CN110247062A - A kind of preparation method of fuel cell membrane electrode - Google Patents

A kind of preparation method of fuel cell membrane electrode Download PDF

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Publication number
CN110247062A
CN110247062A CN201910519860.9A CN201910519860A CN110247062A CN 110247062 A CN110247062 A CN 110247062A CN 201910519860 A CN201910519860 A CN 201910519860A CN 110247062 A CN110247062 A CN 110247062A
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layer
catalyst
gas diffusion
membrane electrode
proton exchange
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CN110247062B (en
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樊建涛
王海江
李辉
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Shenzhen General Hydrogen Energy Technology Co Ltd
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Shenzhen General Hydrogen Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8892—Impregnation or coating of the catalyst layer, e.g. by an ionomer
    • 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
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Dispersion Chemistry (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention discloses a kind of preparation method of fuel cell membrane electrode, include the following steps: to prepare gas diffusion layers, the gas diffusion layers include the first catalyst layer；The coating of perfluorinated sulfonic resin (PFSA) solution is directly carried out on the first catalyst layer of gas-diffusion electrode；It is dried；It prepares proton exchange membrane (PEM)；Catalyst pulp is overlying on to the outer surface of the PEM membrane after drying by certain way；It is dried, obtains the second catalyst layer；It is subsequently heat-treated；Obtain trilamellar membrane electrode CCM.Advantage of the invention is that perfluorinated sulfonic resin PFSA in catalysis layer surface direct formation of film at surface, reduces the resistance of the transmitting proton between Catalytic Layer and proton exchange membrane interface；The Water transport ability between Catalytic Layer and proton exchange membrane is enhanced, proton exchange membrane can be preferably soaked in cell operation；Proton exchange membrane preparation process is merged into the preparation process into membrane electrode, shortens manufacturing cycle.

Description

A kind of preparation method of fuel cell membrane electrode
Technical field
The present invention relates to fuel cell membrane electrode technical field more particularly to a kind of preparation sides of fuel cell membrane electrode Method.
Background technique
Fuel cell is a kind of electrochemical cell, and cardinal principle is to go back the chemical energy in fuel and oxidant through oxidation Original reaction is converted into electric energy.Important branch of the Proton Exchange Membrane Fuel Cells (PEMFC) as fuel cell field, in addition to Possess fuel cell generality feature such as energy high conversion efficiency, it is environmental-friendly except, also have at room temperature that starting speed is fast, body Outstanding advantages of long-pending small, electroless liquid loses, is easy draining, the service life is long, specific power and specific energy are high.It is applicable not only to disperse The construction in formula power station, and it is suitable for mobile power supply.It is a kind of novel dual-use mobile power source.Therefore, proton is handed over Membrane cell is changed with boundless application prospect.
Membrane electrode (Membrane Electrode Assembly, MEA) is the core of Proton Exchange Membrane Fuel Cells Part is the place that fuel cell carries out redox reaction, mainly by perfluorosulfonic acid proton exchange film (Proton Exchange Membrane, PEM), catalyst layer (Catalyst layer, CL), gas diffusion layers (Gas diffusion layer, GDL) And sealing material composition.Trilamellar membrane electrode (CCM) according to the present invention is then by PEM, anode catalyst layer (Anode Catalyst layer, ACL) and cathode catalysis layer (Cathode Catalyst layer, CCL) composition.It is involved in the present invention Five layer membrane electrodes (MEA) be then made of CCM and anode and cathode GDL.Basic unit of the CCM as electrochemical reaction of fuel battery, Its structure designs and prepares the proposition of process program, needs with the basic principles and features of electrochemical reaction of fuel battery for theory Basis, and it is subject to comprehensive consideration in conjunction with its actual operating conditions.It is fuel cell that the structure of CCM, which designs and prepares technology, Key technology, which determine the working performances of fuel cell.
