WO2020252606A1 - 一种燃料电池用膜电极结构、燃料电池膜电极的制备方法及质子交换膜燃料电池系统 - Google Patents

一种燃料电池用膜电极结构、燃料电池膜电极的制备方法及质子交换膜燃料电池系统 Download PDF

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WO2020252606A1
WO2020252606A1 PCT/CN2019/091461 CN2019091461W WO2020252606A1 WO 2020252606 A1 WO2020252606 A1 WO 2020252606A1 CN 2019091461 W CN2019091461 W CN 2019091461W WO 2020252606 A1 WO2020252606 A1 WO 2020252606A1
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layer
membrane electrode
catalyst
fuel cell
preparing
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PCT/CN2019/091461
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English (en)
French (fr)
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樊建涛
王海江
李辉
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深圳市通用氢能科技有限公司
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Priority to PCT/CN2019/091461 priority Critical patent/WO2020252606A1/zh
Publication of WO2020252606A1 publication Critical patent/WO2020252606A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • 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
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • 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
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • 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

Definitions

  • the present invention relates to the technical field of fuel cell membrane electrodes, in particular to a membrane electrode structure for fuel cells, a method for preparing a fuel cell membrane electrode, and a proton exchange membrane fuel cell system.
  • a fuel cell is an electrochemical cell whose main principle is to directly convert the chemical energy in the fuel and oxidant into electrical energy through a redox reaction.
  • the proton exchange membrane fuel cell (PEMFC) has the general characteristics of fuel cell such as high energy conversion efficiency and environmental friendliness. It also has fast startup speed at room temperature, small size, no electrolyte loss, Outstanding advantages such as easy drainage, long life, high specific power and specific energy. It is not only suitable for the construction of distributed power stations, but also for mobile power supply. It is a new type of military and civilian mobile power supply. Therefore, proton exchange membrane fuel cells have very broad application prospects.
  • MEA Membrane Electrode Assembly
  • PEM perfluorosulfonic acid proton exchange membrane
  • Catalyst layer, CL catalyst layer
  • GDL gas diffusion layer
  • the three-layer membrane electrode (CCM) involved in the present invention is composed of a PEM, an anode catalyst layer (ACL), and a cathode catalyst layer (CCL).
  • the five-layer membrane electrode (MEA) involved in the present invention is composed of CCM and cathode and anode GDL.
  • CCM is the basic unit of fuel cell electrochemical reaction.
  • the structural design and preparation process proposal of CCM need to be based on the basic principles and characteristics of fuel cell electrochemical reaction as the theoretical basis, combined with its actual working conditions for comprehensive consideration.
  • the structure design and preparation process technology of CCM is the key technology of fuel cell, which determines the working performance of fuel cell.
  • the existing three-layer membrane electrode (CCM) preparation technology mainly includes (but not limited to) the following: 1. Double transfer method, that is, first coat the catalyst slurry on the substrate film and dry to obtain ACL and CCL, and then pass The ACL and CCL are joined to both sides of the PEM by hot-press transfer; 2.
  • the cathode (or anode) catalyst slurry is directly coated on the outside of the proton exchange membrane (PEM) with the back membrane Cover, prepare PEM with CCL (or ACL), after drying, peel off the PEM coated with CCL (or ACL) from the back film, and then attach the ACL (or CCL) to the other part of the PEM by means of hot press transfer One side; 3, the double-sided coating method, that is, the cathode (or anode) catalyst slurry is directly coated on the outside of the PEM with the back film, and the PEM with CCL (or ACL) is obtained after drying.
  • PEM proton exchange membrane
  • the PEM covered with CCL (or ACL) is peeled off the backing film, and then the anode (or cathode) catalyst slurry is directly applied to the other side of the PEM and dried, or ACL and CCL are applied to both sides of the PEM at the same time And drying;
  • 4, spraying method that is, CCM is prepared by spraying anode catalyst slurry and cathode catalyst slurry on both sides of the PEM;
  • screen printing method direct catalyst slurry through screen printing After printing on the surface of the PEM and drying, the other side of the catalytic layer is printed to make CCM;
  • 6, in-situ preparation method the catalyst is directly grown on both sides of the PEM through chemical and physical methods to form an ordered catalytic layer Structure of CCM.
  • the above-mentioned preparation methods of CCM can be summarized into two categories.
  • First, the catalyst slurry is used to directly prepare the catalytic layer on both sides of the PEM, such as direct coating, spraying or screen printing; second, preparation on the back film
  • the catalytic layer is bonded to the PEM by means of transfer bonding; or a combination of these two methods.
  • the two sides of the CCM obtained by the above method are attached to the GDL to obtain the MEA.
  • Another MEA preparation method is the traditional gas diffusion electrode (Gas Diffusion Electrode, GDE) preparation method (as shown in Figure 1 of this application), that is, the anode catalyst slurry is coated on the GDL to obtain the anode GDE, and the cathode catalyst The slurry is coated on the GDL to obtain the cathode GDE, and then the anode GDE and the cathode GDE are respectively joined to the two sides of the PEM by hot pressing to obtain the MEA.
  • GDE Gas Diffusion Electrode
  • the present invention is mainly aimed at improving the traditional transfer method.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a membrane electrode structure for fuel cells.
  • the membrane electrode When preparing the membrane electrode, if starting from the back membrane, it is to prepare a three-layer membrane electrode; if starting from the gas diffusion layer, it is Prepare five-layer membrane electrode or seven-layer membrane electrode.
  • the present invention provides a membrane electrode structure for a fuel cell, including:
  • the first structure layer with a thickness of 25-300 microns
  • the first catalyst layer provided on the first structure layer
  • PEM Perfluorosulfonic acid proton exchange membrane
  • the second catalyst layer on the perfluorosulfonic acid proton exchange membrane is the second catalyst layer on the perfluorosulfonic acid proton exchange membrane
  • the thickness of the first catalyst layer and the second catalyst layer are respectively 1-50 microns; the first catalyst layer corresponds to the anode or the cathode, and the second catalyst layer corresponds to the other electrode;
  • first catalyst layer and the second catalyst layer are catalytic layers formed by Pt/C catalysts, non-platinum catalysts, or other types of catalysts and ionic polymer resins or binders.
  • the first catalyst layer here can be used as an anode or a cathode respectively; the second catalyst layer can be used as an anode or a cathode respectively.
  • the first layer structure may be a backing film or a gas diffusion layer. If the first layer structure is an ordinary plastic backing film, the prepared three-layer CCM (three-layer membrane electrode); if the first layer structure is a gas diffusion layer, the prepared 5-layer or 7-layer MEA is prepared. Based on the above explanation, the above scheme is further elaborated as follows:
  • the first structure layer is a back film
  • the membrane electrode structure is specifically:
  • a static-free and dust-free back film the thickness of the back film is 25-300 microns;
  • a dry perfluorosulfonic acid proton exchange membrane coated on the first catalyst layer A dry perfluorosulfonic acid proton exchange membrane coated on the first catalyst layer;
  • the thickness of the first catalyst layer and the second catalyst layer are 1-50 microns respectively;
  • the thickness of the back film is 50-100 microns.
  • the coating operation described above can also be replaced by a coating operation.
  • the coating or coating operation can be performed once or multiple times ( ⁇ 2 times).
  • the proton exchange membrane is specifically a perfluorosulfonic acid proton exchange membrane.
  • the back film is specifically one of PTFE film (polytetrafluoroethylene film), FEP film, PET film, PI film.
  • the backing film here is one selected from the above-mentioned materials, and does not involve improving the properties of the listed films.
  • PTFE Poly tetra fluoroethylene, abbreviated as PTFE, Chinese name: polytetrafluoroethylene
  • FEP Fluorinated ethylene propylene, perfluoroethylene propylene copolymer
  • PET Polyethylene terephthalate, polyterephthalate plastic
  • PI Polyimide, polyimide
  • the first structure layer is specifically a gas diffusion layer, and the gas diffusion layer includes two sublayers:
  • the first sub-layer is a conductive and breathable material substrate layer treated with a hydrophobic material (after being hydrophobic, it has a hydrophobic inner surface);
  • the membrane electrode structure further includes:
  • the first catalyst layer provided on the microporous layer
  • Perfluorosulfonic acid proton exchange membrane arranged on the first catalyst layer
  • the second catalyst layer on the perfluorosulfonic acid proton exchange membrane is the second catalyst layer on the perfluorosulfonic acid proton exchange membrane
  • the thickness of the first catalyst layer and the second catalyst layer are 1-50 microns respectively;
  • the membrane electrode structure for a fuel cell of the present invention includes:
  • microporous layer provided on the conductive gas-permeable material substrate layer here, the microporous layer can also be called a porous layer, and the microporous layer is a more general term in the art;
  • a first catalyst layer provided on the microporous layer
  • a proton exchange membrane (PEM) layer provided on the first catalyst layer;
  • a second catalyst layer provided on the proton exchange membrane layer
  • the sprayed glue is preferably a perfluorosulfonic acid ion polymer solution, and the spray thickness is preferably less than 1 micron.
  • the gas diffusion layer can be obtained through preparation, or commercially available from public sources. There are gas diffusion layers on both sides of the original three-layer membrane electrode, and the gas diffusion layer has a two-layer structure, so there are seven layers in total.
  • the conductive and breathable material substrate layer is specifically carbon fiber cloth or carbon fiber paper. It should be noted that carbon fiber cloth or carbon fiber paper is a component inside the gas diffusion layer, which belongs to the outside of the catalytic layer.
  • the microporous layer is specifically a carbon black layer or a carbon nanotube layer.
  • the hydrophobic material is specifically a dispersion of PTFE or white carbon black.
  • the catalysts contained in the first catalyst layer and the second catalyst layer are specifically noble metals or non-noble metals containing a carbon support, and alloys thereof.
  • the catalyst includes Pt/C, Pt/Co/C, Pt/Pd/C, Fe-N-C, etc.
  • the precious metal is specifically platinum (Pt) or palladium (Pd).
  • the first catalyst layer contains an anode catalyst or a cathode catalyst
  • the second catalyst layer contains a catalyst corresponding to the other electrode; the catalyst types of the two catalyst layers are the same as the electrode types. match.
  • the present invention also provides a method for preparing a fuel cell membrane electrode, which includes the following steps:
  • PFSA perfluorosulfonic acid resin
  • the obtained first catalyst layer means that the first catalyst layer has been prepared by the previous steps, or has been provided by purchased commercial products.
  • Step a is further processed on this basis.
  • Step a is the core technology of this application, that is, after a certain process, a precursor with a first catalyst layer is prepared, such as a first catalyst layer supported by a backing film, and then the above step a is performed on the first catalyst layer. Operation, this is the use of the technology of this application.
  • the patented technician purchases the precursor with the first catalyst layer, and then further completes steps a and b on this basis, and realizes the perfluorosulfonic acid resin PFSA on the catalyst layer (catalyst layer) through step a.
  • the surface is directly formed into a film, and then the CCM is further obtained, which also falls within the protection scope of this application.
  • the first catalyst layer and the second catalyst layer mentioned above are only for the convenience of identification, and it does not mean that the catalyst layers are used in the order of the names.
  • the method for preparing a fuel cell membrane electrode of the present invention includes the following steps:
  • the pretreatment in this step mainly refers to cleaning treatment, such as removing dust and solid particles on the surface of the backing film; And include the operation of removing static electricity on the back film.
  • the first catalyst layer of 50 microns (the first catalyst layer here can be used as an anode or a cathode).
  • PFSA perfluorosulfonic acid resin
  • baking treatment at 60-120 degrees Celsius; preparing a PEM film of 10-100 microns; this step is performed one or more times, through Repeat step c several times to make the proton exchange membrane (PEM) reach the target thickness.
  • PEM proton exchange membrane
  • the drying treatment in step b and step d is specifically drying.
  • the drying operation is used to dry the catalyst slurry, thereby two catalyst layers.
  • the intermediate product coated with the catalyst slurry can be placed in an oven for drying.
  • steps of preparing catalyst slurry and perfluorosulfonic acid resin (PFSA) solution can be added between step a and step b, and the prepared slurry or solution is stored for later use.
  • This step is not indispensable.
  • the catalyst slurry and perfluorosulfonic acid resin solution can also be obtained through commercial activities (such as purchase), or they can be prepared in advance by the person implementing the patent before the preparation starts.
  • coating catalyst slurry and perfluorosulfonic acid resin the corresponding materials can be used.
  • the method of obtaining catalyst slurry and perfluorosulfonic acid resin is not limited here, and the method of obtaining it does not affect The shaping of the final product of the present invention.
  • inserting the step of preparing coating raw materials between step a and step b can make the raw materials ready for use with better results.
  • the back film is one of PEFE film, FEP film, PET film or PI film.
  • the same type of film can also be stacked with multiple layers, such as two layers.
  • the back film obtained by stacking the same type of film is also explicitly covered by this application.
  • two layers of PEFE film can be used as a backing film. But the best embodiment of this application is to use a single film.
  • step a the pretreatment is to remove dust and/or static electricity on the surface of the back film.
  • Static elimination is a non-contact operation.
  • step b the catalyst slurry is specifically coated on the backing film substrate by slit coating or spraying, screen printing or gravure printing, and then dried.
  • the catalyst slurry used in step b and step d is a certain proportion of catalyst powder and perfluorosulfonic acid resin solution, and the solvent of this catalyst slurry is aqueous solution, hydroalcoholic solution, or multiple A mixture of solvents;
  • the catalyst powder is a precious metal or non-precious metal containing a carbon carrier, and alloys thereof. More preferably, the precious metal is Pt or Pd.
  • step c As a major improvement to the above technical solution, in step c, the following are also added:
  • Free radical quencher to improve the oxidation resistance of PEM, and/or,
  • Water retention agent used to improve the water retention capacity of PEM, and/or,
  • a porous matrix support material to improve the mechanical strength of CCM is provided.
  • Free radical quencher, water-retaining agent, porous matrix support material the timing of adding these three components is: adding in the polymer slurry preparation process; the added amount: 0.1%-10% of the polymer mass ; The added types are CeO 2 , platinum black, platinum carbon and so on.
