparing a membrane layer 14, a gas diffusion layer 13, a frame assembly 30, an anode plate 21 and a cathode plate 22;
s2: attaching the adhesive layer, attaching the anode plate adhesive layer 41 to the anode plate 21, and attaching the cathode plate adhesive layer 42 to the cathode plate 22;
s3: and (4) performing hot-pressing processing, namely stacking the film layer 14, the gas diffusion layer 13, the inner frame of the frame assembly 30, the outer frame of the frame assembly 30, the anode plate 21 and the cathode plate 22 in sequence and performing hot-pressing operation.
Since the above-described fuel cell integrated unit manufacturing method is used to prepare any of the above-described fuel cell integrated units, the above-described fuel cell integrated unit manufacturing method has the same technical effects as the above-described fuel cell integrated unit, and will not be described in detail herein.
Before the step of hot pressing, the method also comprises the following steps: the frame member 30 is subjected to corona treatment or plasma treatment on the surface to be bonded to the anode plate adhesive layer 41 or the cathode plate adhesive layer 42. The corona treatment or the plasma treatment refers to that the surface of the frame material is pretreated by a corona treatment machine or a plasma treatment machine, so that the molecular structure and the roughness of the surface of the material are changed, and the adhesive force of the surface of the material is improved. With the above arrangement, the surface wetting tension after the treatment needs to be 30N/mm or more.
The step of attaching the adhesive layer comprises: the anode plate adhesive layer 41 and the anode plate 21 are pressurized or heated, and the cathode plate adhesive layer 42 and the cathode plate 22 are pressurized or heated.
In order to ensure the reliability of the bonding, the adhesive layer can be pressed on the polar plate under a larger pressure or a higher heating temperature by means of clamp pressing, rolling or hot pressing and the like, so that bubbles on a bonding interface in the bonding process can be discharged more favorably, and the bonding strength and the flatness can be ensured. And then, after the first surface is attached to the polar plate, removing the second release film 46 and the second release agent 45 to obtain the polar plate attached with the adhesive layer. In the fitting process, the second release film 46 can prevent the adhesive layer from being bonded with the pressing fixture or the fixture. The temperature, pressure and duration of the first surface of the adhesive layer and the pole plate are related to the materials on the two sides.
Preferably, as shown in fig. 12, in the step of hot-pressing, the film layer 14, the gas diffusion layer 13, the inner frame of the frame assembly 30, the outer frame of the frame assembly 30, the anode plate 21 and the cathode plate 22 are formed by one-step hot pressing;
of course, the membrane layer 14, the gas diffusion layer 13, the inner frame of the frame assembly 30, the outer frame of the frame assembly 30, the anode plate 21 and the cathode plate 22 may be formed by multiple hot pressing processes in other manners, for example, in the step of hot pressing process, and the hot pressing components are different in any two hot pressing processes.
Taking two times of hot press forming as an example, a part of the components of the film layer 14, the gas diffusion layer 13, the inner frame of the frame assembly 30, the outer frame of the frame assembly 30, the anode plate 21 and the cathode plate 22 are formed into a first hot press assembly by one time of hot press forming, and the rest components of the film layer 14, the gas diffusion layer 13, the inner frame of the frame assembly 30, the outer frame of the frame assembly 30, the anode plate 21 and the cathode plate 22 and the first hot press assembly are formed into a second hot press assembly by a second time of hot press forming.
In the embodiment of the two-shot thermoforming, the primary thermoforming component may be the film layer 14 and the frame component 30, as shown in fig. 13. That is, the gas diffusion layer 13, the anode plate 21 and the cathode plate 22 are formed by combining a secondary hot press and a primary hot press.
As shown in fig. 14, in the second embodiment of the second hot press forming, the first hot press assembly may be the membrane 14 and the frame assembly 30, and then the gas diffusion layer 13 and the membrane 14 are attached to each other, and then the assembly of the membrane electrode assembly 10 and the frame assembly 30, the anode plate 21 and the cathode plate 22 are formed by the second hot press assembly.