Existing trilamellar membrane electrode (CCM) technology of preparing mainly includes that (but unlimited) is following several: 1, double transfer printings, i.e., first ACL and CCL is obtained after coating catalyst pulp drying on base film, then is engaged ACL and CCL by way of hot-pressing transfer printing To the two sides of PEM；2, single transfer printing, i.e., the outside of the proton exchange membrane (PEM) with notacoria directly carry out cathode (or sun Pole) catalyst pulp coating, prepare the PEM with CCL (or ACL), the PEM of CCL (or ACL) be coated with after dry from back Film stripping, then ACL (or CCL) is conformed to by way of hot-pressing transfer printing the other side of PEM；3, dual coating method is that is, first The direct coating that cathode (or anode) catalyst pulp is first carried out in the outside of the PEM with notacoria, obtains after drying with CCL The PEM of (or ACL), the PEM for being coated with CCL (or ACL) are removed from notacoria, then anode (or cathode) catalyst pulp is direct The other side to PEM and drying are coated, or ACL and CCL is coated on the two sides of PEM simultaneously and is dried；4, spray coating method, i.e., CCM is prepared by way of spraying Anode inks and cathode inks respectively in the two sides of PEM；5, silk screen Catalyst pulp is printed directly to after the skin drying of PEM by silk-screen printing and carries out other side Catalytic Layer again by print process Printing, is made CCM；6, method is prepared in situ, by the method for chemistry and physics directly by catalyst growth in the two sides of PEM, shape At the CCM of ordered catalyst layer structure.
The preparation method of above-mentioned CCM is summarized as two major classes as a result, one, it is direct in the two sides of PEM using catalyst pulp Catalytic Layer is prepared, such as directly painting method, spray coating method or stencil；Two, after preparing Catalytic Layer on notacoria, it is bonded using transfer Mode Catalytic Layer is bonded with PEM；Or the combination by these two kinds of methods.
The two sides CCM obtained by the above method are bonded with GDL respectively and obtain MEA.The preparation method of another MEA is Traditional gas-diffusion electrode (Gas Diffusion Electrode, GDE) the preparation method (as shown in Fig. 1 of this application) that is, will Anode inks, which are coated on GDL, obtains anode GDE, and cathode inks are coated on GDL and obtain cathode GDE, then anode GDE and cathode GDE are joined respectively to by way of hot pressing the two sides of PEM, obtain MEA.
The present invention is improved primarily directed to traditional transfer printing.
Summary of the invention
A kind of membrane-membrane electrode for fuel cell structure is provided it is an object of the invention to overcome the deficiency of the above-mentioned prior art, When preparing membrane electrode, trilamellar membrane electrode is prepared if from notacoria；It is five layers of preparation if from gas diffusion layers Membrane electrode or seven layer membrane electrodes.
To achieve the above object, a kind of membrane-membrane electrode for fuel cell structure provided by the invention, comprising:
With a thickness of 25~300 microns of first structure layer；
The first catalyst layer on first structure layer；
Coated on the perfluorosulfonic acid proton exchange film (PEM) on the first catalyst layer；
The second catalyst layer on perfluorosulfonic acid proton exchange film；
Wherein, first catalyst layer, the second catalyst layer thickness be respectively 1~50 micron；First catalyst layer Corresponding anode or cathode, the second catalyst layer correspond to another electrode；
After above each layer is compound, film electrode structure is formed.It is also pointed out that first catalyst layer, the second catalyst layer It is Pt/C catalyst, non-platinum catalyst or other kinds of catalyst and ionomeric resins or is formed with binder Catalytic Layer.The first catalyst layer herein can also be used as cathode respectively as anode；Second catalyst layer can be distinguished As anode, cathode can also be used as.
It should further be noted that: when carrying out specifically preparing membrane electrode, the first layer structure can be notacoria It can be gas diffusion layers.If first layer structure is common plastics notacoria, what is be prepared is 3 layers of CCM (trilamellar membrane electrode)； If first layer structure is gas diffusion layers, preparation-obtained is 5 layers or 7 layer MEAs.Based on above-mentioned explanation, to above-mentioned Scheme is further elucidated above as follows:
Above-mentioned technical proposal is further improved or limited: the first structure layer is notacoria, film electrode structure tool Body are as follows:
Without electrostatic and dustless notacoria, the notacoria with a thickness of 25~300 microns；
It is coated on the first catalyst layer of the drying on notacoria；
It is coated on the perfluorosulfonic acid proton exchange film of the drying on the first catalyst layer；
It is coated on the second catalyst layer of the drying on the outside of proton exchange membrane；
Wherein, first catalyst layer, the second catalyst layer thickness be respectively 1~50 micron；
After above each layer is compound, the trilamellar membrane electrode CCM of notacoria support is formed.
Further limit above-mentioned technical proposal improvement, the notacoria with a thickness of 50~100 microns.Above-mentioned coating Operation can also be replaced with coating operation.Coating or coating operation can carry out primary or multiple (>=2 times).
As improvement to above-mentioned technical proposal, the proton exchange membrane is specifically perfluorosulfonic acid proton exchange film.