  • the porous matrix support material can be: porous PTFE, ePTFE (expanded PTFE, expanded polytetrafluoroethylene), porous PEEK (polyetheretherketone, PEEK for short, Chinese name: polyether ether ketone) and other porous polymer film support materials.
  • the perfluorosulfonic acid resin (PFSA) solution is an aqueous solution of PFSA or a hydroalcoholic solution or a mixture of multiple solvents.
  • the "multiple solvents” here include organic solvents, and alcohol is also a kind of organic solvents; for hydroalcoholic solutions, the alcohol can be methanol, ethanol, n-propanol, isopropanol, butanol One; "multiple solvents", the solvent contains several alcohols, such as a mixture of methanol, ethanol and isopropanol.
  • the present invention also provides a method for preparing a fuel cell membrane electrode, which includes the following steps:
  • a) Prepare a gas diffusion electrode with a thickness of 30 to 300 microns, the gas diffusion electrode including a first catalyst layer with a thickness of 1 to 50 microns;
  • PFSA perfluorosulfonic acid resin
  • step c Coating the catalyst slurry on the outside surface of the dried PEM membrane in a certain way; drying treatment to obtain a second catalyst layer with a thickness of 1-50 microns; then heat treatment; to obtain a finished three-layer membrane supported by the backing membrane Electrode CCM. It should also be pointed out that the heat treatment operation in step c is a necessary step.
  • the drying process is specifically a drying operation. Such as using oven or drying oven for operation.
  • the preparation method of the fuel cell membrane electrode of the present invention also includes the following steps:
  • the gas diffusion layer is attached.
  • the gas diffusion layer is bonded with the three-layer membrane electrode CCM obtained in step c through certain operations; a seven-layer membrane electrode is prepared.
  • the certain operations in step d are specifically: edge dispensing and bonding, that is, uniform dispensing along the periphery of the gas diffusion layer (manual dispensing or dispensing machines can also be used.
  • the equipment performs a glue dispensing operation), and then glues the gas diffusion layer on the second catalyst layer; or; sprays a layer of glue on the surface of the gas diffusion layer for bonding, and the sprayed glue is perfluorosulfonic acid ion polymer
  • the spray coating thickness is preferably less than or equal to 1 micron.
  • the heat treatment is performed in the range of 120 to 250 degrees Celsius.
  • the catalyst slurry used in step c is a certain proportion of catalyst powder and perfluorosulfonic acid resin solution.
  • the solvent of this catalyst slurry is an aqueous solution, a hydroalcoholic solution, or a mixture of multiple solvents. Liquid;
  • the catalyst powder is a precious metal or non-precious metal containing carbon support, and its alloys. More preferably, the precious metal is Pt or Pd.
  • the catalyst slurry used in the first catalyst layer and the second catalyst layer may be the same or different. Specifically, 1 if the same catalyst slurry is used in step c, only one type of catalyst slurry to be coated needs to be prepared; 2 if two catalyst slurries are used in step c, two catalyst slurries need to be prepared The materials should be stored separately, and should be marked, marked or labelled to distinguish the two catalyst slurries. Then, according to the predetermined design, the two catalyst slurries are respectively coated on the outer surface of the PEM membrane to form the first One catalyst layer, second catalyst layer.
  • a free radical quencher useful to improve the oxidation resistance of PEM is also added in step c. It can be further expanded to scavenging free radicals or reducing the number of free radicals or absorbing free radicals.
  • a water-retaining agent useful to improve the water-holding capacity of the PEM is also added in step c.
  • step c a porous matrix support material for improving the mechanical strength of the CCM is also added.
  • the perfluorosulfonic acid resin (PFSA) solution is an aqueous solution of PFSA or a hydroalcoholic solution or a mixture of multiple solvents.
  • the present invention also provides a method for preparing a fuel cell membrane electrode, which is used to prepare a seven-layer membrane electrode, which specifically includes the following steps:
  • the thickness of the gas diffusion layer is 30-260 microns.
  • PFSA perfluorosulfonic acid resin
  • PEM proton exchange membrane
  • An electrode On the proton exchange membrane obtained in step c, another layer of catalyst slurry is coated to form a second catalyst layer (two coatings are respectively applied to the two surfaces of the proton exchange membrane) to obtain interlayer Connect a good second electrode, the drying thickness of the catalytic layer is 1-50 microns; the polarity of the first electrode and the second electrode are opposite, when the first electrode is an anode or a cathode, the second electrode can only have the opposite polarity.
  • An electrode On the proton exchange membrane obtained in step
  • the glue to be sprayed is a perfluorosulfonic acid ion polymer solution, and the spray thickness is less than or equal to 1 micron.
  • heat treatment is performed in the range of 120-250 degrees Celsius (°C).
  • the gas diffusion layer is a commercial gas diffusion layer (obtained commercially through public channels); or; prepared by a certain method, the specific preparation method is: 1. For carbon fiber paper or carbon fiber cloth Carry out the hydrophobic material immersion sintering and carbonization treatment; 2. Afterwards, the microporous layer is coated to prepare the gas diffusion layer.
  • the catalyst slurry used in step b and step d is a certain proportion of catalyst powder and perfluorosulfonic acid resin solution, and the solvent of this catalyst slurry is aqueous solution, hydroalcoholic solution, or multiple A mixture of solvents;
  • the catalyst powder is a precious metal or non-precious metal containing a carbon carrier, and alloys thereof. More preferably, the precious metal is Pt or Pd.
  • a free radical quencher useful to improve the oxidation resistance of PEM is also added in step c.
  • a water-retaining agent useful to improve the water-holding capacity of the PEM is also added in step c.
  • step c a porous matrix support material for improving the mechanical strength of the CCM is also added.
  • the perfluorosulfonic acid resin (PFSA) solution is an aqueous solution of PFSA or a hydroalcoholic solution or a mixture of multiple solvents.
  • the perfluorosulfonic acid resin polymer can be replaced by any conductive polymer that conducts cations or conducts anions or conducts electrons, for example: sulfonated polyether ether ketone, sulfonated polyether sulfone and other cations Conductive polymers and anionic conductive polymers such as quaternized polyphenylene ether, quaternized polybenzimidazole or polyimidazole. It should also be pointed out that the perfluorosulfonic acid resin polymer and its substitutes (any conductive polymer that conducts cations or conducts anions or conducts electrons) must act as glue, and preferably can also conduct protons. Function, but not required.
  • the present invention also provides a method for preparing a fuel cell membrane electrode, which is used to prepare a seven-layer membrane electrode, which includes the following steps:
  • the equipment or device used for spray coating is: spray gun or spraying equipment.
  • the membrane electrode preparation method of other parts of the present invention uses the backing film as the coating substrate, the backing film is a general polymer film, and the technical solution can not use the backing film
  • the gas diffusion layer is directly used to replace the back membrane to prepare the 7-layer membrane electrode. This is the characteristic of this preparation method and the difference from other preparation methods
  • 2 The first catalyst layer and second catalyst layer located on both sides of the proton exchange membrane The catalyst layer functions as two electrodes (anode and cathode), and is electrically connected to the outside through the first catalyst layer and the second catalyst layer.
  • step g "spray a layer of glue on the surface of the gas diffusion layer", you can also spray a layer of glue on the second catalyst layer to replace the operation of spraying glue on the gas diffusion layer, but this operation
  • the method is not the recommended method; spraying a layer of glue on the surface of the gas diffusion layer is the best method.
  • "Spray a layer of glue” in step g refers to spraying a layer of glue on the surface of the gas diffusion layer. In the actual spraying operation, one spray or several sprays can be used Form the glue layer.
  • the first function of the glue in step g is adhesive effect; the second function is to conduct protons, but it is not necessary.
  • the substrate is selected from carbon fiber cloth or carbon fiber paper.
  • the process of the hydrophobic treatment is: immersing and sintering the carbon fiber paper in a dispersion of hydrophobic materials such as PTFE and silica. It is also necessary to point out: 1The specific conditions of impregnation and sintering: the impregnation is full wet impregnation at room temperature, and the sintering temperature is 300-400 degrees Celsius; 2the equipment used for impregnation and sintering: impregnation tank and oven; An atmosphere can also be used, and the atmosphere is air; more preferably, the atmosphere is selected as clean air, such as filtering and removing dust (removing solid particles in the air) and/or dehumidifying the air before using it as the atmosphere.
  • the catalyst slurry used in step d and step f is a certain proportion of catalyst powder and perfluorosulfonic acid resin solution, and the solvent of this catalyst slurry is an aqueous solution, a hydroalcoholic solution, or multiple Mixture of solvents.
  • the preparation process of the catalytic slurry is: Step 1, fully wet the catalyst with a small amount of water; Step 2, slowly add the perfluorosulfonic acid resin solution for dispersion; Step 3, add water or alcohol to the catalyst
  • the slurry is configured into a catalyst slurry with a mass concentration of 1%-20%; in step 4, the catalyst slurry is uniformly dispersed by ultrasonic dispersion, or a micro-jet homogenizer, a ball mill, or a combination of several dispersion methods.
  • the alcohol used is a monohydric alcohol or a polyhydric alcohol, and the polyhydric alcohol is preferably a dihydric alcohol, such as propylene glycol.
  • the catalyst powder is a carbon-supported noble metal or non-noble metal, and alloys thereof, wherein the noble metal is Pt or Pd. More specifically: 1The particle size of the catalyst powder ranges from 10 to 200nm; 2Precious metals (Pt, Pd) need to complete the catalytic function of hydrogen oxidation and oxygen reduction; 3Non-precious metals include iron, cobalt, nickel, etc.; 4Alloys include Pt/Co alloy, Pt/Ni alloy, etc.
  • a free radical quencher useful to improve the oxidation resistance of PEM is also added in step e.
  • a water-retaining agent useful to improve the water-holding capacity of the PEM is also added in step e.
  • step e a porous matrix support material for improving the mechanical strength of the CCM is also added.
  • the perfluorosulfonic acid resin (PFSA) solution is an aqueous solution of PFSA or a hydroalcoholic solution or a mixture of multiple solvents.
  • the perfluorosulfonic acid resin polymer can be replaced by any conductive polymer that conducts cations or conducts anions or conducts electrons. Furthermore, the perfluorosulfonic acid resin polymer can be replaced by cation exchange resin and anion exchange resin.
  • the present invention also provides a proton exchange membrane fuel cell system, which adopts the above-mentioned membrane electrode structure.
  • the slit coating method in the above-mentioned scheme can be replaced by spraying, screen printing, and gravure printing.
  • a free radical quencher can be added to improve the oxidation resistance of PEM
  • a water-retaining agent can improve the water-holding capacity of PEM
  • a porous matrix support material can improve the mechanical strength of CCM.
  • the above-mentioned perfluorosulfonic acid resin polymer can be replaced by any conductive polymer that conducts cations or conducts anions or conducts electrons.
  • the coating process of the above-mentioned proton exchange membrane can be decomposed into multilayer preparation to achieve the target thickness, that is: the perfluorosulfonic acid resin solution is coated (coated) on the surface of the catalyst layer multiple times, and each coating operation is A proton exchange membrane with a certain thickness can be formed, and the total thickness of the proton exchange membrane can be within a predetermined range through multiple thickness stacking.
  • the first structural layer is an ordinary plastic backing film
  • a 3-layer CCM can be prepared.
  • the prepared MEA is 5-layer or 7-layer MEA.
  • the advantage of the present invention is that the perfluorosulfonic acid resin PFSA directly forms a proton exchange membrane (PEM) on the surface of the catalyst layer. Compared with the transfer method, it has the following advantages: 1 Since the PEM film is directly formed on the surface of the catalyst layer, the catalyst is reduced. The resistance to transfer protons between the layer and the proton exchange membrane interface.
  • the mass transfer contact area is less than or equal to the projected area of the two layers; and the present invention directly forms the PEM on the surface of the catalyst layer Membrane, due to the roughness of the surface of the catalyst layer, the mass transfer contact area is larger than the projected area of the two contact surfaces, so the resistance to transfer protons is reduced, so that the efficiency of the fuel cell's work to the outside world is relatively increased, thus more energy saving; 2Enhanced The water transfer capacity between the catalyst layer and the proton exchange membrane is improved, and the proton exchange membrane can be better wetted during the working process of the battery; 3The preparation process of the proton exchange membrane is integrated into the preparation process of the membrane electrode, which simplifies the preparation process and shortens The preparation cycle, this is because the transfer method needs to prepare the catalyst layer on the back film first, and then the catalyst layer and the PEM are bonded by the transfer bonding method, which requires two steps, so the entire preparation of the transfer method The cycle is longer than the preparation method of the present invention
  • the advantage of the present invention is that after the catalyst layer of the present invention absorbs the solvent, the deformation amount is small, and it will not cause the catalytic layer and the proton exchange membrane to peel off from the back membrane during the coating operation, and can continue to rely on The supporting ability of the backing film to carry out the remaining coating operation makes the whole operation easy to realize.
  • the advantage of the present invention lies in the fact that the preparation method of the present invention (especially step three and step four) can obtain a tighter connection between the catalyst layer and the proton exchange membrane than the traditional transfer method for preparing CCM, that is, increase The strength of the connection between the catalyst layer and the proton exchange membrane; thereby weakening the degradation of battery performance and life due to the physical separation of the catalyst layer and the proton exchange membrane during battery operation.
  • the traditional transfer method requires bonding the catalyst layer and the PEM, and the bonding strength formed by the bonding operation is significantly lower than that of the present invention.
  • the present invention directly forms a film on the catalyst layer, and the transfer method adopts a bonding method (such as a glue bonding method). Therefore, the area of the connection part of the present invention is much larger than that of the traditional transfer method. Therefore, the connection strength of the membrane electrode prepared by the present invention is significantly better than that of the traditional transfer method.
  • PFSA polymer solution is directly coated on the surface of the catalyst layer (or called the catalyst layer). Due to the roughness of the surface of the catalyst layer, the present invention can increase the geometric contact area between the catalyst layer and the proton exchange membrane and increase the ions between the layers.
