WO2021035888A1 - 膜电极组件、制备方法及燃料电池单电池 - Google Patents

膜电极组件、制备方法及燃料电池单电池 Download PDF

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WO2021035888A1
WO2021035888A1 PCT/CN2019/110607 CN2019110607W WO2021035888A1 WO 2021035888 A1 WO2021035888 A1 WO 2021035888A1 CN 2019110607 W CN2019110607 W CN 2019110607W WO 2021035888 A1 WO2021035888 A1 WO 2021035888A1
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layer
gas diffusion
diffusion layer
melt adhesive
hot melt
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PCT/CN2019/110607
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English (en)
French (fr)
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樊帆
郝义国
刘超
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武汉中极氢能产业创新中心有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • 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

Definitions

  • the invention relates to a fuel cell, in particular to a method for preparing a fuel cell membrane electrode assembly with an integrated structure, and a membrane electrode assembly prepared by using the preparation method.
  • Fuel cells have the advantages of high energy conversion rate and environmental friendliness.
  • Proton Exchange Membrane Fuel Cell (PEMFC) has the advantages of low temperature operation and high specific power. Therefore, PEMFC is not only suitable for the establishment of decentralized power stations, but also For mobile power sources, such as electric vehicles, submarines, etc., it is a new type of mobile power source for military and civilian use.
  • the core component of the proton exchange membrane fuel cell is the membrane electrode.
  • the membrane electrode containing only the catalytic layer and the proton exchange membrane is called the 3-layer membrane electrode, also called the Catlyst Coated Membrane (CCM)
  • CCM Catlyst Coated Membrane
  • the five-layer membrane electrode, in addition to the proton exchange membrane, the catalytic layer formed by the catalyst attached to both sides of the proton exchange membrane, and the gas diffusion layer also includes the sealed and electrically insulated membrane electrode assembly, and forms the frame of the gas flow channel.
  • the reactant of the fuel cell is a gas
  • if a leak occurs it will easily cause safety accidents such as combustion, fire, or even explosion to a certain extent. Therefore, the sealing of the fuel cell is particularly important, which is very important for improving the reliability and safety of the battery, and is also an important prerequisite for the practical and commercialization of the fuel cell.
  • the membrane electrodes are prepared by hot pressing.
  • the traditional hot pressing uses two pressings, that is, the frame and the gas diffusion layer are separately pressed. Since the proton exchange membrane is easily damaged during the pressing process, multiple pressings make the proton exchange membrane more likely to be damaged. In addition, during the frame bonding process, due to the presence of air between the upper and lower frames, air bubbles are easily formed during the bonding and pressing process, which makes the appearance of the product poor.
  • Chinese patent application CN201310732881.1 relates to a membrane electrode frame process, which includes a polymer film and a glue layer, and the glue layer plays the role of bonding and sealing. The steps are cumbersome and bubbles are prone to appear.
  • Chinese patent application CN201810606372.7 relates to a fuel cell and a method of manufacturing a fuel cell, which connects the frame and the membrane electrode assembly through a bonding part that surrounds the entire membrane electrode assembly. Because the resin of the bonding part bonds the frame and the membrane electrode assembly through the outer periphery, the adhesive will inevitably adhere to the surface of the gas diffusion layer on both sides of the membrane electrode assembly and the inside of the pores to obstruct the flow of gas.
  • the prior art requires an integrated membrane electrode assembly preparation method that is not easy to generate bubbles during the preparation process, and has simple steps and does not hinder gas flow, and a membrane electrode assembly prepared by this preparation method.
  • the invention aims to provide a method for preparing a membrane electrode assembly, a membrane electrode assembly and a fuel cell single cell, which is not easy to generate bubbles during the pressing process and is formed by one-time hot pressing.
  • the first aspect of the present invention provides a method for preparing a membrane electrode assembly, including the step of pressing the following laminates, wherein the laminates include:
  • the first gas diffusion layer is the first gas diffusion layer
  • the second gas diffusion layer and
  • the intermediate layer includes a proton exchange membrane (CCM) with catalyst, a frame and a hot melt adhesive layer, wherein the frame surrounds the proton exchange membrane with catalyst at a certain interval so that the proton exchange membrane with catalyst and the A gap G is formed between the frames, and the hot melt adhesive layer is located between the gap G and the first gas diffusion layer or between the gap G and the second gas diffusion layer.
  • CCM proton exchange membrane
  • the pressing is hot pressing at 110°C to 150°C and 0.5 to 1.5Mpa; preferably, the temperature of the hot pressing is 130°C to 140°C; preferably, the pressure of the hot pressing is 1 to 1.2Mpa; More preferably, the hot pressing maintains the pressure for 1 to 5 minutes, and then the temperature is lowered to room temperature.
  • the interval is 2 to 5 mm.
  • the hot-melt adhesive layer has a width larger than the interval, and preferably, the width of the hot-melt adhesive layer is 5-50 mm.
  • the hot melt adhesive layer has an intermediate reinforcement layer sandwiched between the hot melt adhesive layer, and the thickness of the intermediate reinforcement layer is 5-20 microns.
  • the melting point of the material of the intermediate reinforcing layer is higher than the melting point of the material of the hot melt adhesive layer, preferably the melting point of the material of the intermediate reinforcing layer is higher than 150°C.
  • the bonding structure is simple, and it is a one-time molding.
  • the bonding and sealing of the components and the frame of the membrane electrode assembly can be completed by only one step of hot pressing, which reduces the hot pressing Therefore, the probability of damage to the proton exchange membrane with the catalyst is reduced.
  • the second aspect of the present invention provides a membrane electrode assembly, including
  • the first gas diffusion layer is the first gas diffusion layer
  • the second gas diffusion layer and
  • the intermediate layer includes a proton exchange membrane with catalyst, a frame and a hot melt adhesive layer, wherein the frame surrounds the proton exchange membrane with catalyst at a certain interval so that the proton exchange membrane with catalyst and the frame A gap G is formed therebetween, the hot melt adhesive layer is located between the gap G and the first gas diffusion layer or between the gap G and the second gas diffusion layer, and the gap G is completely covered by the hot melt adhesive. filling.