The primary thermocompression assembly may be the membrane layer 14, the gas diffusion layer 13, the inner frame of the frame assembly 30, and the outer frame of the frame assembly 30. That is, the anode plate 21 and the cathode plate 22 are formed by combining the primary hot pressing assembly and the secondary hot pressing assembly.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (13)
1. A fuel cell integrated unit, comprising:
the membrane electrode assembly (10), the membrane electrode assembly (10) includes the membrane layer (14) and gas diffusion layer (13), the gas diffusion layer (13) locates at one side of the membrane layer (14);
the frame assembly (30) comprises an inner frame and an outer frame, the inner side end of the inner frame exceeds the inner side end of the outer frame, and the inner side end is one end, facing the membrane electrode assembly (10), of the frame assembly (30); the edge area of the inner frame, which exceeds the outer frame, is an inner frame connecting part connected with the membrane electrode assembly (10), a first surface of the inner frame connecting part is in contact with one surface of the membrane layer (14), and a second surface of the inner frame connecting part is in contact with one surface, facing the membrane layer (14), of the gas diffusion layer (13); a gap is formed between the inner side end of the outer frame and the membrane electrode assembly (10).
2. The fuel cell integrated unit according to claim 1, wherein the membrane layer (14) includes a membrane layer portion (11) and two catalytic layers (12), the catalytic layers (12) are two and respectively include an anode catalytic layer (12A) and a cathode catalytic layer (12C), and the anode catalytic layer (12A) and the cathode catalytic layer (12C) are respectively disposed on both sides of the membrane layer (14);
the number of the gas diffusion layers (13) is two, and the gas diffusion layers are respectively an anode gas diffusion layer (13A) and a cathode gas diffusion layer (13C);
the anode gas diffusion layer (13A) is located on one face, back to the membrane layer portion (11), of the anode catalyst layer (12A), and the cathode gas diffusion layer (13C) is located on one face, back to the membrane layer portion (11), of the cathode catalyst layer (12C).
3. The fuel cell integrated unit according to claim 2, wherein the frame members (30) are two in number and are a first frame member and a second frame member, respectively;
the first frame component comprises a first inner frame (31) and a first outer frame (33), and the second frame component comprises a second inner frame (35) and a second outer frame (37);
wherein the content of the first and second substances,
the inner end of the first inner frame (31) exceeds the inner end of the first outer frame (33), and the inner end is the end, facing the membrane electrode assembly (10), of the frame assembly (30); the edge area of the first inner frame (31) exceeding the first outer frame (33) is a first inner frame (31) connecting part connected with the membrane electrode assembly (10), and a gap is formed between the inner side end of the first outer frame (33) and the membrane electrode assembly (10);
and/or the inner end of the second inner frame (35) exceeds the inner end of the second outer frame (37), wherein the inner end is the end of the frame assembly (30) facing the membrane electrode assembly (10); the edge area of the second inner frame (35) exceeding the second outer frame (37) is a second inner frame (35) connecting part connected with the membrane electrode assembly (10), and a gap is formed between the inner side end of the second outer frame (37) and the membrane electrode assembly (10).
4. The fuel cell integrated unit according to claim 2, wherein the frame assembly (30) includes a first inner frame (31), a second inner frame (35) and a second outer frame (37) arranged in this order;
the inner ends of the first inner frame (31) and the second inner frame (35) exceed the inner end of the second outer frame (37), and the inner end is one end of the frame assembly (30) facing the membrane electrode assembly (10);
the edge area of the first inner frame (31) exceeding the second outer frame (37) is a first inner frame (31) connecting part connected with the membrane electrode assembly (10), and a gap is reserved between the inner side end of the second outer frame (37) and the membrane electrode assembly (10);
the edge area of the second inner frame (35) exceeding the second outer frame (37) is a second inner frame (35) connecting part connected with the membrane electrode assembly (10), and a gap is formed between the inner side end of the second outer frame (37) and the membrane electrode assembly (10).
5. The fuel cell integrated unit according to claim 2, wherein the frame assembly (30) includes a first outer frame (33), a second inner frame (35), and a second outer frame (37) arranged in this order;
the inner side end of the second inner frame (35) exceeds the inner side ends of the first outer frame (33) and the second outer frame (37), and the inner side end is one end, facing the membrane electrode assembly (10), of the frame assembly (30); the edge area of the second inner frame (35) beyond the first outer frame (33) and the second outer frame (37) is a second inner frame (35) connecting part connected with the membrane electrode assembly (10);
a gap is reserved between the inner ends of the first outer frame (33) and the second outer frame (37) and the membrane electrode assembly (10).