  • Conductivity When protons shuttle through the catalyst layer and the proton exchange membrane, the mass transfer contact area of the present invention is relatively large. This is because the proton conduction between the catalytic layer and the proton exchange membrane is determined by the connection area between the two layers, and the straight connection surface is smaller than the rough surface connection surface.
  • the coating of perfluorosulfonic acid resin on the catalytic layer can effectively improve the interlayer bonding force between the catalytic layer and the proton exchange membrane (adhesion and adhesion of the perfluorosulfonic acid resin) and increase the life span;
  • Coating the catalytic layer directly on the microporous layer can effectively prevent the separation of the microporous layer and the catalytic layer during the operation of PEMFC, and effectively improve the electronic conductivity between the two layers and the uniformity of gas dispersion;
  • Coating the catalytic layer directly on the microporous layer can effectively prevent the separation of the microporous layer and the catalytic layer during the operation of the PEMFC, and prevent the water generated in the battery from stagnating between the two layers and hindering the gas transmission to the catalytic layer ;
  • the reason for preventing water retention the close contact between the microporous layer and the catalytic layer prevents the generated water from staying in the gap due to the gap between the two layers;
  • the reason for hindering gas transmission to the catalyst layer if in two layers The formation of a water film will affect the gas passing through the gas diffusion layer to the inside of the catalytic layer;
  • This invention overcomes the phenomenon that the PEM is peeled from the back film caused by the direct coating of the catalyst slurry on the PEM in the method of preparing CCM by the single-sided coating method or the double-sided coating method, and realizes the stable preparation of CCM and simplifies the CCM Preparation process: directly coat the catalyst slurry on the PEM. Since the coated catalyst slurry contains a certain amount of water and alcohol, it has a certain swelling property to the PEM, which makes the size mismatch between the PEM and the backing film resulting in peeling; The present invention uses perfluorosulfonic acid resin (PFSA) solution to be coated on the surface of the catalyst layer. After the catalyst layer absorbs the solvent (water and alcohol), its deformation is small, which overcomes the existing PEM peeling from the back film problem;
  • PFSA perfluorosulfonic acid resin
  • the preparation process of the gas diffusion layer (GDL) can be integrated into the preparation process of the seven-layer membrane electrode, further saving time and cost.
  • FIG. 1 is a schematic diagram of an embodiment of the prior art, that is, a preparation method of MEA mentioned in the background technology part of the specification, that is, a traditional gas diffusion electrode (GDE) preparation method;
  • GDE gas diffusion electrode
  • FIG. 2 is a schematic diagram of the structure of the seven-layer membrane electrode of the present invention.
  • FIG. 3 is a schematic diagram of Embodiment 1 of the present invention.
  • FIG. 4 is a schematic diagram of Embodiment 2 of the present invention.
  • FIG. 5 is a schematic diagram of Embodiment 3 of the present invention.
  • Figure 6 is a schematic diagram of the fourth embodiment of the present invention.
  • FIG. 7 is a schematic diagram of an embodiment of the membrane electrode structure of the present invention.
  • Fig. 8 is a schematic flow chart of a preparation method of the present invention.
  • the invention discloses a preparation method of a fuel cell membrane electrode. Specifically include the following steps:
  • a) Start with a polymer film with a smooth and flat surface or its corresponding release film (such as: PEFE, FEP, PET, PI, PEEK, PSU film), etc., to remove dust and static electricity;
  • a polymer film with a smooth and flat surface or its corresponding release film such as: PEFE, FEP, PET, PI, PEEK, PSU film, etc.
  • this method can increase the geometric contact area between the catalytic layer and the proton exchange membrane, improve the ion conductivity between the layers, and effectively improve the interlayer bonding force between the catalytic layer and the proton exchange membrane. Can improve the life of membrane electrodes.
  • the invention can be extended to start with a gas diffusion layer with a catalytic layer, that is, from a traditional gas diffusion electrode (GDE) as the backing film.
  • GDE gas diffusion electrode
  • This method integrates the gas diffusion layer (GDL) into the entire preparation process, and can simply and effectively prepare 7-layer membrane electrodes.
  • GDL gas diffusion layer
  • the present invention discloses a method for preparing a fuel cell membrane electrode. Specifically include the following steps:
  • the carbon fiber paper 10 is used as the base material to perform hydrophobic treatment with PTFE or white carbon black dispersion, and after drying, the carbon black, carbon nanotubes and other materials are coated on the surface of the base material and dried to obtain a gas diffusion layer;
  • This method can integrate the process of preparing the gas diffusion layer into the seven-layer membrane electrode preparation method of this invention, and can obtain a membrane electrode with good contact between the gas diffusion layer and the catalytic layer, and the catalytic layer and the proton exchange membrane with low mass transfer resistance. , The whole process can greatly simplify the preparation process of membrane electrodes.
  • a method for preparing a fuel cell membrane electrode including the following steps:
  • Step 1 Remove dust and static electricity.
  • the details are as follows: select a back film (BL) with a thickness of 25-150 microns, such as PEFE, FEP, PET, PI film, etc., as the base material of this embodiment, and perform dust removal and static removal treatment on the surface of the back film;
  • Step 2 Coating of catalyst slurry.
  • the so-called catalyst layer coating refers to the coating of the first catalyst layer 20.
  • the specific operation is as follows: the catalyst slurry is coated on the backing film substrate by slit coating and dried, wherein the catalyst slurry is a certain proportion of catalyst powder and perfluorosulfonic acid resin solution.
  • the solvent is an aqueous solution, a hydroalcoholic solution, or a mixed solution of multiple solvents, the drying thickness of the catalytic layer is 1-50 microns, and the catalyst can be precious or non-precious metals such as Pt and Pd containing carbon supports, and alloys thereof;
  • Step 3 Polymer preparation.
  • the preparation process of the catalytic slurry is: step 1, fully wet the catalyst with a small amount of water; step 2, slowly add the perfluorosulfonic acid resin solution for dispersion; step 3, add water or alcohol to configure the catalyst slurry to 1% ⁇ A catalyst slurry with a concentration of 20% by mass; step 4, the catalyst slurry is uniformly dispersed by ultrasonic dispersion, or a micro-jet homogenizer, a ball mill, or a combination of several dispersion methods.
  • PFSA solution is diluted to a certain polymer ratio with water or alcohol based on the purchased PFSA polymer solution, and stirred and dispersed at room temperature.
  • the viscosity of the PFSA solution can be changed by means of ultrasound and heating, and the viscosity control range is adjustable from 50 to 5000 cps;
  • the formula and preparation method of the glue refer to the formula and preparation method of the PFSA solution, which are the same.
  • Step 4 Coating the catalytic layer.
  • the coating of the catalyst layer here refers to the coating of the second catalyst layer.
  • the specific operation is as follows: directly apply the perfluorosulfonic acid resin (PFSA) solution on the surface of the catalytic layer, and dry at 60-120 degrees Celsius (oven or oven, roll-to-roll coating preferably cut-off oven) to prepare 10-100 Micron PEM membrane, in which the PFSA solution is PFSA aqueous solution, hydroalcoholic solution or a mixture of multiple solvents.
  • PFSA perfluorosulfonic acid resin
  • this method can increase the geometric contact area of the catalytic layer and the proton exchange membrane to improve the ion conductivity between the layers, and this method integrates the preparation process of the proton exchange membrane into the preparation process of the membrane electrode, which greatly reduces the operating cost;
  • Step 5 Coating and drying the catalyst slurry on the outer surface side of the dried PEM.
  • the drying thickness of the catalytic layer is 1-50 microns, and the heat treatment is performed in the range of 120-250 degrees Celsius, namely The finished three-layer membrane electrode CCM supported by the back film is obtained.
  • drying operations in the present invention can be carried out with an oven or an oven.
  • a method for preparing a membrane electrode of a fuel cell includes the following steps:
  • Step 1 Polymer preparation. Refer to the polymer preparation part of Example 1.
  • the coated substrate can be extended to a gas diffusion electrode, and the thickness of the gas diffusion layer electrode can be 30-300 microns;
  • Step 2 Catalytic layer coating. Specifically: directly coating the perfluorosulfonic acid resin on the catalytic layer of the gas diffusion electrode, drying and heat treatment to obtain a proton exchange membrane with a thickness of 5 to 200 microns.
  • This method can effectively improve the gap between the catalytic layer and the proton exchange membrane. Due to the roughness of the surface of the catalytic layer, this method can increase the geometric contact area between the catalytic layer and the proton exchange membrane to improve the ion conductivity between the layers; another layer of catalyst is coated on the proton exchange membrane , To obtain another electrode with excellent interlayer connection, the thickness of the catalyst layer after drying is 1-50 microns;
  • Step three bonding of the gas diffusion layer. Specifically: Finally, the commercial gas diffusion layer or the gas diffusion layer obtained in step 2 is bonded.
  • This method can be simple edge dispensing and bonding, or spraying a layer of glue on the surface of the gas diffusion layer for bonding.
  • the sprayed glue is preferably a perfluorosulfonic acid ion polymer solution, and the spray thickness is preferably less than 1 micron.
  • the 7-layer membrane electrode prepared by this method greatly weakens the contact resistance between each layer of the membrane electrode and improves the mass transfer performance. It has good comprehensive performance, low cost, simple and easy to implement, suitable for mass centralized production, and has great practicality. value.
  • Step 1 Catalytic layer coating.
  • the specific operation is as follows:
  • the coated substrate can be directly preferably a gas diffusion layer, and the thickness of the gas diffusion layer can be 30-260 microns;
  • the catalyst is coated on the surface of the microporous layer, and the drying thickness of the catalytic layer is 1-50 microns
  • the catalyst can be precious metals or non-precious metals such as Pt and Pd containing carbon support, or non-precious metals, and their alloys.
  • Direct coating of the catalytic layer on the microporous layer can effectively prevent the separation of the microporous layer and the catalytic layer during the operation of PEMFC. It effectively improves the electronic conductivity between the two layers and the uniformity of gas dispersion, and prevents the water generated in the battery from stagnating between the two layers and hindering the gas transmission to the catalytic layer; this step forms the first catalyst layer.
  • Step 2 Polymer preparation (refer to the polymer preparation part of Example 1). After the perfluorosulfonic acid resin is prepared, the following steps are also included.
  • the catalyst layer is coated with perfluorosulfonic acid resin, dried and heat treated to obtain a proton exchange membrane with a thickness of 5 to 200 microns.
  • This method can effectively improve the interlayer bonding force between the catalyst layer and the proton exchange membrane.
  • the roughness of the surface of the layer this method can increase the geometric contact area of the catalytic layer and the proton exchange membrane to improve the ion conductivity between the layers.
  • Step 3 Catalytic layer coating.
  • Another layer of catalyst is coated on the upper layer of the proton exchange membrane to obtain another electrode with excellent interlayer connection (the general traditional method such as the transfer method cannot obtain a strong interlayer connection between the PEM and the catalytic layer Interface, and the preparation method of this application can be realized), the drying thickness of the catalytic layer is 1-50 microns; this step forms the second catalytic layer.
  • Step 4 The gas diffusion layer is attached.
  • the specific steps are as follows: Finally, the commercial gas diffusion layer or the gas diffusion layer obtained in step 2 is bonded.
  • This method can be simple edge dispensing and bonding, or spraying a layer of glue on the surface of the gas diffusion layer.
  • the sprayed glue is preferably a perfluorosulfonic acid ionomer solution, and the spray thickness is preferably less than 1 micron.
  • the 7-layer membrane electrode prepared by this method greatly weakens the contact resistance between each layer of the membrane electrode and improves the mass transfer performance. It has good comprehensive performance, low cost, simple and easy to implement, suitable for mass centralized production, and has great practicality. value.
  • Step 1 Hydrophobic treatment.
  • the coated substrate is a conductive air-permeable material such as carbon fiber cloth or carbon paper of 20 to 200 microns, preferably carbon fiber paper.
  • Hydrophobic treatment is carried out on carbon paper.
  • the process of hydrophobic treatment is to immerse and sinter the carbon paper in a solution of hydrophobic materials such as PTFE and silica.
  • the mass of the hydrophobic material accounts for 10%-50%.
  • the hydrophobic treatment can be It improves the ability of PEMFC to drain and breathe in the operating environment and basically maintain the electronic conductivity of the matrix material.
  • Step 2 Microporous layer coating.
  • the details are as follows: the hydrophobically treated carbon paper is coated with a porous layer of carbon black or carbon fiber, and the thickness after coating and drying is 10-60 microns.
  • the microporous layer 20 can further refine the gas passing through the gas diffusion layer. The partial pressure improves the uniformity of gas dispersion, improves the efficiency of water removal, and can provide physical buffer protection for the catalytic layer and the proton exchange membrane.
  • Step 3 Catalytic layer coating.
  • the details are as follows: the catalyst is coated on the surface of the microporous layer, and the drying thickness of the catalyst layer is 1-50 microns.
  • the catalyst can be Pt, Pd and other precious metals or non-precious metals containing carbon supports, and their alloys. Coating on the microporous layer can effectively prevent the separation of the microporous layer and the catalytic layer during the operation of the PEMFC, effectively improve the electronic conductivity between the two layers and the uniformity of gas dispersion, and eliminate the generation in the battery The water stays between the two layers and hinders gas transmission to the catalytic layer; this step forms the first catalytic layer.
  • Step 4 Polymer preparation (refer to the polymer preparation part of Example 1).
  • the perfluorosulfonic acid resin After the perfluorosulfonic acid resin is prepared, it also includes the following steps: coating the perfluorosulfonic acid resin on the catalytic layer, drying and heat treatment to obtain a proton exchange membrane with a thickness of 5 to 200 microns.
  • the method can effectively improve the interlayer bonding force between the catalytic layer and the proton exchange membrane. Due to the rough surface of the catalytic layer, this method can increase the geometric contact area between the catalytic layer and the proton exchange membrane and improve the ion conductivity between the layers.