  • the hot melt adhesive layer is located between the first gas diffusion layer and the gap G, and the first gas diffusion layer is a cathode gas diffusion layer.
  • the interval is 2 to 5 mm.
  • the material of the hot melt adhesive layer is thermoplastic elastomer or thermoplastic resin, preferably the thermoplastic elastomer is polyurethane elastomer TPU, styrene butadiene rubber or ethylene propylene rubber; preferably the thermoplastic resin is poly Ethersulfone resin PES or ethylene-vinyl acetate EVA.
  • the hot melt adhesive layer has an intermediate reinforcement layer sandwiched between the hot melt adhesive layer, and the thickness of the intermediate reinforcement layer is 5-20 microns.
  • the melting point of the material of the intermediate reinforcing layer is higher than the melting point of the material of the hot melt adhesive layer, preferably the melting point of the material of the intermediate reinforcing layer is higher than 150°C.
  • the frame has a pair of cathode gas manifolds, a pair of anode gas manifolds, and a pair of coolant manifolds.
  • a third aspect of the present invention provides a single fuel cell cell, which includes the membrane electrode assembly as described above.
  • a fuel cell stack which includes the single fuel cell cell described above.
  • the membrane electrode assembly and the fuel cell single cell prepared according to the preparation method of the present invention will not have bubbles, reduce the number of hot pressings, ensure the high quality of the membrane electrode assembly and the fuel cell single cell, and reduce the proton exchange with the catalyst. The probability of membrane damage.
  • Figure 1 is a flow chart of the traditional preparation method (A) of the membrane electrode assembly and the preparation method (B) of the present invention
  • FIG. 2 is a schematic diagram of the composition structure of a membrane electrode assembly of a single fuel cell
  • Figure 3 is a schematic diagram of laminated materials on a heating plate
  • Fig. 4 is a schematic diagram of the specific structure of the membrane electrode prepared by the present invention.
  • the traditional method of preparing the membrane electrode assembly is to first coat the anode surface and cathode surface of the proton exchange membrane with an anode catalyst layer and a cathode catalyst layer respectively, and then cover the anode sealing frame and the cathode sealing frame respectively, and then cover the anode separately.
  • the gas diffusion layer and the anode gas diffusion layer are used to prepare the membrane electrode assembly.
  • the present invention provides a membrane electrode assembly and a process for one-time compression molding, which reduces the process flow and the risk of air leakage of the proton exchange membrane.
  • the "proton exchange membrane” used herein is a type of polymer electrolyte membrane, which is composed of a polymer electrolyte, has a branched chain with sulfonate groups, and the polymer does not contain other groups that can be ionized in an aqueous solution. polymer. In fuel cells, membranes are usually based on perfluorosulfonic acid materials, such as with Wait.
  • the film can also be a composite material, which contains materials that can conduct protons and other materials that can perform certain properties, such as high temperature resistance and mechanical properties.
  • the film may also be a polymer film with acidic groups, or other suitable materials known in the art.
  • the thickness of the proton exchange membrane with catalyst may generally be 10-50 microns, more preferably less than 40 microns, and more preferably less than 20 microns.
  • the “anode catalytic layer” and “cathode catalytic layer” used herein can use any suitable catalyst.
  • carbon-supported catalyst particles can be used, and the carbon support can include graphite, carbon black, carbon nanotubes, and carbon fibers.
  • the carbon-supported catalyst particles are 50 to 90% by weight of carbon and 10 to 50% by weight of catalyst metal.
  • the catalyst metal includes Pt for the cathode and Pt and Ru in a weight ratio of 2:1 for the anode.
  • Other metals such as Pd, Rh, Ir, Os, Au or Ag can also be used, or other suitable materials known to those skilled in the art.
  • the proton exchange membrane in which the catalyst is applied in the form of catalyst ink can also be applied to the proton exchange membrane in other suitable ways.
  • the "gas diffusion layer” used herein refers to a porous material layer that helps the reaction gas to diffuse uniformly and quickly to the catalytic layer.
  • the gas diffusion layer can be composed of a gas diffusion layer matrix and a dense microporous layer, for example, the gas diffusion layer matrix includes carbon paper Woven carbon fabric or non-woven carbon fiber mesh, and the microporous layer is generally graphite or a mixture of carbon black and a polymer such as polytetrafluoroethylene (PTFE), or other suitable materials known to those skilled in the art.
  • the thickness of the gas diffusion layer is generally between 50 and 300 microns, preferably between 100 and 300 microns, and more preferably between 150 and 300 microns.
  • the gas diffusion layers on both sides can be the same or different, as long as they can clamp the frame.
  • the hot melt adhesive used in this article plays the role of bonding each layer of the membrane electrode.
  • the hot melt temperature of the hot melt adhesive should be greater than the operating temperature of the fuel cell.
  • the melting point of the hot melt adhesive is 110 to 150 degrees Celsius, making the hot melt adhesive When the fuel cell is working, it will not be melted and penetrate into the gas diffusion layer to contaminate the electrode. At the same time, it can reduce the loss of the proton exchange membrane with the catalyst during the hot pressing.
  • the hot melt adhesive is a thermoplastic elastomer or resin (such as thermoplastic polyurethane elastomer TPU, styrene butadiene rubber, ethylene propylene rubber), or a thermoplastic elastomer or resin (such as ethylene-vinyl acetate EVA, polyethersulfone resin PES),
  • the hot melt adhesive is a thermoplastic polyurethane elastomer TPU.
  • the hot melt adhesive can also be the above-mentioned materials with an intermediate reinforcement layer, and the intermediate reinforcement layer can be polyester or polyimide with a melting point higher than the melting point of the hot melt adhesive, such as materials such as PI, PET, PEN, etc., more preferably, Polyester or polyimide with a melting point higher than 150°C.
  • the thickness of the middle reinforcement layer is 5-20 microns.