As improvement to above-mentioned technical proposal, the notacoria is specifically PTFE film (polytetrafluoroethylene film), fep film, PET One of film, PI film film.Notacoria herein is to select one kind from the film of above each material, is not related to listed film Property improve.Wherein: (Poly tetra fluoroethylene, is abbreviated as PTFE, Chinese name: polytetrafluoroethyl-ne to PTFE Alkene)；FEP (Fluorinated ethylene propylene, fluorinated ethylene propylene copolymer)；PET(Polyethylene Terephthalate, poly terephthalic acid class plastics)；PI (Polyimide, polyimides).
As the further improvement to inventive film electrode structure, the first structure layer is specially gas diffusion layers, The gas diffusion layers include two sublayers:
First sublayer, using hydrophobic material, treated that conductive gas permeable material substrate layer (after hydrophobic treatment, has and dredges Water inner surface)；
Second sublayer, the microporous layers for the conductive gas permeable material substrate layer surface being coated on；
The film electrode structure further includes having:
The first catalyst layer on microporous layers；
Perfluorosulfonic acid proton exchange film on the first catalyst layer；
The second catalyst layer on perfluorosulfonic acid proton exchange film；
Wherein, first catalyst layer, the second catalyst layer thickness be respectively 1~50 micron；
After above each layer is compound, seven layer membrane electrode structures are formed.
As the further improvement to inventive film electrode structure, membrane-membrane electrode for fuel cell structure of the invention, packet It includes:
Conductive gas permeable material substrate layer；
Set on the microporous layers of the conductive gas permeable material substrate layer；Microporous layers herein can also be referred to as porous layer, micro- Aperture layer is the more generally applicable noun in this field；
The first catalyst layer on the microporous layers；
Proton exchange membrane (PEM) layer on first catalyst layer；
The second catalyst layer on the proton exchange membrane layer；
The gas diffusion layers (GDL) being glued on second catalyst layer；Wherein, gas diffusion layers and the second catalysis Oxidant layer forms gas-diffusion electrode；Further limit gluing operation herein: gluing operation can be simple marginal point Glue laminating；Can also be bonded for gas diffusion layer surface is sprayed one layer of glue, the glue sprayed be preferably perfluorinated sulfonic acid from Sub- polymer solution, spraying thickness is preferably 1 micron or less.
After above each layer is compound, seven layer membrane electrode structures are formed.The gas diffusion layers (GDL), which can be, passes through preparation Obtained from, or be commercially available from open channel.There is gas expansion respectively in the two sides of original trilamellar membrane electrode Layer is dissipated, and gas diffusion layers are by double-layer structure, so total seven-layer structure.
As improvement to above-mentioned technical proposal, the conduction gas permeable material substrate layer is specially carbon cloth or carbon fiber Paper.It should be noted that carbon cloth or carbon fiber paper are a component parts inside gas diffusion layers, belong in Catalytic Layer Outside.
As improvement to above-mentioned technical proposal, the microporous layers are specially carbon black layer or carbon nanotube layer.
As improvement to above-mentioned technical proposal, the hydrophobic material is specially the dispersion liquid of PTFE or white carbon black.
As improvement to above-mentioned technical proposal, the catalyst contained in first catalyst layer, the second catalyst layer, Tool
Body is the noble metal containing carbon carrier or base metal and its alloy.Further to improve, catalyst includes Pt/ C, Pt/Co/C, Pt/Pd/C, Fe-N-C etc..
More preferably, the noble metal is specially platinum (Pt) or palladium (Pd).
As the further improvement to above-mentioned technical proposal, anode catalyst or yin are contained in first catalyst layer Electrode catalyst contains catalyst corresponding with another electrode in the second catalyst layer；The catalyst type of two catalyst layers Match with type of electrodes.
The present invention also provides a kind of preparation methods of fuel cell membrane electrode, include the following steps:
A) perfluorinated sulfonic resin (PFSA) solution is directly coated and (such as uses the method being coated with, coating is one kind of coating Mode) in the surface of the first obtained catalyst layer；It is dried；PEM membrane is prepared；
B) catalyst pulp is coated on to the outer surface of the PEM membrane after drying by certain way；It is dried, obtains Second catalyst layer；It is subsequently heat-treated；Obtain the main structure of membrane electrode, i.e. first the second catalyst of catalyst layer-PEM- Three layer main body structures of layer.The specific effect of heat treatment herein is: so that PEM forms the network of stable structure, increasing PEM's Performance and mechanical life.