  • Step 5 Catalytic layer coating.
  • the specific steps are as follows: another layer of catalyst is coated on the proton exchange membrane to obtain another electrode with excellent interlayer connection, and the drying thickness of the catalytic layer is 1-50 microns; in this step, the second catalyst layer 50 is prepared.
  • Step 6 The gas diffusion layer 70 is attached.
  • the specific steps are as follows: Finally, the commercial gas diffusion layer or the gas diffusion layer obtained in step 2 is bonded.
  • This method can be simple edge dispensing and bonding, or spraying a layer of glue on the surface of the gas diffusion layer.
  • the sprayed glue is preferably a perfluorosulfonic acid ionomer solution, and the spray thickness is preferably less than 1 micron.
  • the 7-layer membrane electrode prepared by this method greatly weakens the contact resistance between each layer of the membrane electrode and improves the mass transfer performance. It has good comprehensive performance, low cost, simple and easy to implement, suitable for mass centralized production, and has great practicality. value.
  • the present invention provides a membrane electrode structure for a fuel cell, including:
  • the first structure layer with a thickness of 25-300 microns
  • the first catalyst layer provided on the first structure layer
  • Perfluorosulfonic acid proton exchange membrane arranged on the first catalyst layer
  • the second catalyst layer on the perfluorosulfonic acid proton exchange membrane is the second catalyst layer on the perfluorosulfonic acid proton exchange membrane
  • the thickness of the first catalyst layer and the second catalyst layer are 1-50 microns respectively;
  • the first structure layer is a backing film
  • the membrane electrode structure is specifically:
  • a static-free and dust-free back film the thickness of the back film is 25-300 microns;
  • the thickness of the first catalyst layer and the second catalyst layer are 1-50 microns respectively;
  • the proton exchange membrane is specifically a perfluorosulfonic acid proton exchange membrane.
  • the back film is specifically one of PEFE film, FEP film, PET film, and PI film.
  • the backing film here is one selected from the above-mentioned materials, and does not involve improving the properties of the listed films.
  • the first structure layer is specifically a gas diffusion layer, and the gas diffusion layer includes two sublayers:
  • the first sub-layer is a conductive and breathable material substrate layer treated with a hydrophobic material
  • the membrane electrode structure further includes:
  • the first catalyst layer provided on the microporous layer
  • Perfluorosulfonic acid proton exchange membrane arranged on the first catalyst layer
  • the second catalyst layer on the perfluorosulfonic acid proton exchange membrane is the second catalyst layer on the perfluorosulfonic acid proton exchange membrane
  • the thickness of the first catalyst layer and the second catalyst layer are 1-50 microns respectively.
  • the membrane electrode structure for a fuel cell of the present invention includes:
  • microporous layer provided on the conductive gas-permeable material substrate layer can also be referred to as a porous layer;
  • a first catalyst layer provided on the microporous layer
  • a proton exchange membrane (PEM) layer provided on the first catalyst layer;
  • a second catalyst layer provided on the proton exchange membrane layer
  • the conductive and breathable material substrate layer is specifically carbon fiber cloth or carbon fiber paper.
  • the microporous layer is specifically a carbon black layer or a carbon nanotube layer.
  • the hydrophobic material is specifically a solution of PTFE or white carbon black.
  • the catalysts contained in the first catalyst layer and the second catalyst layer are specifically noble metals or non-noble metals containing a carbon support, and alloys thereof.
  • the precious metal is specifically platinum (Pt) or palladium (Pd).
  • the first catalyst layer is an anode catalyst layer
  • the second catalyst layer is a cathode catalyst layer
  • the prepared membrane electrode structure is similar to the membrane electrode obtained by the traditional method, compared with the traditional method, the connection strength between the functional layers of the membrane electrode of this invention is greatly enhanced.
  • the functional layers of the membrane electrode of the present application are in close surface contact, while the functional layers of the existing membrane electrode often have partial surface contact or partial point contact. Therefore, the membrane electrode of the present invention is different from the structure
  • the above is also distinguished from the existing membrane electrodes. This difference is mainly due to the large difference in the interface between adjacent functional layers.
  • the invention also discloses a proton exchange membrane fuel cell system, which adopts the membrane electrode structure prepared in the above-mentioned embodiment.
  • the fuel cell system can be applied in the automotive field, such as new energy vehicles (such as new energy cars, new energy buses, etc.) containing the fuel cell system. Due to the use of the membrane electrode of the present invention, the bumps and jitters of the vehicles are also It is not easy to damage the membrane electrode, which improves the working stability of the fuel cell, so that the fuel cell can be used in more complicated and harsh working conditions.
  • the fuel cell can also be used in the field of unmanned aerial vehicles to supply electric energy for unmanned aerial vehicles.
  • the fuel cell can also be used in the field of robotics to provide electrical energy for robots.
  • the fuel cell of the present invention is applied to industrial robots.

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Abstract