  • the present invention has no particular limitation on the thickness of the hot melt adhesive. It is better to completely fill the gap between the proton exchange membrane with catalyst and the frame after hot melting, and the thickness of the hot melt adhesive should not be too thick to avoid excessive heat melting. Penetrate into the surface of carbon paper and cause pollution.
  • the thickness of the hot melt adhesive without an intermediate reinforcement layer is usually 30 to 70 microns.
  • the thickness of the hot-melt adhesive on both sides of the hot-melt adhesive with an intermediate reinforcing layer is 10-30 microns, and the thickness of the hot-melt adhesive on both sides can be equal.
  • the term "frame” as used herein refers to a material that can isolate the cathode and anode gases outside the set reaction area.
  • the frame of the present invention has a cathode gas manifold through which cathode gas flows, an anode gas manifold through which anode gas flows, and a coolant manifold through which water or coolant flows.
  • the frame material is selected from polyamide, heat-resistant polyamide, polyethylene terephthalate, polybutylene terephthalate, ABS resin, polypropylene, polytetrafluoroethylene, acrylic, polycarbonate, poly Imide, polypropylene PPN, polyethylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol or ethylene copolymer may also be other suitable materials known to those skilled in the art.
  • the frame material is preferably polyethylene naphthalate PEN, polyethylene terephthalate PET, polyimide PI, and most preferably polyethylene naphthalate PEN.
  • the thickness of the frame is equivalent to the thickness of the proton exchange membrane with catalyst, usually 20-50 microns.
  • Figure 1 shows a comparison of the process flow between the conventional membrane electrode assembly preparation method (A) and the method (B) of the present invention.
  • the conventional membrane electrode assembly preparation method is to laminate in two steps. First, provide a proton exchange membrane with a catalyst (ie, provide CCM), and then attach the frame to the proton exchange membrane with a catalyst. , And finally attach the gas diffusion layer to the proton exchange membrane with catalyst. In the method of the present invention, the bonding of the frame and the bonding of the gas diffusion layer are completed in one step.
  • FIG. 2 shows the exploded structure of the membrane electrode assembly of the present invention.
  • the membrane electrode assembly of the present invention has the following structure: a frame 100, a first gas diffusion layer 104, a second gas diffusion layer 105, a proton exchange membrane 106 with a catalyst, and a hot melt adhesive layer 107.
  • the frame 100 also has a first manifold 101, a second manifold 102 and a third manifold 103.
  • a specific stacking relationship of the components shown in Fig. 2 is shown.
  • the proton exchange membrane 106 with catalyst is embedded in the middle of the frame 100 at a certain distance from the inner periphery of the frame 100, thereby forming a gap G between the outer periphery of the proton exchange membrane 106 with catalyst and the inner periphery of the frame 100.
  • the width of the gap G is usually 2 to 5 mm.
  • the first gas diffusion layer 104 and the second gas diffusion layer 105 are laminated on both sides of the proton exchange membrane 106 with catalyst, respectively.
  • the hot melt adhesive layer 107 is arranged on the first gas diffusion layer 104 and below the gap G. According to another lamination method, the hot melt adhesive layer 107 is arranged below the second gas diffusion layer 105 and above the gap G.
  • the hot melt adhesive layer 107 has a shape corresponding to the gap G. It is typically a hollow "Hui" shape, but it is not limited to this.
  • the hot melt adhesive layer 107 has a width corresponding to the gap G, preferably slightly larger than the width of the gap G.
  • the specific width of the hot melt adhesive layer 107 may be 5-50 mm, preferably 7-25 mm. Specifically, it may be 10 mm, 15 mm, 20 mm, and preferably 10 mm, for example.
  • the hot melt adhesive layer 107 has a wider width than the gap G, so that its inner periphery partially overlaps with the catalyst-carrying proton exchange membrane 106, and the outer periphery partially overlaps the frame 100, thereby providing a bonding surface with each other.
  • hot melt adhesive The overlapping portion between the layer 107, the frame and the proton exchange membrane with catalyst is preferably 2 to 10 mm.
  • this method can complete the bonding and sealing of the two sides only by installing hot melt adhesive on one side, which significantly reduces the amount of hot melt adhesive, thereby reducing the hot melt adhesive on the various parts of the membrane electrode assembly. The adverse effects.
  • the hot melt adhesive layer 107 may also have an intermediate reinforcement layer (not shown).
  • the middle reinforcing layer may be a material with a melting point higher than the melting point of the hot melt adhesive.
  • the present invention has no particular limitation on the material of the intermediate reinforcement layer. Generally, polyester or polyimide, such as PI, PET, PEN, etc., can be used.
  • the melting point of the middle reinforcing layer may be higher than 150°C, and the thickness may be 5-20 microns.
  • the thickness of the hot melt adhesive layer 107 without an intermediate reinforcement layer is generally 30-70 microns. In other specific embodiments, the thickness of the hot melt adhesive on both sides of the hot melt adhesive layer 107 with an intermediate reinforcing layer may be 10-30 microns, and the thickness of the hot melt adhesive on both sides is preferably equal.
  • the addition of the intermediate reinforcing layer can further enhance the barrier properties of the hot melt adhesive layer to the cathode and anode gases on the one hand, and on the other hand can enhance the strength of the hot melt adhesive layer.
  • the arrangement of the hot melt adhesive layer 107 shown in FIG. 3 is such that when the laminated components are hot pressed, the melted hot melt adhesive can enter the gap G (see FIG. 4), thereby forming the first gas diffusion layer 104 A thin layer is formed between the proton exchange membrane 106 with the catalyst, the frame 100 and the second gas diffusion layer 105 to bond the components together and simultaneously make the first gas diffusion layer 104 and the second gas diffusion layer 105 Insulate and isolate each other.
  • the hot melt adhesive layer 107 After the hot melt adhesive layer 107 is melted, it will extend to both ends, thereby reducing the area of the catalytic layer with the gas diffusion layer.
  • the hot melt adhesive layer 107 is placed on the cathode side, so that the cathode catalytic area is smaller than the anode catalytic area, so as to avoid free radicals from damaging the edge of the proton exchange membrane with catalyst.