6. The fuel cell integrated unit of claim 1, wherein the frame assembly (30) further comprises a glue film layer disposed on a side of the inner frame and the outer frame facing the film layer (14);
the inner frame and the outer frame are resin frames.
7. The fuel cell integrated unit according to claim 1, wherein the membrane electrode assembly (10) is disposed between an anode plate (21) of the fuel cell integrated unit and a cathode plate (22) of the fuel cell integrated unit;
one surface of the frame component (30) facing the anode plate (21) is connected with the anode plate (21) through an anode plate adhesive layer (41), and one surface of the frame component (30) facing the cathode plate (22) is connected with the cathode plate (22) through a cathode plate adhesive layer (42).
8. The fuel cell integrated unit according to claim 7, wherein the anode plate (21) and the cathode plate (22) are a metal plate, a graphite-resin composite plate, or a conductive plastic plate;
and/or the surfaces of the anode plate (21) and the cathode plate (22) are provided with conductive coatings;
and/or the surfaces of the anode plate (21) and the cathode plate (22) are provided with a primer layer for increasing the bonding strength of the anode plate and the cathode plate with an adhesive layer.
9. The fuel cell integrated unit of claim 1, wherein the fuel cell integrated unit is a proton exchange membrane fuel cell, the membrane layer (14) being a proton exchange membrane;
or, the fuel cell integrated unit is a solid electrolyte membrane fuel cell, and the membrane layer (14) is a solid electrolyte membrane.
10. A fuel cell integrated unit manufacturing method for preparing the fuel cell integrated unit according to any one of claims 1 to 9, comprising:
preparing a component, namely preparing a membrane layer (14), a gas diffusion layer (13), a frame assembly (30), an anode plate (21) and a cathode plate (22);
the anode plate adhesive layer (41) is attached to the anode plate (21), and the cathode plate adhesive layer (42) is attached to the cathode plate (22);
and (3) hot-pressing, namely stacking the film layer (14), the gas diffusion layer (13), the inner frame of the frame assembly (30), the outer frame of the frame assembly (30), the anode plate (21) and the cathode plate (22) in sequence and performing hot-pressing operation.
11. The method of manufacturing a fuel cell integrated unit according to claim 10, wherein the step of hot-pressing is preceded by the step of: the frame assembly (30) is used for carrying out corona treatment or plasma treatment on the surface attached with the anode plate adhesive layer (41) and/or the cathode plate adhesive layer (42).
12. The method of manufacturing a fuel cell integrated unit according to claim 10, wherein said step of attaching an adhesive layer comprises: and pressurizing or heating the anode plate adhesive layer (41) and the anode plate (21), and pressurizing or heating the cathode plate adhesive layer (42) and the cathode plate (22).
13. The method for manufacturing a fuel cell integrated unit according to any one of claims 10 to 12, wherein in the step of hot press working, the membrane layer (14), the gas diffusion layer (13), the inner frame of the frame assembly (30), the outer frame of the frame assembly (30), the anode plate (21) and the cathode plate (22) are formed by one-time hot press;
or in the step of hot-pressing, the film layer (14), the gas diffusion layer (13), the inner frame of the frame assembly (30), the outer frame of the frame assembly (30), the anode plate (21) and the cathode plate (22) are formed by hot pressing for multiple times, and the hot-pressed parts are different in the processes of any two hot-pressing operations.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210915302.6A CN115188985A (en) | 2022-07-29 | 2022-07-29 | Fuel cell integrated unit and fuel cell integrated unit manufacturing method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115799583A (en) * | 2022-12-05 | 2023-03-14 | 中汽创智科技有限公司 | Membrane electrode preparation method, membrane electrode and fuel cell |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115799583A (en) * | 2022-12-05 | 2023-03-14 | 中汽创智科技有限公司 | Membrane electrode preparation method, membrane electrode and fuel cell |
| CN115799583B (en) * | 2022-12-05 | 2023-09-01 | 中汽创智科技有限公司 | Membrane electrode preparation method, membrane electrode and fuel cell |
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