本发明公开了一种燃料电池用膜电极结构，包括：厚度为25～300微米的第一结构层；设于第一结构层之上的第一催化剂层；设于第一催化剂层之上的全氟磺酸质子交换膜；设于全氟磺酸质子交换膜之上的第二催化剂层；其中，所述第一催化剂层、第二催化剂层的厚度分别为1～50微米；以上各层复合后，形成膜电极结构。本发明的优势在于全氟磺酸树脂PFSA在催化层表面直接成膜，降低了催化层与质子交换膜界面间的传递质子的阻力；增强了催化层与质子交换膜间的水传递能力，在电池操作过程中可更好的润湿质子交换膜；将质子交换膜制备过程融合入膜电极的制备过程，缩短了制备周期。

Description

一种燃料电池用膜电极结构、燃料电池膜电极的制备方法及质子交换膜燃料电池系统 技术领域
本发明涉及燃料电池膜电极技术领域，尤其涉及一种燃料电池用膜电极结构，还涉及一种燃料电池膜电极的制备方法，还涉及一种质子交换膜燃料电池系统。
背景技术
燃料电池是一种电化学电池，其主要原理是将燃料和氧化剂中的化学能经氧化还原反应直接转化为电能。质子交换膜燃料电池(PEMFC)作为燃料电池领域的重要分支，除了拥有燃料电池一般性特点如能量转换效率高、环境友好之外，还具有室温下启动速度快、体积小、无电解液损失、容易排水、寿命长、比功率和比能量高等突出优点。它不仅适用于分散式电站的建设，而且适用于移动供电。它是一种新型的军用和民用移动电源。因此，质子交换膜燃料电池具有非常广阔的应用前景。
膜电极(Membrane Electrode Assembly,MEA)是质子交换膜燃料电池的核心部件，是燃料电池进行氧化还原反应的场所，主要由全氟磺酸质子交换膜(Proton Exchange Membrane,PEM)、催化剂层(Catalyst layer,CL)、气体扩散层(Gas diffusion layer,GDL)以及密封材料组成。本发明所涉及的三层膜电极(CCM)则由PEM、阳极催化层(Anode Catalyst layer,ACL)及阴极催化层(Cathode Catalyst layer,CCL)组成。本发明所涉及的五层膜电极(MEA)则由CCM及阴阳极GDL组成。CCM作为燃料电池电化学反应的基本单元，其结构设计和制备工艺方案的提出，需要以燃料电池电化学反应的基本原理和特性为理论基础，并结合其实际工作条件加以综合考量。CCM的结构设计和制备工艺技术是燃料电池的关键技术，其决定了燃料电池的工作性能。
现有的三层膜电极(CCM)制备技术主要包含(但不限)如下几种：1，双转印法，即先在基体膜上涂覆催化剂浆料干燥后得到ACL及CCL，再通过热压转印的方式将ACL及CCL接合到PEM的两侧；2，单转印法，即在具有背膜的质子交换膜(PEM)的外侧直接进行阴极(或阳极)催化剂浆料的涂覆，制备具有CCL(或ACL)的PEM，干燥后将涂覆有CCL(或ACL)的PEM从背膜剥离，再通过热压转印的方式将ACL(或CCL)贴合至PEM的另外一侧；3，双面涂覆法，即首先在具有背膜的PEM的外侧进行阴极(或阳极)催化剂浆料的直接涂覆，烘干后得到具有CCL(或ACL)的PEM，将涂覆有CCL(或ACL)的PEM从背膜剥离，再将阳极(或阴极)催化剂浆料直接涂覆至PEM的另一侧并烘干，或同时将ACL及CCL涂覆于PEM的两侧并进行烘干；4，喷涂法,即在PEM的两侧分别通过喷涂阳极催化剂浆料及阴极催化剂浆料的方式制备得到CCM；5，丝网印刷法，通过丝网印刷将催化剂浆料直接印刷至PEM的表面烘干后再进行另一侧催化层的印刷，制成CCM；6，原位制备法，通过化学及物理的方法直接将催化剂生长于PEM的两侧，形成有序催化层结构的CCM。
由此，将上述CCM的制备方法总结为两大类，一，利用催化剂浆料在PEM的两侧直接制备催化层，如直接涂覆法、喷涂法或丝印法；二，在背膜上制备催化层后，再经过转印贴合的方式将催化层与PEM贴合；或是由这两类方法的结合。
将上述方法得到的CCM两侧分别与GDL贴合即得到MEA。另外一种MEA的制备方法为传统的气体扩散电极(Gas Diffusion Electrode,GDE)制备法(如本申请的图1所示)，即将阳极催化剂浆料涂覆于GDL之上得到阳极GDE，阴极催化剂浆料涂覆于GDL之上得到阴极GDE，再通过热压的方式 将阳极GDE与阴极GDE分别接合到PEM的两侧，得到MEA。
本发明主要是针对传统的转印法进行改进。
发明内容
本发明的目的在于克服上述现有技术之不足而提供一种燃料电池用膜电极结构，在制备膜电极时，若从背膜出发则为制备三层膜电极；若从气体扩散层出发则为制备五层膜电极或者七层膜电极。
为实现上述目的，本发明提供的一种燃料电池用膜电极结构，包括：
厚度为25～300微米的第一结构层；
设于第一结构层之上的第一催化剂层；
涂覆于第一催化剂层之上的全氟磺酸质子交换膜(PEM)；
设于全氟磺酸质子交换膜之上的第二催化剂层；
其中，所述第一催化剂层、第二催化剂层的厚度分别为1～50微米；第一催化剂层对应阳极或者阴极，第二催化剂层对应另一电极；
以上各层复合后，形成膜电极结构。还需指出，所述第一催化剂层、第二催化剂层是Pt/C催化剂、非铂催化剂、或其他类型的催化剂与离子聚合物树脂或者与粘结剂形成的催化层。此处的第一催化剂层可以分别作为阳极，也可以作为阴极；第二催化剂层可以分别作为阳极，也可以作为阴极。
还需要指出的是：在进行具体制备膜电极的时候，所述第一层结构可以是背膜也可以是气体扩散层。若第一层结构为普通塑料背膜，其制备得到的是3层CCM(三层膜电极)；若第一层结构为气体扩散层，其所制备得到的是5层或者7层MEA。基于上述的解释，对上述方案进一步的阐述如下：
对上述技术方案进一步的改进或限定：所述第一结构层为背膜，该膜电极结构具体为：
无静电且无尘的背膜，所述背膜的厚度为25～300微米；
涂布于背膜之上的干燥的第一催化剂层；
涂布于第一催化剂层之上的干燥的全氟磺酸质子交换膜；
涂布于质子交换膜外侧的干燥的第二催化剂层；
其中，所述第一催化剂层、第二催化剂层的厚度分别为1～50微米；
以上各层复合后，形成背膜支撑的三层膜电极CCM。
对上述技术方案进一步的限定改进，所述背膜的厚度为50～100微米。上述的涂布操作也可以用涂覆操作进行代替。涂布或涂覆操作可以进行一次或者多次(≥2次)。
作为对上述技术方案的改进，所述质子交换膜具体是全氟磺酸质子交换膜。
作为对上述技术方案的改进，所述背膜具体是PTFE膜(聚四氟乙烯膜)、FEP膜、PET膜、PI膜中的一种膜。此处的背膜是从以上各材质的膜中选择一种，并不涉及对所列出的膜的性质进行改进。其中：PTFE(Poly tetra fluoroethylene，简写为PTFE，中文名：聚四氟乙烯)；FEP(Fluorinated ethylene propylene，全氟乙烯丙烯共聚物)；PET(Polyethylene terephthalate，聚对苯二甲酸类塑料)；PI(Polyimide，聚酰亚胺)。
作为对本发明膜电极结构的进一步的改进，所述第一结构层具体为气体扩散层，所述气体扩散层包括两个子层：
第一子层，采用疏水材料处理后的导电透气材料基材层(经过疏水处理后，具有疏水内表面)；
第二子层，涂覆于的导电透气材料基材层表面的微孔层；
所述膜电极结构还包括有：
设于微孔层之上的第一催化剂层；
设于第一催化剂层之上的全氟磺酸质子交换膜；
设于全氟磺酸质子交换膜之上的第二催化剂层；
其中，所述第一催化剂层、第二催化剂层的厚度分别为1～50微米；
以上各层复合之后，形成七层膜电极结构。
作为对本发明膜电极结构的进一步的改进，本发明的燃料电池用膜电极结构，包括：
导电透气材料基材层；
设于所述导电透气材料基材层的微孔层；此处的微孔层也可以称之为多孔层，微孔层是本领域更为通用的名词；
设于所述微孔层之上的第一催化剂层；
设于所述第一催化剂层之上的质子交换膜(PEM)层；
设于所述质子交换膜层之上的第二催化剂层；
胶合于所述第二催化剂层之上的气体扩散层(GDL)；其中，气体扩散层与第二催化剂层形成气体扩散电极；对此处的胶合操作进一步的限定：胶合操作可以为简单的边缘点胶贴合；也可为将气体扩散层表面喷覆一层胶水进行贴合，喷覆的胶水优选为全氟磺酸离子聚合物溶液，喷覆厚度优选为1微米以下。
以上各层复合之后，形成七层膜电极结构。所述气体扩散层(GDL)可以是通过制备而得到的，或者是从公开渠道商业购买得到的。在原来的三层膜电极的两侧分别有气体扩散层，而气体扩散层由两层结构，所以共计七层结构。
作为对上述技术方案的改进，所述导电透气材料基材层具体为碳纤维布或碳纤维纸。需要说明的，碳纤维布或碳纤维纸是气体扩散层里面的一个组成部分，属于在催化层的外侧。
作为对上述技术方案的改进，所述微孔层具体为碳黑层或碳纳米管层。
作为对上述技术方案的改进，所述疏水材料具体为PTFE或白炭黑的分散液。
作为对上述技术方案的改进，所述第一催化剂层、第二催化剂层中含有的催化剂，具体为含有碳载体的贵金属或非贵金属、及其合金。进一步的改进，催化剂包括Pt/C，Pt/Co/C，Pt/Pd/C，Fe-N-C等。
更为优选的，所述贵金属具体为铂(Pt)或钯(Pd)。
作为对上述技术方案的进一步的改进，所述第一催化剂层中含有阳极催化剂或阴极催化剂，第二催化剂层中含有与另一电极相对应的催化剂；两个催化剂层的催化剂种类与电极种类相匹配。
本发明还提供一种燃料电池膜电极的制备方法，包括如下步骤：
a)将全氟磺酸树脂(PFSA)溶液直接涂覆(如采用涂布的方法，涂布是涂覆的一种方式)于已得到的第一催化剂层的表面；干燥处理；制备得到PEM膜；
b)通过一定方式将催化剂浆料涂覆于干燥后的PEM膜的外侧表面；干燥处理，得到第二催化剂层；然后热处理；即得到膜电极的主体结构，即第一催化剂层-PEM-第二催化剂层的三层主体结构。此处的热处理的具体作用是：使得PEM形成结构稳定的网络，增加PEM的性能及机械寿命。
此处所说的，已得到的第一催化剂层是指，该第一催化剂层已经由之前的步骤制备得到，或者，已有购买的商业产品所提供。步骤a在此基础上进一步的进行加工。步骤a是本申请核心的技术，即经过一定的过程，制备得到具有第一催化剂层的前驱体，如由背膜支撑的第一催化剂层，然后在该第一催化 剂层上进行上述步骤a的操作，这就是利用了本申请的技术。或者说，实施专利技术者购买得到这种具有第一催化剂层的前驱体，然后在此基础上进一步的完成步骤a、步骤b，通过步骤a实现全氟磺酸树脂PFSA在催化剂层(催化层)表面直接成膜，然后进一步得到CCM，这也是落入本申请的保护范围之内的。上述所称谓的第一催化剂层、第二催化层仅仅是为了标识上的方便，并不意味着催化剂层在使用上依照此命名的先后次序进行。
作为对上述技术方案的进一步的限定，本发明的燃料电池膜电极制备方法，包括如下步骤：
a)准备背膜(此处的背膜是作为涂布基材)，并对背膜进行预处理；本步骤所谓的预处理主要指清洁处理，如去除背膜表面的灰尘、固形物颗粒；以及包括去除背膜上静电的操作。
b)通过一定方式将催化剂浆料覆于预处理后的背膜之上；干燥(此处的干燥可优选为烘干，烘干是干燥的一种实现方式)处理；制备得到厚度为1～50微米的第一催化剂层(此处的第一催化剂层可以作为阳极或者阴极)。
c)将全氟磺酸树脂(PFSA)溶液直接涂布于第一催化剂层的表面；60～120摄氏度烘干处理；制备得到10～100微米的PEM膜；该步骤执行一次或多次，通过将步骤c重复操作多次，使质子交换膜(PEM)达到目标厚度。还需指出：涂布采用狭缝涂布、凹版涂布、逗号刮刀、丝网印刷、喷涂等方式或工具。
d)通过一定方式将催化剂浆料覆于干燥后的PEM膜的外侧表面；干燥处理，得到厚度为1～50微米的第二催化剂层(此处的第二催化剂层可以作为另一电极)；然后在120～250摄氏度范围内进行热处理；即得到有背膜支撑的成品三层膜电极CCM。背膜还起到支撑作用。
作为对上述技术方案的改进，步骤b、步骤d中的干燥处理具体是烘干。采用烘干操作使催化剂浆料干燥，从而两个催化剂层。可以将涂覆有催化剂浆料的中间产品放置于烘箱之中，进行烘干。
作为对上述技术方案的改进，步骤a、步骤b之间，还可以增加制备催化剂浆料、全氟磺酸树脂(PFSA)溶液的步骤，制备好的浆料或溶液存放备用。该步骤并非并不可少，催化剂浆料、全氟磺酸树脂溶液也可以通过商业行为(如购买)而获得，也可以在制备开始之前就已经由实施本专利技术者提前准备好。在涂覆催化剂浆料，涂覆全氟磺酸树脂的时候，有相应的物料可以使用即可，此处并不限定催化剂浆料、全氟磺酸树脂的获取方式，其获取方式并不影响本发明的最终产品的成形。当然，在步骤a、步骤b之间插入制备涂覆原料的步骤，可使原料现配现用，效果更佳。
作为对上述技术方案的改进，所述背膜是PEFE膜、FEP膜、PET膜或PI膜中的一种。当然，同一种类的膜还可以叠加多层，如叠加两层，经过叠加同种膜而得到的背膜也是本申请所明确涵盖的。比如，2层PEFE膜叠加作为一个背膜使用。但本申请最佳之实施方案是单独使用一层膜。
作为对上述技术方案的改进，步骤a中，所述预处理是对背膜的表面进行除尘和\或除静电。除静电是非接触式操作。
作为对上述技术方案的改进，步骤b中，具体是通过狭缝涂布或喷涂或丝网印刷或凹版印刷的方式将催化剂浆料涂覆于背膜基材之上，并进行干燥处理。
作为对上述技术方案的改进，步骤b、步骤d中所使用的催化剂浆料为一定比例的催化剂粉末及全氟磺酸树脂溶液，此催化剂浆料的溶剂为水溶液、水醇溶液、或多种溶剂的混合液；催化剂粉末为含有碳载体贵金属或非贵金属、及其合金。更为优选的，所述贵金属为Pt或Pd。
作为对上述技术方案一个较大的改进，在步骤c中还添加有：
用以提高PEM的抗氧化性的自由基淬灭剂，和\或，
用以提高PEM的保水能力的保水剂，和\或，
用以提高CCM的机械强度的多孔基体支撑材料。
对于上述的改进，需要指出的是：
1.在这个改进中，共涉及三种可添加的组分，这些组分可以单独添加一种、两种或三种。即，基于各种目的，而选择添加不同的组分或者组分的组合。
2.自由基淬灭剂、保水剂、多孔基体支撑材料，这三种组分的加入时机为：在聚合物浆料制备过程中加入；加入的量为：聚合物质量的0.1％～10％；加入的种类为CeO 2、铂黑、铂碳等。
3.如果加入自由基淬灭剂、保水剂、多孔基体支撑材料中的两种或三种，互相之间不会干扰各自的正常功能。
4.多孔基体支撑材料可以是：多孔PTFE、ePTFE(expanded PTFE，膨体聚四氟乙烯)、多孔PEEK(polyetheretherketone，简称PEEK，中文名：聚醚醚酮)等多孔聚合物薄膜支撑材料。