  • the hot melt adhesive that can be used in the present invention can be selected from thermoplastic elastomers or resins (such as thermoplastic polyurethane elastomer TPU, styrene butadiene rubber, ethylene propylene rubber), or thermoplastic elastomers or resins (such as ethylene-vinyl acetate EVA, polyethersulfone). Resin PES). Most preferably, the hot melt adhesive is a thermoplastic polyurethane elastomer TPU.
  • the first gas diffusion layer 104 is a cathode gas diffusion layer
  • the second gas diffusion layer 105 is an anode gas diffusion layer.
  • the gas diffusion layer is rectangular, such as a square.
  • the first gas diffusion layer 104 is composed of a relatively dense microporous layer 202 and a gas diffusion matrix layer 203.
  • the microporous layer 202 is adjacent to the proton exchange layer 106.
  • the microporous layer can effectively discharge the liquid water produced by the reaction. Maintain gas transmission.
  • the side adjacent to the second gas diffusion layer 105 and the proton exchange layer 106 may also have a denser microporous layer, and the second gas diffusion layer may also have a gas diffusion matrix layer.
  • the first gas diffusion layer 104 and the second gas diffusion layer 105 can be the same size, or one large (with glue side) and one small (with no glue side), but the gas diffusion layer must be able to clamp the frame.
  • the frame 100 has a plurality of manifolds, which respectively flow cathode gas, anode gas and coolant.
  • the first manifold 101 is a cathode gas manifold, in which cathode gas, such as oxygen, flows;
  • the second manifold 102 is an anode gas manifold, in which anode gas, such as hydrogen, flows;
  • the third manifold 103 is a coolant manifold , In which there is a coolant, such as water.
  • the frame material is preferably polyethylene naphthalate PEN, polyethylene terephthalate PET, polyimide PI, and most preferably polyethylene naphthalate PEN.
  • the catalyst-carrying proton exchange membrane 106 has a thickness of 20-50 microns, and its two sides are coated with a cathode catalyst layer and an anode catalyst layer, which respectively catalyze the reduction and oxidation reactions of oxygen and hydrogen to generate electric energy.
  • the cathode catalyst layer is in contact with the cathode gas diffusion layer
  • the anode catalyst layer is in contact with the anode gas diffusion layer.
  • the area of the cathode catalyst layer and the anode catalyst layer may be the same or different.
  • the preparation method of the membrane electrode assembly of the present invention is shown in Figure 1.
  • the frame and the gas diffusion layer are prepared, the above materials are laminated (as shown in Figure 3), and then pressed at one time Molding:
  • the first layer is the first gas diffusion layer 104
  • the second layer is the middle layer
  • the third layer is the second gas diffusion layer 105
  • the middle layer is divided into two layers
  • the first layer is the hot melt adhesive layer 107
  • the second layer is the proton exchange membrane 106 with catalyst and the frame 100; wherein the frame 100 surrounds the proton exchange membrane 106 with catalyst, and there is a gap between the proton exchange membrane 106 with catalyst and the frame 100 G.
  • the preparation method further includes a hot pressing step, placing the above-mentioned laminated materials between the plates 201 with heating pipes, heating the plates 201 on both sides, and then applying the plate on one side to the plate on the other side. Press, maintain the pressure for 1 to 5 minutes, and then lower the temperature to room temperature.
  • the plates on both sides are heated to a temperature higher than 100°C, preferably 110 to 150°C, more preferably 140°C
  • the pressure applied from one side of the flat plate to the other side is 0.5-1.5Mpa, preferably 1Mpa.
  • the hot melt adhesive 107 when the hot melt adhesive 107 is heated to a viscous fluid state, the hot melt adhesive 107 will be preferentially pressed into the gap G during the hot pressing process, and since the second gas diffusion layer 105 is a porous material, When the hot melt adhesive is pressed into the gap G, the gas in G can be smoothly squeezed out to complete bonding with the second gas diffusion layer 105 without the generation of bubbles.
  • this method can complete the bonding and sealing of all components by only installing hot melt adhesive on one side of the proton exchange membrane with catalyst, which reduces the amount of hot melt adhesive and saves costs. The risk of hot melt glue contaminating the electrode is reduced.
  • the membrane electrode of the present invention can be press-formed at one time by laminating in advance and then performing hot pressing, which reduces the risk of gas leakage from the process flow and the proton exchange membrane with catalyst.
  • FIG. 4 A specific structure of the membrane electrode assembly prepared by the method of the present invention is shown in FIG. 4.
  • the membrane electrode assembly shown in FIG. 4 includes a first gas diffusion layer 104, a second gas diffusion layer 105, and an intermediate layer sandwiched between the first and second gas diffusion layers.
  • the intermediate layer includes a proton exchange membrane 106 with a catalyst, a hot melt adhesive layer 107 and a frame 100.
  • the frame 100 surrounds the proton exchange membrane 106 with catalyst, and there is a gap G between the proton exchange membrane 106 with catalyst and the frame 100, and the hot melt adhesive layer 107 is located between the first gas diffusion layer 104 and the gap G , And completely fill the gap G.
  • the hot melt adhesive layer 107 may be located between the second gas diffusion layer 105 and the gap G, and completely fill the gap G.
  • the melt adhesive layer 107 may also have an intermediate reinforcement layer, which may be polyester or polyimide with a melting point higher than the melting point of the hot melt adhesive, such as PI, PET, PEN And other materials.
  • an intermediate reinforcement layer which may be polyester or polyimide with a melting point higher than the melting point of the hot melt adhesive, such as PI, PET, PEN And other materials.
  • the proton exchange membrane 106 with catalyst is coated with a catalytic layer.
  • the hot melt adhesive layer 107 is placed on the cathode side so that the cathode catalytic area is smaller than the anode catalytic area. This embodiment can prevent the free radicals generated by the cathode from damaging the edge of the proton exchange membrane with the catalyst.
  • the above-mentioned membrane electrode assembly is further assembled with components such as bipolar plates to obtain a single fuel cell.
  • the present invention has no special restrictions on components such as bipolar plates, and suitable bipolar plates in the field can be used in the present invention.