作为对上述技术方案的改进，步骤c中，全氟磺酸树脂(PFSA)溶液为PFSA的水溶液或水醇溶液或多种溶剂的混合液。还需要指出的是：此处的“多种溶剂”包含有机溶剂，另外醇也是有机溶剂的一种；水醇溶液，醇可以是甲醇、乙醇、正丙醇、异丙醇、丁醇中的一种；“多种溶剂”，溶剂里面含有几种醇类，例如有甲醇、乙醇和异丙醇的混合液。
本发明还提供燃料电池膜电极的制备方法，包括如下步骤：
a)准备厚度为30～300微米的气体扩散电极，该气体扩散电极包括有厚度分别为1～50微米的第一催化剂层；
b)在气体扩散电极的第一催化剂层上直接进行全氟磺酸树脂(PFSA)溶液的涂覆；干燥(优选为烘干，烘干为干燥方式的一种)处理；制备得到厚度为5～200微米的质子交换膜(PEM)；
c)通过一定方式将催化剂浆料覆于干燥后的PEM膜的外侧表面；干燥处理，得到厚度为1～50微米的第二催化剂层；然后热处理；即得到有背膜支撑的成品三层膜电极CCM。还需指出，步骤c中的热处理操作为必须的步骤。
作为对上述技术方案的改进，干燥处理具体为烘干操作。如采用烘箱或者干燥箱进行操作。
作为对上述技术方案的改进，本发明的燃料电池膜电极的制备方法，还包括有如下步骤:
d)气体扩散层贴合，通过一定操作将气体扩散层与步骤c得到的三层膜电极CCM进行黏合；制备得到七层膜电极。
作为对上述技术方案的改进，步骤d中的一定操作，具体是：边缘点胶贴合，即沿着气体扩散层的周缘均匀的点胶(可以手动的点胶，也可以采用点胶机等设备进行点胶操作)，然后将气体扩散层胶黏在第二催化剂层之上；或者；将气体扩散层表面喷覆一层胶水进行贴合，喷覆的胶水为全氟磺酸离子聚合物溶液，喷覆厚度优选为小于等于1微米,。
作为对上述技术方案的改进，所述热处理是在120～250摄氏度范围内进行热处理。
作为对上述技术方案的改进，步骤c中所使用的催化剂浆料为一定比例的催化剂粉末及全氟磺酸树脂溶液，此催化剂浆料的溶剂为水溶液、水醇溶液、或多种溶剂的混合液；催化剂粉末为含有碳载体贵金属或非贵金属、及其合金。更为优选的，所述贵金属为Pt或Pd。
还需要指出的是，步骤c中，在第一催化剂层、第二催化剂层中所使用的催化剂浆料可以为同一种，也可以不是同一种。具体的，①若步骤c中采用同一种催化剂浆料，则只需要准备将涂覆的一种催化剂浆料即可；②若步骤c中采用两种催化剂浆料，则需要准备两种催化剂浆料并分开存放，且应当做好标记、记号或标签，以使两种催化剂浆料区别开，然后按照预定的设计，将两种催化剂浆料分别涂覆于PEM膜的外表面，分别形成第一催化剂层、第二催化剂层。
作为对上述技术方案的改进，在步骤c中还添加有用以提高PEM的抗氧化性的自由基淬灭剂。还可以更进一步的拓展为清除自由基或者降低自由基数量或者吸收自由基的物质。
作为对上述技术方案的改进，在步骤c中还添加有用以提高PEM的保水能力的保水剂。
作为对上述技术方案的改进，在步骤c中还添加用以提高CCM的机械强度的多孔基体支撑材料。
作为对上述技术方案的改进，步骤c中，全氟磺酸树脂(PFSA)溶液为PFSA的水溶液或水醇溶液或多种溶剂的混合液。
本发明还提供一种燃料电池膜电极的制备方法，用于制备七层膜电极，具体包括如下步骤：
a)准备两份气体扩散层，气体扩散层的厚度为30～260微米。
b)在第一份气体扩散层的微孔层的表面进行催化剂浆料的涂覆，烘干，得到厚度为1～50微米的第一催化剂层；第一催化剂层为第一电极。
c)在催化层上进行全氟磺酸树脂(PFSA)溶液的涂覆，烘干，热处理，得到厚度为5～200微米的质子交换膜(PEM)。
d)在经步骤c得到的质子交换膜上，再进行一层催化剂浆料的涂覆，形成第二催化剂层(两次涂覆分别涂覆于质子交换膜的两个表面)，得到层间连接优良的第二电极，催化层烘干厚度为1～50微米；第一电极、第二电极的极性相反，当第一电极为阳极或阴极时，第二电极只能相反极性的另一种电极。
e)采用一定贴合方法将另一气体扩散层与第二催化剂层贴合；优选的，所述贴合方法为边缘点胶贴合，或，将气体扩散层表面喷覆一层胶水进行贴合，喷覆的胶水为全氟磺酸离子聚合物溶液，喷覆厚度小于等于1微米。
作为对上述技术方案的改进，在120～250摄氏度(℃)范围内进行热处理。
作为对上述技术方案的改进，所述气体扩散层为商业气体扩散层(通过公开渠道商业购买而获得)；或；通过一定方法制备而成，具体制备方法是：1，对碳纤维纸或碳纤维布进行疏水材料浸渍烧结及碳化处理；2，之后进行微孔层的涂布，制备得到气体扩散层。
作为对上述技术方案的改进，步骤b、步骤d中所使用的催化剂浆料为一定比例的催化剂粉末及全氟磺酸树脂溶液，此催化剂浆料的溶剂为水溶液、水醇溶液、或多种溶剂的混合液；催化剂粉末为含有碳载体贵金属或非贵金属、及其合金。更为优选的，所述贵金属为Pt或Pd。
作为对上述技术方案的改进，在步骤c中还添加有用以提高PEM的抗氧化性的自由基淬灭剂。
作为对上述技术方案的改进，在步骤c中还添加有用以提高PEM的保水能力的保水剂。
作为对上述技术方案的改进，在步骤c中还添加用以提高CCM的机械强度的多孔基体支撑材料。
作为对上述技术方案的改进，步骤c中，全氟磺酸树脂(PFSA)溶液为PFSA的水溶液或水醇溶液或多种溶剂的混合液。
作为对上述技术方案的改进，所述全氟磺酸树脂聚合物可由任何传导阳离子或者传导阴离子或传导电子的导电聚合物代替，例如：如磺化聚醚醚酮，磺化聚醚砜等阳离子导电聚合物及季铵化聚苯醚、季铵化聚苯并咪唑或聚咪唑等阴离子导电聚合物等。还需要指出的是：全氟磺酸树脂聚合物及其替代物(任何传导阳离子或者传导阴离子或传导电子的导电聚合物)，都必须起到胶水的作用，最好是也能起到传导质子作用，但不是必须的。
本发明还提供一种燃料电池膜电极的制备方法，用于制备七层膜电极，包括如下步骤：
a)选择20～200微米厚的导电透气材料为涂布的基材；
b)对基材进行疏水处理；
c)在疏水处理后的基材上进行微孔层的涂布；
d)在微孔层的表面进行催化剂浆料的涂覆，烘干(也可以选择其它的干燥方式)，形成厚度为1～50微米的第一催化剂层；第一催化剂层作为第一电极；
e)在催化层上进行全氟磺酸树脂的涂覆，烘干(也可以选择其它的干燥方式)、热处理得到厚度为5～200微米厚的质子交换膜(PEM)；
f)在质子交换膜上再进行一层催化剂浆料的涂覆，得到层间连接优良的另外一个电极(第二电极)，烘干，得到厚度为1～50微米的第二催化剂层；第一电极、第二电极为极性相反的两个电极；
g)采用一定贴合方法将另一气体扩散层与第二催化剂层贴合；优选的，所述贴合方法为边缘点胶贴合，或，将气体扩散层表面喷覆一层胶水进行贴合，喷覆的胶水为全氟磺酸离子聚合物溶液，喷覆厚度小于等于(≤)1微米。步骤G中，喷覆所用的设备或装置为：喷枪，或者喷涂设备。
对于上述的制备方法，还需要指出的是：①本发明其它部分的膜电极制备方法是以背膜作为涂布基材的，背膜为一般的聚合物薄膜，而本技术方案可以不用背膜，直接用气体扩散层来代替背膜来进行7层膜电极的制备，这是本制备方法的特点、与其它制备方法的区别点；②位于质子交换膜两侧的第一催化剂层、第二催化剂层，起到了两个电极(阳极和阴极)的功能，通过第一催化剂层、第二催化剂层与外界进行电连接。③步骤g中，“将气体扩散层表面喷覆一层胶水”，也可以在第二催化剂层上喷覆一层胶水，用以替代在气体扩散层上喷覆胶水的操作，但是这种操作方式并不是建议的方式；在气体扩散层表面喷覆一层胶水的方式为最佳方式。④步骤g中的“喷覆一层胶水”，指的是在气体扩散层的表面喷覆形成一层胶水层，在实际的喷覆操作中，可以通过一次喷覆或者数次的喷覆操作形成该胶水层。⑤步骤g中的胶水，第一功能是胶黏作用；第二个功能为可以传导质子，但不是必须。
作为对上述技术方案的改进，所述基材选自碳纤维布或碳纤维纸。
作为对上述技术方案的改进，所述疏水处理的过程为：将碳纤维纸在疏水材料如PTFE、白炭黑的分散液进行浸渍并烧结处理。还需要指出的是：①浸渍、烧结的具体条件：浸渍为常温下全湿式浸渍，烧结温度为300～400摄氏度；②浸渍、烧结各自采用的设备：浸渍池，烘箱；③在烧结过程中，还可以采用气氛，所述气氛为空气；更为优选的，气氛选为洁净的空气，如将空气进行过滤除尘(去除空气中的固体颗粒杂质)和\或除湿操作后再作为气氛使用。
作为对上述技术方案的改进，步骤d、步骤f中所使用的催化剂浆料为一定比例的催化剂粉末及全氟磺酸树脂溶液，此催化剂浆料的溶剂为水溶液、水醇溶液、或多种溶剂的混合液。还需要指出的是：①催化浆料的制备过程为：步骤1，将催化剂用少量水充分润湿；步骤2，缓慢加入全氟磺酸树脂溶液进行分散；步骤3，加入水或者醇将催化剂浆料配置成1％～20％质量浓度的催化剂浆料；步骤4，通过超声分散、或者微射流匀质机或者球磨机或者几种分散方式的组合将催化剂浆料分散均匀。②水醇溶液中，所使用的醇是一元醇或者多元醇，多元醇中优选为二元醇，如丙二醇。
作为对上述技术方案的改进，催化剂粉末为含有碳载体贵金属或非贵金属、及其合金，其中，所述贵金属为Pt或Pd。更为具体的：①该催化剂粉末的粒径范围为10～200nm；②贵金属(Pt、Pd)需要完成氢氧化和氧还原的催化功能；③非贵金属包括铁、钴、镍等；④合金包括Pt/Co合金、Pt/Ni合金等。
作为对上述技术方案的改进，在步骤e中还添加有用以提高PEM的抗氧化性的自由基淬灭剂。
作为对上述技术方案的改进，在步骤e中还添加有用以提高PEM的保水能力的保水剂。
作为对上述技术方案的改进，在步骤e中还添加用以提高CCM的机械强度的多孔基体支撑材料。
作为对上述技术方案的改进，步骤e中，全氟磺酸树脂(PFSA)溶液为PFSA的水溶液或水醇溶液或多种溶剂的混合液。
作为对上述技术方案的改进，所述全氟磺酸树脂聚合物可由任何传导阳离子或者传导阴离子或传导电子的导电聚合物代替。更进一步的，所述全氟磺酸树脂聚合物可由阳离子交换树脂及阴离子交换树脂代替。
本发明还提供一种质子交换膜燃料电池系统，所述燃料电池系统采用上述的膜电极结构。
还需要指出的是，本申请中的技术方案还存在一些替代方案，这些替代方案也落入本申请的保护范围之内：
a)上述所述方案中的狭缝涂布方式可以用喷涂、丝网印刷、凹版印刷代替。
b)上述发明制备PEM过程中可以添加自由基淬灭剂提高PEM的抗氧化性、保水剂提高PEM的保水能力、以及多孔基体支撑材料提高CCM的机械强度。
c)上述全氟磺酸树脂聚合物可以替代为任何传导阳离子或者传导阴离子或传导电子的导电聚合物。
d)上述质子交换膜的涂布过程可以分解为多层制备达到目标厚度，即：将全氟磺酸树脂溶液通过多次的涂布(涂覆)于催化剂层表面，每一次涂覆操作都可以形成一定厚度的质子交换膜，通过多次的厚度叠加可以使总的质子交换膜厚度位于所预先规定的区间范围之内。
本发明的有益效果是：
1.在本发明中，若第一结构层为普通塑料背膜，则可以制备得到3层CCM。若第一结构层为气体扩散层，其所制备得到的是5层或者7层MEA。本发明的优势在于全氟磺酸树脂PFSA在催化层表面直接形成质子交换膜(PEM)，相较于转印法，具有如下的优点：①由于直接在催化剂层表面形成PEM膜，降低了催化剂层与质子交换膜界面间的传递质子的阻力，由于转印法需要将催化剂层与PEM贴合，所以传质接触面积小于等于两层的投影面积；而本发明直接在催化剂层表面直接形成PEM膜，由于催化剂层表面的粗糙特性，所以传质接触面积大于两层接触面的投影面积，所以降低了传递质子的阻力，从而使燃料电池向外界做功的效率相对增加，从而更加节能；②增强了催化剂层与质子交换膜间的水传递能力，在电池工作过程中可更好的润湿质子交换膜；③将质子交换膜制备过程融合入膜电极的制备过程，简化了制备工艺，缩短了制备周期，这是由于转印法需要先再背膜上制备催化剂层，再经过转印贴合的方式将催化剂层与PEM贴合，这就需要两步操作，所以转印法的整个的制备周期就比本发明的制备方法要长，本发明相比直接买来质子交换膜进行涂布的制备工艺简单，连续。
2.本发明的优势还在于：本发明的催化剂层在吸收溶剂后，形变量较小，在涂布操作过程中不会导致催化层及质子交换膜从背膜剥离的情况出现，可继续依靠背膜的支撑能力来进行剩余的涂布操作，使整个操作易于实现。
3.本发明的优势最后还在于本发明的制备方法(尤其是步骤三及步骤四)相较于传统转印法制备CCM可得到更紧密的催化剂层与质子交换膜间的连接，即增加了催化剂层、质子交换膜之间的连接强度；从而削弱了由于电池运行过程中因催化层与质子交换膜的物理剥离而导致的电池性能及寿命的衰减。传统的转印法由于需要将催化剂层与PEM贴合，而贴合操作所形成的连接强度是显著低于本发明的。本发明通过在催化剂层直接成膜，而转印法采用贴合的方式(如点胶贴合方式)，所以，本发明的连接部位的面积远大于传统转印法的连接部位的面积，所以，本 发明制备的膜电极，其连接强度显著优于传统的转印法。
4.本申请的关键技术点：
a)将PFSA聚合物溶液直接涂布与催化剂层(或称之为催化层)表面，由于催化剂层表面的粗糙特性，本发明可提高催化剂层与质子交换膜的几何接触面积提高层间的离子导通能力；质子穿梭催化剂层、质子交换膜时，本发明的传质接触面积较大。这是由于催化层与质子交换膜间的质子传导决定于两层之间连接的面积，直线的连接面要小于粗糙表面的连接面。
b)在催化层上进行全氟磺酸树脂的涂覆可有效提高催化层与质子交换膜间的层间结合力(全氟磺酸树脂的胶粘、粘合作用)，提高寿命；
c)将催化层直接涂覆于微孔层之上可有效预防PEMFC在运行过程中微孔层和催化层的分离，有效的提高了两层之间的电子传导能力及气体分散的均匀度；
d)将催化层直接涂覆于微孔层之上可有效预防PEMFC在运行过程中微孔层和催化层的分离，杜绝了电池中产生的水在两层间滞留并阻碍气体传输至催化层；杜绝水的滞留的原因：微孔层和催化层间紧密的接触使得产生的水不会因为两层之间存在空隙而滞留在空隙内；阻碍气体传输至催化剂层的原因：如果在两层间产生水膜则会影响气体穿过气体扩散层到达催化层内部；
e)此发明克服了单面涂布法或双面涂布法制备CCM的方法中，在PEM直接涂布催化剂浆料导致的PEM从背膜剥离的现象，实现了稳定制备CCM以及简化了CCM制备过程；直接在PEM上涂布催化剂浆料，由于涂布的催化剂浆料包含一定的水和醇，其对PEM有一定的溶胀性，使得PEM与背膜间形成尺寸不匹配而导致剥离；而本发明采用在催化剂层表面涂覆全氟磺酸树脂(PFSA)溶液，催化剂层在吸收溶剂(含水和醇)后，其形变量较小，就克服了现有了PEM从背膜剥离的问题；
f)将质子交换膜(PEM)的制备过程直接融入三层膜电极(CCM)的制备流程中，节约成本；
g)可将气体扩散层(GDL)的制备过程融入到七层膜电极的制备流程中，进一步节约时间及成本。
附图说明
图1是现有技术一实施例的示意图，即说明书背景技术部分提及的一种MEA的制备方法，即传统的气体扩散电极(GDE)制备法；
图2是本发明的七层膜电极结构示意图；
图3是本发明实施例一的示意图；
图4是本发明实施例二的示意图；
图5是本发明实施例三的示意图；
图6是本发明实施例四的示意图；
图7是本发明的膜电极结构的一实施例的示意图；
图8是本发明一制备方法的流程示意图。
附图标记：
碳纤维纸层，10；微孔层，20；第一催化剂层，30；质子交换膜，40；第二催化剂层，50；气体扩散电极，60；气体扩散层，70；
背膜，11。
本发明目的的实现、功能特点及优点将结合实施例，参照附图做进一步说明。
具体实施方式
本发明公开了一种燃料电池膜电极的制备方法。具体包括如下步骤：
a)以表面光滑平整的聚合物薄膜或者与其对应的离型膜(如：PEFE、FEP、PET、PI、PEEK、PSU膜)等开始，进行除尘及除静电处理；
b)对背膜11进行催化剂浆料的涂覆，烘干得到催化层；
c)在催化层上再进行质子交换膜30的涂布，烘干，并进行热处理；
d)在质子交换膜外侧再进行一层催化剂的涂布，烘干，热处理；得到三层膜电极CCM。
由于催化层表面的粗糙特性，此法可提高催化层与质子交换膜的几何接触面积、提高层间的离子导通能力，并可有效提高催化层与质子交换膜间的层间结合力，还能提高膜电极寿命。
在此基础上此发明可扩展为从具有催化层气体扩散层开始，即从传统的气体扩散电极(GDE)为背膜开始。该燃料电池膜电极的制备方法，具体包括如下步骤：
a)在气体扩散层的催化剂层上进行质子交换膜的涂布，烘干，并进行热处理；
b)在质子交换膜外侧再进行一层催化剂浆料的涂布，烘干，热处理；
c)将上述所制备产品与已有的气体扩散层进行贴合处理，得到完整的7层膜电极。
此种方法将气体扩散层(GDL)融入到整个制备流程中，可简单、有效的制备得到7层膜电极。
再进一步的扩展，本发明公开了一种燃料电池膜电极的制备方法。具体包括如下步骤：
a)将碳纤维纸10作为基材用PTFE或白炭黑分散液进行疏水处理，烘干后将碳黑、碳纳米管等材料涂覆于基材表面，烘干，得到气体扩散层；
b)在气体扩散层70的表面进行催化剂浆料涂布，烘干，得到第一催化剂层；
c)对上述涂覆有催化剂层的气体扩散层催化剂侧进行质子交换膜的涂布，烘干，并进行热处理；
d)在质子交换膜外侧再进行一层催化剂的涂布，烘干，热处理；得到第二催化剂层；
e)将上述所制备的产品与已有的气体扩散层进行贴合处理(将气体扩散层分别贴合在第一催化剂层、第二催化剂层的表面)，得到完整的7层膜电极(如图2所示)。
此种方法可将制备气体扩散层的过程融入到此发明的七层膜电极制备方法之中，可以得到气体扩散层与催化层、催化层与质子交换膜间良好接触传质阻力小的膜电极，整个流程可大大简化膜电极的制备过程。
实施例一
请参阅图3，一种燃料电池膜电极的制备方法，包括如下步骤：
a)步骤一：除尘除静电。具体如下，选择25～150微米厚度的背膜(BL)，如PEFE、FEP、PET、PI膜等，作为此实施方案的基体材料，对背膜表面进行除尘及除静电等处理；
b)步骤二：催化剂浆料的涂布。所谓的催化层涂布指的是第一催化剂层20的涂布。具体操作如下：通过狭缝涂布将催化剂浆料涂覆于背膜基材上，并进行干燥处理，其中催化剂浆料为一定比例的催化剂粉末及全氟磺酸树脂溶液，此催化剂浆料的溶剂为水溶液、水醇溶液、或多种溶剂的混合液，催化层烘干厚度为1～50微米，催化剂可为含有碳载体的Pt、Pd等贵金属 或非贵金属、及其合金；
c)步骤三：聚合物制备。催化浆料的制备过程为：步骤1，将催化剂用少量水充分润湿；步骤2，缓慢加入全氟磺酸树脂溶液进行分散；步骤3，加入水或者醇将催化剂浆料配置成1％～20％质量浓度的催化剂浆料；步骤4，通过超声分散、或者微射流匀质机或者球磨机或者几种分散方式的组合将催化剂浆料分散均匀。全氟磺酸树脂溶液的配方和制备方法：PFSA溶液，为在购买得到的PFSA聚合物溶液的基础上用水或者醇类稀释到一定的聚合物的比例，室温下搅拌分散。可通过超声及加热的方式改变PFSA溶液的粘度，粘度控制范围为50～5000cps可调；胶水的配方和制备方法参照PFSA溶液配方和制备方法，二者相同。
d)步骤四：催化层涂布。此处的催化层涂布指的是第二催化剂层的涂布。具体操作如下：将全氟磺酸树脂(PFSA)溶液直接涂布于催化层的表面，60～120摄氏度烘干(烘箱或烤炉，卷对卷涂布优选隔断烘箱)，制备得到10～100微米的PEM膜，其中PFSA溶液为PFSA的水溶液、水醇溶液或多种溶剂的混合液，此方法可有效提高催化层与质子交换膜间的层间结合力提高寿命，并且由于催化层表面的粗糙特性，此法可提高催化层与质子交换膜的几何接触面积提高层间的离子导通能力，再而此方法将质子交换膜的制备过程融入膜电极的制备流程，大大降低了操作成本；
e)步骤五：在干燥后的PEM的外表面侧再进行一步催化剂浆料的涂布，烘干，催化层烘干厚度为1～50微米，并在120～250摄氏度范围内进行热处理，即得到有背膜支撑的成品三层膜电极CCM。
还需指出：在本发明中出现的烘干操作都可以用烘箱或烤炉进行。
实施例二
请参阅图4，一种燃料电池膜电极的制备方法，包括如下步骤：
a)步骤一：聚合物制备。参照实施例一种的聚合物制备部分。
此外，涂布基材可扩展为气体扩散电极，气体扩散层电极的厚度可为30～300微米；
b)步骤二：催化层涂布。具体是：在气体扩散电极的催化层上直接进行全氟磺酸树脂的涂覆，烘干热处理得到厚度为5～200微米厚的质子交换膜，此方法可有效提高催化层与质子交换膜间的层间结合力，由于催化层表面的粗糙特性，此法可提高催化层与质子交换膜的几何接触面积提高层间的离子导通能力；在质子交换膜上再进行一层催化剂的涂覆，得到层间连接优良的另外一个电极，催化剂层烘干后厚度为1～50微米；
c)步骤三：气体扩散层贴合。具体是：最后进行商业气体扩散层或由步骤二得到的气体扩散层的贴合，此法可以为简单的边缘点胶贴合，也可为将气体扩散层表面喷覆一层胶水进行贴合，喷覆的胶水优选为全氟磺酸离子聚合物溶液，喷覆厚度优选为1微米以下。
此法制备得到的7层膜电极极大的削弱了膜电极各层间的接触电阻提高传质性能，综合性能好、成本低廉、简单易行、适合批量化集中式生产，具有很大实用化价值。
实施例三
请参阅图5，一种燃料电池膜电极的制备方法，包括如下步骤：
a)步骤一：催化层涂布。具体操作如下：涂布基材可直接优选为气体扩散层，气体扩散层的厚度可为30～260微米；在微孔层的表面进行催化剂的涂覆，催化层烘干厚度为1～50微米，催化剂可为含有碳载体的Pt、Pd等贵金属或非贵金属、及其合金，将催化层直接涂覆于微孔层之上可有效预防PEMFC在运行过程中微孔层和催化层的分离，有效的提高了两层之间的电 子传导能力及气体分散的均匀度，并杜绝了电池中产生的水在两层间滞留并阻碍气体传输至催化层；此步骤形成第一催化剂层。
b)步骤二：聚合物制备(参照实施例一的聚合物制备部分)。在制备得到全氟磺酸树脂后，还包括如下的步骤。在催化层上进行全氟磺酸树脂的涂覆，烘干热处理得到厚度为5～200微米厚的质子交换膜，此方法可有效提高催化层与质子交换膜间的层间结合力，由于催化层表面的粗糙特性，此法可提高催化层与质子交换膜的几何接触面积提高层间的离子导通能力。
c)步骤三：催化层涂布。具体步骤如下：在质子交换膜上层再进行一层催化剂的涂覆，得到层间连接优良的另外一个电极(一般的传统方法如转印法，并不能得到PEM与催化层层间连接很强的界面，而本申请的制备方法可以实现)，催化层烘干厚度为1～50微米；此步骤形成第二催化剂层。
d)步骤四：气体扩散层贴合。具体步骤如下：最后进行商业气体扩散层或由步骤二得到的气体扩散层的贴合，此法可以为简单的边缘点胶贴合，也可为将气体扩散层表面喷覆一层胶水进行贴合，喷覆的胶水优选为全氟磺酸离子聚合物溶液，喷覆厚度优选为1微米以下。
此法制备得到的7层膜电极极大的削弱了膜电极各层间的接触电阻提高传质性能，综合性能好、成本低廉、简单易行、适合批量化集中式生产，具有很大实用化价值。
实施例四
请参阅图6，一种燃料电池膜电极的制备方法，包括如下步骤：
a)步骤一：疏水处理。具体如下：涂布的基材为20～200微米的碳纤维布或碳纸等导电透气材料，优选为碳纤维纸。在碳纸上进行疏水处理，疏水处理的过程为将碳纸在疏水材料如PTFE、白炭黑的溶液等进行浸渍并烧结处理，疏水材料质量占比为10％～50％，疏水处理的可在提高PEMFC在操作使用环境中排水透气的能力并基本维持基体材料的电子导电能力。
b)步骤二：微孔层涂布。具体如下：对疏水处理的碳纸进行炭黑或碳纤维等的多空层的涂布，涂布烘干后厚度为10～60微米，微孔层20可进一步将通过气体扩散层的气体进行细分压提高气体的分散均匀度，提高水排除的效率，并可以对催化层及质子交换膜提供物理缓冲保护。
c)步骤三：催化层涂布。具体如下：在微孔层的表面进行催化剂的涂覆，催化层烘干厚度为1～50微米，催化剂可为含有碳载体的Pt、Pd等贵金属或非贵金属、及其合金，将催化层直接涂覆于微孔层之上可有效预防PEMFC在运行过程中微孔层和催化层的分离，有效的提高了两层之间的电子传导能力及气体分散的均匀度，并杜绝了电池中产生的水在两层间滞留并阻碍气体传输至催化层；本步骤形成第一催化剂层。
d)步骤四：聚合物制备(参考实施例一种的聚合物制备部分)。在制备得到全氟磺酸树脂后，还包括有如下的步骤：在催化层上进行全氟磺酸树脂的涂覆，烘干、热处理后，得到厚度为5～200微米的质子交换膜，此方法可有效提高催化层与质子交换膜间的层间结合力，由于催化层表面的粗糙特性，此法可提高催化层与质子交换膜的几何接触面积提高层间的离子导通能力。
e)步骤五：催化层涂布。具体步骤如下：在质子交换膜上层再进行一层催化剂的涂覆，得到层间连接优良的另外一个电极，催化层烘干厚度为1～50微米；此步骤制备得到第二催化剂层50。
f)步骤六：气体扩散层70贴合。具体步骤如下：最后进行商业气体扩散层或由步骤二得到的气体扩散层的贴合，此法可以为简单的边缘点胶贴合，也可为将气体扩散层表面喷覆一层胶水 进行贴合，喷覆的胶水优选为全氟磺酸离子聚合物溶液，喷覆厚度优选为1微米以下。
此法制备得到的7层膜电极极大的削弱了膜电极各层间的接触电阻提高传质性能，综合性能好、成本低廉、简单易行、适合批量化集中式生产，具有很大实用化价值。
实施例五
本发明提供的一种燃料电池用膜电极结构，包括：
厚度为25～300微米的第一结构层；
设于第一结构层之上的第一催化剂层；
设于第一催化剂层之上的全氟磺酸质子交换膜；
设于全氟磺酸质子交换膜之上的第二催化剂层；
其中，所述第一催化剂层、第二催化剂层的厚度分别为1～50微米；
以上各层复合后，形成背膜支撑的三层膜电极CCM。
对上述技术方案进一步的改进：所述第一结构层为背膜，该膜电极结构具体为：
无静电且无尘的背膜，所述背膜的厚度为25～300微米；
涂布于背膜之上的干燥的第一催化剂层；
涂布于第一催化剂层之上的干燥的质子交换膜；
涂布于质子交换膜外侧的干燥的第二催化剂层；
其中，所述第一催化剂层、第二催化剂层的厚度分别为1～50微米；
以上各层复合后，形成背膜支撑的三层膜电极CCM。
作为对上述技术方案的改进，所述质子交换膜具体是全氟磺酸质子交换膜。
作为对上述技术方案的改进，所述背膜具体是PEFE膜、FEP膜、PET膜、PI膜中的一种膜。此处的背膜是从以上各材质的膜中选择一种，并不涉及对所列出的膜的性质进行改进。
作为对本发明膜电极结构的进一步的改进，所述第一结构层具体为气体扩散层，所述气体扩散层包括两个子层：
第一子层，采用疏水材料处理后的导电透气材料基材层；
第二子层，涂覆于的导电透气材料基材层表面的微孔层；
所述膜电极结构还包括有：
设于微孔层之上的第一催化剂层；
设于第一催化剂层之上的全氟磺酸质子交换膜；
设于全氟磺酸质子交换膜之上的第二催化剂层；
其中，所述第一催化剂层、第二催化剂层的厚度分别为1～50微米。
作为对本发明膜电极结构的进一步的改进，本发明的燃料电池用膜电极结构，包括：
导电透气材料基材层；
设于所述导电透气材料基材层的微孔层；此处的微孔层也可以称之为多孔层；
设于所述微孔层之上的第一催化剂层；
设于所述第一催化剂层之上的质子交换膜(PEM)层；
设于所述质子交换膜层之上的第二催化剂层；
胶合于所述第二催化剂层之上的气体扩散层(GDL)；其中，气体扩散层与第二催化剂层形成气体扩散电极60；
以上各层复合之后，形成七层膜电极结构。
作为对上述技术方案的改进，所述导电透气材料基材层具体为碳纤维布或碳纤维纸。
作为对上述技术方案的改进，所述微孔层具体为碳黑层或碳纳米管层。
作为对上述技术方案的改进，所述疏水材料具体为PTFE或白炭黑的溶液。
作为对上述技术方案的改进，所述第一催化剂层、第二催化剂层中含有的催化剂，具体为含有碳载体的贵金属或非贵金属、及其合金。
更为优选的，所述贵金属具体为铂(Pt)或钯(Pd)。
作为对上述技术方案的进一步的改进，，所述第一催化剂层是阳极催化剂层，所述第二催化剂层是阴极催化剂层。
虽然制备得到的膜电极结构与传统方法得到的膜电极大体结构相类似，但相较于传统方式，此发明的膜电极的各功能层间的连接强度要大大增强。本申请的膜电极的各功能层之间为紧密的面接触，而现有的膜电极的各功能层之间往往是局部的面接触或局部的点接触，所以，本发明的膜电极从结构上也与现有的膜电极进行了区分，这种区别主要是相邻的功能层之间的界面的较大差异。
实施例六
本发明还公开一种质子交换膜燃料电池系统，采用上述实施例制备得到的膜电极结构。
该燃料电池系统可以应用在汽车领域，如包含该燃料电池系统的新能源车辆(如新能源小汽车、新能源公交车等)，由于采用了本发明的膜电极，车辆的颠簸、抖动等也不容易使膜电极损坏，提升了燃料电池的工作稳定性，使燃料电池可以应用在更加复杂、恶劣的工况之下。该燃料电池还可以应用在无人机领域，为无人机供应电能。
该燃料电池还可以应用在机器人领域，为机器人提供电能。比如，将本发明的燃料电池应用在工业机器人上。