Abstract

本发明提供了膜电极组件、制备方法及燃料电池单电池，具体地，提供了一种膜电极组件的制备方法，包括对以下叠层进行压制的步骤，其中，所述叠层包括：第一气体扩散层，第二气体扩散层，和布置在所述第一气体扩散层和所述第二气体扩散层之间的中间层，所述中间层包括带催化剂的质子交换膜，边框和热熔胶层，其中，所述边框以一定间隔包围所述带催化剂的质子交换膜从而在所述带催化剂的质子交换膜和所述边框之间形成空隙G，所述热熔胶层位于所述空隙G与第一气体扩散层之间或者位于所述空隙G与第二气体扩散层之间。本发明的方法不产生气泡，并且一次成型，减少热压次数，而减小了带催化剂的质子交换膜损坏的几率。

Description

膜电极组件、制备方法及燃料电池单电池 技术领域
本发明涉及燃料电池，特别是涉及一种具有一体化结构的燃料电池膜电极组件的制备方法，以及使用这种制备方法制备的膜电极组件。
背景技术
随着石油资源的日益紧缺和人们环保意识的提高，全球的能源体系正在发生根本性的改变，发展高效的清洁能源代替石油已经成为大多数国家的共识，而其中最为重要的一种则是采用燃料电池进行发电，使氢气与空气发生电化学反应，产生电能而产物只有水，这种燃料电池尤其将会运用到汽车上，成为汽车的清洁能源。
燃料电池具有能量转换率高、环境友好等优点，而质子交换膜燃料电池(Proton Exchange Membrane Fuel Cell，PEMFC)更具有低温运行、比功率高等优点，因此PEMFC不仅可适用于建立分散电站，也适用于可移动动力源，如电动汽车、潜艇等，是军、民通用的新型可移动动力源。
质子交换膜燃料电池的核心部件为膜电极。通常把只含有催化层和质子交换膜的膜电极称为3层膜电极，也称催化剂涂层膜(Catlyst Coated Membrane，CCM)，而把含有气体扩散层、催化层和膜的膜电极称为5层膜电极，除质子交换膜、附着于质子交换膜两侧的催化剂形成的催化层，以及气体扩散层外，还包括密封并电绝缘膜电极组件，并形成气体流道的边框。
由于燃料电池的反应物质是气体，如果发生泄漏，到一定程度容易引起燃烧、起火、甚至爆炸等安全事故。因此，燃料电池的密封特别重要，这对于提高电池的可靠性、安全性非常重要，也是燃料电池能够走向实用 化和商业化的重要前提。
同时，膜电极大多采用热压制备，传统的热压采用两次压制，即将边框和气体扩散层分开压制，由于压制过程中容易损坏质子交换膜，多次压制使得质子交换膜更易出现损坏。除此之外，在边框贴合过程中，由于上下两层边框中间空气的存在，在贴合压制过程中容易形成气泡，从而使得产品的外观不良。
中国专利申请CN201310732881.1涉及了一种膜电极边框工艺，包括聚合物膜和胶层，胶层起到粘结和密封的作用。其步骤繁琐并且容易出现气泡。
中国专利申请CN201810606372.7涉及了一种燃料电池和制造燃料电池的方法，其通过包围整个膜电极组件的粘结部将边框和膜电极组件连接起来。由于其粘结部的树脂是通过外周包围的形式粘结边框和膜电极组件，使得粘结剂会不可避免的附着在膜电极组件两侧的气体扩散层表面及孔隙内部阻碍气体的流通。
因此，现有技术需要一种在制备过程中不易产生气泡，并且步骤简单也不会阻碍气体流通的一体成型的膜电极组件制备方法以及通过这种制备方法制备的膜电极组件。
发明内容
本发明旨在提供一种在压制过程中不易产生气泡，且一次热压成型的膜电极组件制备方法以及膜电极组件和燃料电池单电池。
本发明的第一方面提供一种膜电极组件的制备方法，包括对以下叠层进行压制的步骤，其中，所述叠层包括：
第一气体扩散层，
第二气体扩散层，和
布置在所述第一气体扩散层和所述第二气体扩散层之间的中间层，
所述中间层包括带催化剂的质子交换膜(CCM)，边框和热熔胶层，其中，所述边框以一定间隔包围所述带催化剂的质子交换膜从而在所述带催化剂的质子交换膜和所述边框之间形成空隙G，所述热熔胶层位于所述空隙G与第一气体扩散层之间或者位于所述空隙G与第二气体扩散层之间。
进一步地，所述压制为在110℃～150℃、0.5～1.5Mpa下的热压制；优选地，热压制的温度为130℃～140℃；优选地，热压制的压力为1～1.2Mpa；更优选地，所述热压制保持压力1～5min，随后降温至室温。
在一个具体实施方案中，所述间隔为2～5mm。
在一个具体实施方案中，所述热熔胶层具有大于所述间隔的宽度，优选地，所述热熔胶层的宽度为5～50mm。
在一个具体实施方案中，所述热熔胶层具有夹在所述热熔胶层中间的中间增强层，所述中间增强层的厚度为5～20微米。
进一步地，所述中间增强层的材料的熔点高于所述热熔胶层的材料的熔点，优选所述中间增强层的材料的熔点高于150℃。
使用本发明的制备方法，不会产生气泡，且粘接结构简单，而且是一次性成型，仅通过一步热压就可以完成膜电极组件的各部件以及边框的粘结和密封，减少了热压次数，从而减小了带催化剂的质子交换膜损坏的几率。
本发明的第二方面提供一种膜电极组件，包括
第一气体扩散层，
第二气体扩散层，和
布置在所述第一气体扩散层和所述第二气体扩散层之间的中间层，
所述中间层包括带催化剂的质子交换膜，边框和热熔胶层，其中，所述边框以一定间隔包围所述带催化剂的质子交换膜从而在所述带催化剂的质子交换膜和所述边框之间形成空隙G，所述热熔胶层位于所述空隙G与 第一气体扩散层之间或者位于所述空隙G与第二气体扩散层之间，且所述空隙G被热熔胶完全填充。