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在不脱离本发明的原理和宗旨的情况下在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (51)

  1. 一种燃料电池用膜电极结构，其特征在于，包括：
    厚度为25～300微米的第一结构层；
    设于第一结构层之上的第一催化剂层；
    涂覆于第一催化剂层之上的全氟磺酸质子交换膜(PEM)；
    设于全氟磺酸质子交换膜之上的第二催化剂层；
    其中，所述第一催化剂层、第二催化剂层的厚度分别为1～50微米；第一催化剂层对应阳极或者阴极，第二催化剂层对应另一电极；
    以上各层复合后，形成膜电极结构。
  2. 根据权利要求1所述的燃料电池用膜电极结构，其特征在于，
    所述第一结构层为背膜，该膜电极结构具体为：
    无静电且无尘的厚度为25～300微米的背膜；
    涂布于背膜之上的干燥的第一催化剂层；
    涂布于第一催化剂层之上的干燥的全氟磺酸质子交换膜；
    涂布于质子交换膜外侧的干燥的第二催化剂层；
    其中，所述第一催化剂层、第二催化剂层的厚度分别为1～50微米；第一催化剂层对应阳极或者阴极，第二催化剂层对应另一电极；
    以上各层复合后，形成背膜支撑的三层膜电极CCM。
  3. 根据权利要求1所述的燃料电池用膜电极结构，其特征在于，所述背膜具体是PTFE膜、FEP膜、PET膜、PI膜中的一种膜。
  4. 根据权利要求1所述的燃料电池用膜电极结构，其特征在于，所述第一结构层具体为气体扩散层，所述气体扩散层包括两个子层：
    第一子层，采用疏水材料处理后的导电透气材料基材层；
    第二子层，涂覆于的导电透气材料基材层表面的微孔层；
    所述膜电极结构还包括有：
    设于微孔层之上的第一催化剂层；
    设于第一催化剂层之上的全氟磺酸质子交换膜；
    设于全氟磺酸质子交换膜之上的第二催化剂层；
    其中，所述第一催化剂层、第二催化剂层的厚度分别为1～50微米；
    以上各层复合之后，形成七层膜电极结构。
  5. 根据权利要求4所述的燃料电池用膜电极结构，其特征在于，包括：
    导电透气材料基材层；
    设于所述导电透气材料基材层的微孔层；
    设于所述微孔层之上的第一催化剂层；
    设于所述第一催化剂层之上的全氟磺酸质子交换膜(PEM)层；
    设于所述质子交换膜层之上的第二催化剂层；
    胶合于所述第二催化剂层之上的另一气体扩散层(GDL)；其中，气体扩散层与第二催化剂层 形成气体扩散电极；
    以上各层复合之后，形成七层膜电极结构。
  6. 根据权利要求5所述的燃料电池用膜电极结构，其特征在于，所述导电透气材料基材层具体为碳纤维布或碳纤维纸。
  7. 根据权利要求5所述的燃料电池用膜电极结构，其特征在于，所述微孔层具体为碳黑层或碳纳米管层。
  8. 根据权利要求5所述的燃料电池用膜电极结构，其特征在于，所述疏水材料具体为PTFE或白炭黑的分散液。
  9. 根据权利要求1所述的燃料电池用膜电极结构，其特征在于，所述第一催化剂层、第二催化剂层中含有的催化剂，具体为含有碳载体的贵金属或非贵金属、及其合金，所述贵金属具体为铂(Pt)或钯(Pd)。
  10. 根据权利要求1至9任一项所述的燃料电池用膜电极结构，其特征在于，所述第一催化剂层中含有阳极催化剂或阴极催化剂，第二催化剂层中含有与另一电极相对应的催化剂；两个催化剂层的催化剂种类与电极种类相匹配。
  11. 一种燃料电池膜电极的制备方法，其特征在于，包括如下步骤：
    a)将全氟磺酸树脂(PFSA)溶液直接涂覆于已得到的第一催化剂层的表面；干燥处理；制备得到PEM膜；
    b)通过一定方式将催化剂浆料涂覆于干燥后的PEM膜的外侧表面；干燥处理，得到第二催化剂层；然后热处理；即得到膜电极结构。
  12. 根据权利要求11所述的燃料电池膜电极的制备方法，其特征在于，包括如下步骤：
    a)准备背膜，并对背膜进行预处理；
    b)通过一定方式将催化剂浆料涂覆于预处理后的背膜之上；干燥处理；制备得到厚度为1～50微米的第一催化剂层；
    c)将全氟磺酸树脂(PFSA)溶液直接涂布于第一催化剂层的表面；60～120摄氏度烘干处理；制备得到10～100微米的质子交换膜(PEM)；该步骤执行一次或多次，通过将步骤c重复操作多次，使质子交换膜(PEM)达到目标厚度；
    d)通过一定方式将催化剂浆料覆于干燥后的质子交换膜(PEM)的外侧表面；干燥处理，得到厚度为1～50微米的第二催化剂层；然后在120～250摄氏度范围内进行热处理；即得到有背膜支撑的成品三层膜电极CCM。
  13. 根据权利要求12所述的燃料电池膜电极的制备方法，其特征在于，步骤b、步骤d中的干燥处理具体是烘干。
  14. 根据权利要求12所述的燃料电池膜电极的制备方法，其特征在于，步骤a、步骤b之间，还可以增加制备催化剂浆料和\或全氟磺酸树脂(PFSA)溶液的步骤，制备好的浆料或溶液存放备用。
  15. 根据权利要求12所述的燃料电池膜电极的制备方法，其特征在于，步骤a中，所述背膜是PEFE膜、FEP膜、PET膜或PI膜中的一种。
  16. 根据权利要求12所述的燃料电池膜电极的制备方法，其特征在于，步骤a中，所述预处理是对背膜的表面进行除尘和\或除静电。
  17. 根据权利要求12所述的燃料电池膜电极的制备方法，其特征在于，步骤b中，具体是通过狭缝涂布或喷涂或丝网印刷或凹版印刷的方式将催化剂浆料涂覆于背膜基材之上，并进行干燥处 理。
  18. 根据权利要求12所述的燃料电池膜电极的制备方法，其特征在于，步骤b、步骤d中所使用的催化剂浆料为一定比例的催化剂粉末及全氟磺酸树脂溶液，此催化剂浆料的溶剂为水溶液、水醇溶液、或多种溶剂的混合液；催化剂粉末为含有碳载体贵金属或非贵金属、及其合金，其中，所述贵金属为Pt或Pd。
  19. 根据权利要求12所述的燃料电池膜电极的制备方法，其特征在于，在步骤c中还添加有：
    用以提高PEM的抗氧化性的自由基淬灭剂，和\或，
    用以提高PEM的保水能力的保水剂，和\或，
    用以提高CCM的机械强度的多孔基体支撑材料。
  20. 根据权利要求12所述的燃料电池膜电极的制备方法，其特征在于，步骤c中，全氟磺酸树脂(PFSA)溶液为PFSA的水溶液或水醇溶液或多种溶剂的混合液。
  21. 根据权利要求11所述的燃料电池膜电极的制备方法，其特征在于，包括如下步骤：
    a)准备厚度为30～300微米的气体扩散层，所述气体扩散层包括厚度为1～50微米的第一催化剂层；
    b)在气体扩散电极的第一催化剂层上直接进行全氟磺酸树脂(PFSA)溶液的涂覆；干燥处理；制备得到厚度为5～200微米的质子交换膜(PEM)；
    c)通过一定方式将催化剂浆料覆于干燥后的PEM膜的外侧表面；干燥处理，得到厚度为1～50微米的第二催化剂层；然后热处理；即得到三层膜电极CCM。
  22. 根据权利要求21所述的燃料电池膜电极的制备方法，其特征在于，干燥处理具体为烘干。
  23. 根据权利要求21所述的燃料电池膜电极的制备方法，其特征在于，还包括有如下步骤：
    d)气体扩散层贴合，即，通过一定操作将气体扩散层与步骤c得到的三层膜电极CCM进行黏合；制备得到七层膜电极。
  24. 根据权利要求23所述的燃料电池膜电极的制备方法，其特征在于，步骤d中的一定操作，具体是：边缘点胶贴合；或者；将气体扩散层表面喷覆一层胶水进行贴合，喷覆的胶水为全氟磺酸离子聚合物溶液，喷覆厚度小于等于1微米。
  25. 根据权利要求23所述的燃料电池膜电极的制备方法，其特征在于，在120～250摄氏度范围内进行热处理。
  26. 根据权利要求23所述的燃料电池膜电极的制备方法，其特征在于，步骤c中所使用的催化剂浆料为一定比例的催化剂粉末及全氟磺酸树脂溶液，此催化剂浆料的溶剂为水溶液、水醇溶液、或多种溶剂的混合液；催化剂粉末为含有碳载体贵金属或非贵金属、及其合金，其中，所述贵金属为Pt或Pd。
  27. 根据权利要求23所述的燃料电池膜电极的制备方法，其特征在于，在步骤c中还添加有用以提高PEM的抗氧化性的自由基淬灭剂。
  28. 根据权利要求23所述的燃料电池膜电极的制备方法，其特征在于，在步骤c中还添加有用以提高PEM的保水能力的保水剂。
  29. 根据权利要求23所述的燃料电池膜电极的制备方法，其特征在于，在步骤c中还添加 用以提高CCM的机械强度的多孔基体支撑材料。
  30. 根据权利要求12所述的燃料电池膜电极的制备方法，其特征在于，步骤c中，全氟磺酸树脂(PFSA)溶液为PFSA的水溶液或水醇溶液或多种溶剂的混合液。
  31. 根据权利要求11所述的燃料电池膜电极的制备方法，用于制备七层膜电极，其特征在于，包括如下步骤：
    a)准备两份气体扩散层，气体扩散层的厚度为30～260微米；
    b)在第一份气体扩散层的微孔层的表面进行催化剂浆料的涂覆，烘干，得到厚度为1～50微米的第一催化剂层；
    c)在催化层上进行全氟磺酸树脂(PFSA)溶液的涂覆，烘干，热处理，得到厚度为5～200微米的质子交换膜(PEM)；
    d)在经步骤c得到的质子交换膜上，再进行一层催化剂浆料的涂覆，形成第二催化剂层，催化层烘干厚度为1～50微米；
    e)采用一定贴合方法将另一气体扩散层与第二催化剂层贴合；所述贴合方法为边缘点胶贴合，或，将气体扩散层表面喷覆一层胶水进行贴合，喷覆的胶水为全氟磺酸离子聚合物溶液，喷覆厚度小于等于1微米。
  32. 根据权利要求31所述的燃料电池膜电极的制备方法，其特征在于，在120～250摄氏度范围内进行热处理。
  33. 根据权利要求31所述的燃料电池膜电极的制备方法，其特征在于，所述气体扩散层为商业气体扩散层。
  34. 根据权利要求31所述的燃料电池膜电极的制备方法，其特征在于，步骤b、步骤d中所使用的催化剂浆料为一定比例的催化剂粉末及全氟磺酸树脂溶液，此催化剂浆料的溶剂为水溶液、水醇溶液、或多种溶剂的混合液；催化剂粉末为含有碳载体贵金属或非贵金属、及其合金，其中，所述贵金属为Pt或Pd。
  35. 根据权利要求31所述的燃料电池膜电极的制备方法，其特征在于，在步骤c中还添加有用以提高PEM的抗氧化性的自由基淬灭剂。
  36. 根据权利要求31所述的燃料电池膜电极的制备方法，其特征在于，在步骤c中还添加有用以提高PEM的保水能力的保水剂。
  37. 根据权利要求31所述的燃料电池膜电极的制备方法，其特征在于，在步骤c中还添加用以提高CCM的机械强度的多孔基体支撑材料。
  38. 根据权利要求31所述的燃料电池膜电极的制备方法，其特征在于，步骤c中，全氟磺酸树脂(PFSA)溶液为PFSA的水溶液或水醇溶液或多种溶剂的混合液。
  39. 根据权利要求31所述的燃料电池膜电极的制备方法，其特征在于，所述全氟磺酸树脂聚合物可由任何传导阳离子或者传导阴离子或传导电子的导电聚合物代替。
  40. 根据权利要求11所述的燃料电池膜电极的制备方法，用于制备七层膜电极，其特征在于，包括如下步骤：
    a)选择20～200微米厚的导电透气材料为涂布的基材；
    b)对基材进行疏水处理；
    c)在疏水处理后的基材上进行微孔层的涂布；
    d)在微孔层的表面进行催化剂浆料的涂覆，烘干，形成厚度为1～50微米的第一催化剂层；
    e)在催化层上进行全氟磺酸树脂的涂覆，烘干、热处理得到厚度为5～200微米厚的质子交换膜(PEM)；
    f)在质子交换膜上再进行一层催化剂浆料的涂覆，得到层间连接优良的另外一个电极，烘干，得到厚度为1～50微米的第二催化剂层；
    g)采用一定贴合方法将另一气体扩散层与第二催化剂层贴合；所述贴合方法为边缘点胶贴合，或，将气体扩散层表面喷覆一层胶水进行贴合，喷覆的胶水为全氟磺酸离子聚合物溶液，喷覆厚度小于等于1微米。
  41. 根据权利要求40所述的燃料电池膜电极的制备方法，其特征在于，所述基材是碳纤维布或碳纤维纸。
  42. 根据权利要求40所述的燃料电池膜电极的制备方法，其特征在于，所述疏水处理的过程为：将碳纤维纸采用疏水材料进行浸渍并烧结处理。
  43. 根据权利要求42所述的燃料电池膜电极的制备方法，其特征在于，所述疏水材料是聚四氟乙烯(PTFE)或白炭黑的溶液。
  44. 根据权利要求40所述的燃料电池膜电极的制备方法，其特征在于，步骤d、步骤f中所使用的催化剂浆料为一定比例的催化剂粉末及全氟磺酸树脂溶液，此催化剂浆料的溶剂为水溶液、水醇溶液、或多种溶剂的混合液。
  45. 根据权利要求44所述的燃料电池膜电极的制备方法，其特征在于，催化剂粉末为含有碳载体贵金属或非贵金属、及其合金；所述贵金属为Pt或Pd。
  46. 根据权利要求40所述的燃料电池膜电极的制备方法，其特征在于，在步骤e中还添加有用以提高PEM的抗氧化性的自由基淬灭剂。
  47. 根据权利要求40所述的燃料电池膜电极的制备方法，其特征在于，在步骤e中还添加有用以提高PEM的保水能力的保水剂。
  48. 根据权利要求40所述的燃料电池膜电极的制备方法，其特征在于，在步骤e中还添加用以提高CCM的机械强度的多孔基体支撑材料。
  49. 根据权利要求40所述的燃料电池膜电极的制备方法，其特征在于，步骤e中，全氟磺酸树脂(PFSA)溶液为PFSA的水溶液或水醇溶液或多种溶剂的混合液。
  50. 根据权利要求40所述的燃料电池膜电极的制备方法，其特征在于，所述全氟磺酸树脂聚合物可由任何传导阳离子或者传导阴离子或传导电子的导电聚合物代替。
  51. 一种质子交换膜燃料电池系统，其特征在于，采用如权利要求1所述的膜电极结构。
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Publication number Priority date Publication date Assignee Title
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