进一步地，所述热熔胶层位于第一气体扩散层与所述空隙G之间，所述第一气体扩散层为阴极气体扩散层。
在一个具体实施方案中，所述间隔为2～5mm。
在一个具体实施方案中，所述热熔胶层的材料是热塑性弹性体或热塑性树脂，优选所述热塑性弹性体为聚氨酯弹性体TPU、丁苯橡胶或乙丙橡胶；优选所述热塑性树脂为聚醚砜树脂PES或乙烯-醋酸乙烯EVA。
在一个具体实施方案中，所述热熔胶层具有夹在所述热熔胶层中间的中间增强层，所述中间增强层的厚度为5～20微米。
进一步地，所述中间增强层的材料的熔点高于所述热熔胶层的材料的熔点，优选所述中间增强层的材料的熔点高于150℃。
在一个具体实施方案中，所述边框上具有一对阴极气体歧管、一对阳极气体歧管和一对冷却剂歧管。
本发明的第三方面，提供一种燃料电池单电池，其包括如上所述的膜电极组件。
本发明的第四方面，提供了一种燃料电池堆，其包括如上所述的燃料电池单电池。
按照本发明制备方法制备得到的膜电极组件和燃料电池单电池，不会存在气泡，减少了热压次数保证了膜电极组件和燃料电池单电池的高质量，也减小了带催化剂的质子交换膜损坏的几率。
附图说明
图1为膜电极组件传统制备方法(A)和本发明制备方法(B)的流程图；
图2为燃料电池单电池的膜电极组件的组成结构示意图；
图3为在加热平板上的层叠材料的示意图；
图4为本发明制备的膜电极的具体结构示意图。
具体实施方式
传统的膜电极组件制备方法，是先质子交换膜的阳极面和阴极面分别涂覆有阳极催化层和阴极催化层，然后再分别覆合阳极密封边框和阴极密封边框，然后再分别覆合阳极气体扩散层和阳极气体扩散层，制得膜电极组件。
而本发明则提供一种一次性压制成型的膜电极组件和工艺，减少了工艺流程和质子交换膜漏气的风险。
术语定义
本文所用的“质子交换膜”是聚合物电解质薄膜的一种，其是由聚合物电解质组成，具有带磺酸根基团的支链且聚合物中不含有在水溶液中可以电离的其它基团的聚合物。在燃料电池中，薄膜通常基于全氟磺酸材料，例如
Figure PCTCN2019110607-appb-000001
和
Figure PCTCN2019110607-appb-000002
等。薄膜还可以是复合材料，其包含可传导质子的材料以及可以某些性能，如耐高温、机械性能的其他材料。薄膜还可以是具有酸性基团的高分子薄膜，或者是本领域知晓的其余合适的材料。
所述带催化剂的质子交换膜的厚度通常可为10～50微米，更优选小于40微米，更优选小于20微米。
本文所用的“阳极催化层”和“阴极催化层”可以使用任何合适的催化剂。一般来说，可使用碳负载的催化剂颗粒，碳载体可以包括石墨、炭黑、纳米碳管以及碳纤维等。通常，碳负载的催化剂颗粒是50～90重量％的碳和10～50重量％的催化剂金属，所述催化剂金属包括用于阴极的Pt和用于阳极的重量比为2:1的Pt和Ru，还可以使用其它诸如Pd、Rh、Ir、Os、Au或Ag等金属，也可以是本领域技术人员知晓的其它合适的材料。将催 化剂以催化剂油墨的形式施加的所述质子交换膜上，也可以采用其它合适的方式施加到质子交换膜上。
本文所用的“气体扩散层”是指帮助反应气体均匀、快速扩散至催化层的一种多孔材料层。气体扩散层例如可由气体扩散层基质和致密的微孔层组成，气体扩散层基质包括碳纸
Figure PCTCN2019110607-appb-000003
纺织的碳织物或者无纺碳纤维网，而微孔层则一般为石墨或者炭黑和聚合物诸如聚四氟乙烯(PTFE)的混合物，也可以是本领域技术人员知晓的其它合适的材料。气体扩散层的厚度一般在50～300微米之间，优选100～300微米之间，更优选150～300微米之间。两侧的气体扩散层可以一样大，也可以不一样大，只需能够夹住边框。
本文所用的“热熔胶”起着粘结膜电极各层的作用，热熔胶的热熔温度应该大于燃料电池的工作温度，例如热熔胶的熔点为110～150摄氏度，使得热熔胶在燃料电池工作时不会热熔而渗入气体扩散层污染电极，同时这样可以在热压时减少对带催化剂的质子交换膜的损失。优选地，热熔胶为热塑性弹性体或树脂(例如热塑性聚氨酯弹性体TPU、丁苯橡胶，乙丙橡胶)，或者热塑性弹性体或树脂(例如乙烯～醋酸乙烯EVA、聚醚砜树脂PES)，最优选地，热熔胶为热塑性聚氨酯弹性体TPU。
热熔胶还可以是带有中间增强层的上述材料，中间增强层可以是熔点高于热熔胶熔点的聚酯或聚酰亚胺，例如PI、PET、PEN等材料，更优选地，为熔点高于150℃的聚酯或聚酰亚胺。中间增强层的厚度为5～20微米。
本发明对于热熔胶的厚度没有特别的限定，以热熔后完全填充带催化剂的质子交换膜和边框之间的空隙为佳，而热熔胶的厚度也不能过厚，以免热熔后过度渗入碳纸表面而造成污染。通常，无中间增强层的热熔胶的厚度通常为30～70微米。而有中间增强层的热熔胶的两侧热熔胶厚度为10～30微米，两侧热熔胶厚度可相等。
本文所用的术语“边框”是指在设置反应区域以外可以隔绝阴阳极气体的材料。根据一种实施方式，本发明的边框具有通阴极气体的阴极气体歧管、通阳极气体的阳极气体歧管以及通水或者冷却剂的冷却剂歧管。边框材料选自聚酰胺、耐热聚酰胺、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、ABS树脂、聚丙烯、聚四氟乙烯、亚克力、聚碳酸酯、聚酰亚胺、聚丙烯PPN、聚乙烯、聚苯乙烯、聚氯乙烯、聚偏二氯乙烯、聚乙烯醇或乙烯共聚物，也可以是本领域技术人员知晓的其它合适的材料。边框材料优选为聚萘二甲酸乙二醇酯PEN、聚对苯二甲酸乙二酯PET、聚酰亚胺PI，最优选为聚萘二甲酸乙二醇酯PEN。边框的厚度与带催化剂的质子交换膜的厚度相当，通常为20～50微米。
以下结合附图所示的具体实施方式来详细说明本发明。
图1中示出了常规的膜电极组件制备方法(A)与本发明方法(B)的工艺流程的对比。如前所述，常规的膜电极组件制备方法是分两步进行贴合的，首先提供带催化剂的质子交换膜(即，提供CCM)，然后再将边框贴合至带催化剂的质子交换膜上，最后再将气体扩散层贴合到带催化剂的质子交换膜上。而本发明的方法中，边框的贴合和气体扩散层的贴合是一步完成的。
图2示出了本发明膜电极组件的分解结构。如图2所示，本发明的膜电极组件具有如下结构：边框100、第一气体扩散层104、第二气体扩散层105、带催化剂的质子交换膜106和热熔胶层107。边框100上还具有第一歧管101、第二歧管102以及第三歧管103。
进一步参见图3，其中示出了图2所示各部件的一种具体的层叠关系。其中，带催化剂的质子交换膜106以与边框100的内周边相距一定距离的方式嵌入边框100的中间，从而在带催化剂的质子交换膜106的外周边与边框100的内周边之间形成空隙G。空隙G的宽度通常为2～5mm。
在带催化剂的质子交换膜106的两侧分别层叠第一气体扩散层104和第二气体扩散层105。
图3所示的层叠方式中，热熔胶层107布置在第一气体扩散层104之上，在空隙G的下方。根据另一层叠方式，热熔胶层107布置在第二气体扩散层105之下，在空隙G的上方。
热熔胶层107具有对应空隙G的形状。典型地为中空的“回”字形形状，但不限于此。热熔胶层107具有对应空隙G的宽度，优选地略大于空隙G的宽度。热熔胶层107的具体宽度可为5～50mm，优选7～25mm。具体地，例如可为10mm、15mm、20mm，优选10mm。
热熔胶层107具有比空隙G更宽的宽度，从而其内周与带催化剂的质子交换膜106部分重叠，外周与边框100部分重叠，从而提供彼此的粘结面，具体地，热熔胶层107与边框以及带催化剂的质子交换膜之间的重合部分优选为2～10mm。
通过上述的设计，该方法仅在一边设置热熔胶就可以完成对两边的粘合和密封，这样显著减少了热熔胶的用量，从而也减小了热熔胶对膜电极组件的各部件的不利影响。
热熔胶层107还可以带有中间增强层(未示出)。中间增强层可以是熔点高于热熔胶熔点的材料。本发明对中间增强层材料没有特别限制，通常可采用聚酯或聚酰亚胺，例如PI、PET、PEN等材料。中间增强层的熔点可高于150℃，其厚度可为5～20微米。
在一些具体实施方式中，无中间增强层的热熔胶层107的厚度通常为30～70微米。在另一些具体实施方式中，有中间增强层的热熔胶层107的两侧热熔胶厚度可为10～30微米，两侧热熔胶厚度优选相等。
中间增强层的加入一方面可以进一步增强热熔胶层对阴阳极气体的阻隔性，另一方面可增强热熔胶层的强度。
如图3所示的热熔胶层107的布置方式使得当对层叠的各组件进行热压时，熔化的热熔胶可以进入空隙G中(参见图4)，从而在第一气体扩散层104与带催化剂的质子交换膜106、边框100以及第二气体扩散层105之间形成薄层，从而将所述部件粘合在一起，并同时使第一气体扩散层104和第二气体扩散层105之间相互绝缘并隔离。
所述热熔胶层107热熔之后，会向两端延伸，从而减小与气体扩散层的催化层的面积。优选将热熔胶层107放置在阴极侧，使得阴极催化区域小于阳极催化区域，以避免自由基对于带催化剂的质子交换膜边缘的损伤。
可用于本发明的热熔胶可选自热塑性弹性体或树脂(例如热塑性聚氨酯弹性体TPU、丁苯橡胶，乙丙橡胶)，或者热塑性弹性体或树脂(例如乙烯～醋酸乙烯EVA、聚醚砜树脂PES)。最优选地，热熔胶为热塑性聚氨酯弹性体TPU。
在一个具体的实施方案中，第一气体扩散层104为阴极气体扩散层，第二气体扩散层105为阳极气体扩散层。通常，气体扩散层为矩形，如正方形。
所述第一气体扩散层104由较为致密的微孔层202和气体扩散基质层203构成，所述微孔层202与质子交换层106相邻，微孔层可以有效排出反应产生的液态水并保持气体传输。
第二气体扩散层105与质子交换层106相邻的一侧可同样具有一层较为致密的微孔层，第二气体扩散层也同样具有气体扩散基质层。
第一气体扩散层104和第二气体扩散层105可以一样大，也可以一大(有胶侧)一小(无胶侧)，但气体扩散层必须能够夹住边框。
在一个具体的实施方案中，边框100具有多个歧管，分别流动阴极气体、阳极气体和冷却剂。第一歧管101为阴极气体歧管，其中流动有阴极气体，例如氧气；第二歧管102为阳极气体歧管，其中流动有阳极气体， 例如氢气；第三歧管103为冷却剂歧管，其中流动有冷却剂，例如水。
边框材料优选为聚萘二甲酸乙二醇酯PEN、聚对苯二甲酸乙二酯PET、聚酰亚胺PI，最优选为聚萘二甲酸乙二醇酯PEN。
带催化剂的质子交换膜106的厚度为20～50微米，其的两侧涂布有阴极催化层和阳极催化层，分别催化氧气和氢气发生还原和氧化反应，从而产生电能。其中，阴极催化层与阴极气体扩散层接触，阳极催化层与阳极气体扩散层接触。阴极催化层和阳极催化层的面积可以是相同的也可以是不同的。
本发明的膜电极组件的制备方法，如图1所示，待带催化剂的质子交换膜、边框和气体扩散层备好之后，对上述材料进行层叠(如图3所示)，然后一次性压制成型：第一层为第一气体扩散层104，第二层为中间层，第三层为第二气体扩散层105；所述中间层分为两层，第一层为热熔胶层107，第二层为带催化剂的质子交换膜106和边框100；其中，所述边框100将带催化剂的质子交换膜106包围在内，且所述带催化剂的质子交换膜106和边框100之间存在空隙G。
进一步地，所述制备方法还包括热压步骤，将上述层叠的材料放入加装具有加热管的平板201之间，加热两侧平板201，然后使其中一侧的平板向另一侧平板施压，保持压力1～5min，随后降温至室温。
在一个优选的实施方案中，两侧平板加热到高于100℃，优选110～150℃，更优选为140℃
在另一个优选的实施方案中，一侧平板向另一侧平板施压的压力为0.5～1.5Mpa，优选为1Mpa。
使用本发明的制备方法，当热熔胶107被加热到粘流态时，在热压过程中热熔胶107会优先被压入空隙G中，而由于第二气体扩散层105为多孔材料，在热熔胶被压入空隙G的过程中就可以顺利的挤出G中的气体， 与第二气体扩散层105完成粘结而没有气泡的产生。
除此之外，该方法仅在带催化剂的质子交换膜的一侧设置热熔胶就可以完成对所有部件的粘合和密封，这样就减少了热熔胶的用量节约了成本，同时也减小了热熔胶污染电极的风险。
另外，通过提前层叠好再进行热压的方式，使得本发明的膜电极可以一次压制成型，减少了工艺流程和带催化剂的质子交换膜漏气的风险。
本发明的方法制备得到的膜电极组件的一种具体结构如图4所示。
图4所示的膜电极组件包括第一气体扩散层104、第二气体扩散层105和夹在第一和第二气体扩散层之间的中间层。所述中间层包括带催化剂的质子交换膜106、热熔胶层107以及边框100。边框100将带催化剂的质子交换膜106包围在内，且所述带催化剂的质子交换膜106和边框100之间存在空隙G，并且，热熔胶层107位于第一气体扩散层104和空隙G之间，且完全填充空隙G。
在又一个具体的实施方案中，所述热熔胶层107可位于第二气体扩散层105和空隙G之间，且完全填充空隙G。
在又一个具体的实施方案中，所述熔胶层107还可以带有中间增强层，中间增强层可以是熔点高于热熔胶熔点的聚酯或聚酰亚胺，例如PI、PET、PEN等材料。
该实施例中带催化剂的质子交换膜106上涂布有催化层，优选地，将热熔胶层107放置在阴极侧，使得阴极催化区域小于阳极催化区域。该实施方式可以避免阴极产生的自由基对于带催化剂的质子交换膜边缘的损伤。
上述膜电极组件进一步与双极板等部件组装可得到燃料电池单电池。本发明对双极板等部件没有特别限制，本领域中适宜的双极板均可用于本发明。
以上所述，仅为本发明的较佳实施例而已，并非用于限定本发明的保护范围。

Claims (11)

  1. 一种膜电极组件的制备方法，包括对以下叠层进行压制的步骤，其中，所述叠层包括：
    第一气体扩散层，
    第二气体扩散层，和
    布置在所述第一气体扩散层和所述第二气体扩散层之间的中间层，
    所述中间层包括带催化剂的质子交换膜，边框和热熔胶层，其中，所述边框以一定间隔包围所述带催化剂的质子交换膜从而在所述带催化剂的质子交换膜和所述边框之间形成空隙G，所述热熔胶层位于所述空隙G与第一气体扩散层之间或者位于所述空隙G与第二气体扩散层之间。
  2. 根据权利要求1所述的方法，进一步地，所述压制为在110℃～150℃、0.5～1.5Mpa下的热压制；优选地，热压制的温度为130℃～140℃；优选地，热压制的压力为1～1.2Mpa；更优选地，所述热压制保持压力1～5min，随后降温至室温。
  3. 根据权利要求1或2所述的方法，其中，所述间隔为2～5mm。
  4. 根据权利要求1～3所述的方法，其中，所述热熔胶层具有夹在所述热熔胶层中间的中间增强层，所述中间增强层的厚度为5～20微米。
  5. 一种膜电极组件，包括
    第一气体扩散层，
    第二气体扩散层，和
    布置在所述第一气体扩散层和所述第二气体扩散层之间的中间层，
    所述中间层包括带催化剂的质子交换膜，边框和热熔胶层，其中，所述边框以一定间隔包围所述带催化剂的质子交换膜从而在所述带催化剂的质子交换膜和所述边框之间形成空隙G，所述热熔胶层位于所述空隙G与第一气体扩散层之间或者位于所述空隙G与第二气体扩散层之间，且所述 空隙G被热熔胶完全填充。
  6. 根据权利要求5所述的膜电极组件，其中，所述热熔胶层位于第一气体扩散层与所述空隙G之间，所述第一气体扩散层为阴极气体扩散层。
  7. 根据权利要求5或6所述的膜电极组件，其中，所述间隔为2～5mm。
  8. 根据权利要求5～7所述的膜电极组件，其中，所述热熔胶层的材料是热塑性弹性体或热塑性树脂，优选所述热塑性弹性体为聚氨酯弹性体TPU、丁苯橡胶或乙丙橡胶；优选所述热塑性树脂为聚醚砜树脂PES或乙烯-醋酸乙烯EVA。
  9. 根据权利要求5～8所述的膜电极组件，其中，所述热熔胶层具有夹在所述热熔胶层中间的中间增强层，所述中间增强层的厚度为5～20微米。
  10. 一种燃料电池单电池，包括权利要求5～9中任一项所述的膜电极组件。
  11. 一种燃料电池堆，包括权利要求10所述的燃料电池单电池。
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