Described herein, the first obtained catalyst layer refers to, first catalyst layer is via the step of system before It is standby to obtain, alternatively, the commercial product for having purchase is provided.Step a is further processed on this basis.Step a is The technology of the application core passes through certain process, the presoma with the first catalyst layer is prepared, such as by notacoria branch Then first catalyst layer of support carries out the operation of above-mentioned steps a on first catalyst layer, here it is the application is utilized Technology.In other words, implement patented technology person and be commercially available this presoma with the first catalyst layer, it is then basic herein Upper further completion step a, step b, realize perfluorinated sulfonic resin PFSA on catalyst layer (Catalytic Layer) surface by step a Then direct formation of film at surface further obtains CCM, this is also to fall within the scope of the present application.The first of above-mentioned institute's appellation Catalyst layer, the second Catalytic Layer are not meant to catalyst layer in use according to this life just for the sake of the convenience in mark The precedence of name carries out.
As the further restriction to above-mentioned technical proposal, fuel cell membrane electrode preparation method of the invention, including Following steps:
A) prepare notacoria (notacoria herein is as painting cloth base material), and notacoria is pre-processed；This step is so-called Pretreatment refers mainly to cleaning treatment, such as removes dust, the solid particle on notacoria surface；And including electrostatic on removal notacoria Operation.
B) catalyst pulp is overlying on pretreated notacoria by certain way；It is dry that (drying herein can be excellent It is selected as drying, drying is a kind of dry implementation) processing；The first catalyst layer with a thickness of 1~50 micron is prepared (the first catalyst layer herein can be used as anode or cathode).
C) perfluorinated sulfonic resin (PFSA) solution is directly coated to the surface of the first catalyst layer；60~120 degrees Celsius Drying and processing；10~100 microns of PEM membrane is prepared；The step execute it is one or many, by by step c repetitive operation Repeatedly, proton exchange membrane (PEM) is made to reach target thickness.It is also pointed out that: coating is scraped using slot coated, intaglio plate coating, comma The modes such as knife, silk-screen printing, spraying or tool.
D) catalyst pulp is overlying on to the outer surface of the PEM membrane after drying by certain way；It is dried, obtains thickness The second catalyst layer that degree is 1~50 micron (the second catalyst layer herein can be used as another electrode)；Then 120~ It is heat-treated in 250 degree Celsius ranges；Obtain the finished product trilamellar membrane electrode CCM of notacoria support.Notacoria also acts as support Effect.
As improvement to above-mentioned technical proposal, step b, the drying process in step d is specifically to dry.It is grasped using drying Work keeps catalyst pulp dry, thus two catalyst layers.The intermediate products that can be coated with catalyst pulp are placed in baking Among case, dried.
As improvement to above-mentioned technical proposal, step a, between step b, it can also increase and prepare catalyst pulp, complete The step of perfluorosulfonic acid resin (PFSA) solution, slurry or the solution storage prepared are spare.The step is not and indispensable, catalysis Agent slurry, perfluor sulfoacid resin solution can also be obtained by commercial activity (as bought), can also be before preparation starts Just it is ready in advance via implementation the art of this patent person.Have when coating perfluorinated sulfonic resin in coating catalyst pulp Corresponding material can be used, herein not acquisition modes of defined catalyst slurry, perfluorinated sulfonic resin, acquisition side Formula has no effect on the forming of final products of the invention.Certainly, insertion prepares the step for coating raw material between step a, step b Suddenly, raw material can be made ready-to-use, better effect.
As improvement to above-mentioned technical proposal, the notacoria is one of PEFE film, fep film, PET film or PI film. Certainly, same kind of film can also be superimposed multilayer, such as two layers of superposition, be also this Shen by notacoria obtained from superposition same film Please clearly it cover.For example, 2 layers of PEFE film superposition are used as a notacoria.But the best embodiment of the application is single Solely use a tunic.
As improvement to above-mentioned technical proposal, in step a, the pretreatment be the surface of notacoria is dusted and Or it destatics.Destaticing is contactless operation.
As improvement to above-mentioned technical proposal, in step b, particular by slot coated or spraying or silk-screen printing or Catalyst pulp is coated on notacoria substrate by the mode of intaglio printing, and is dried.
As improvement to above-mentioned technical proposal, step b, catalyst pulp used in step d is a certain proportion of Catalyst fines and perfluor sulfoacid resin solution, the solvent of this catalyst pulp are aqueous solution, water-alcohol solution or multi-solvents Mixed liquor；Catalyst fines are to contain carbon carrier noble metal or base metal and its alloy.More preferably, the noble metal For Pt or Pd.
As to one biggish improvement of above-mentioned technical proposal, also it is added in step c:
Improving the antioxidative free radical quencher of PEM, and or,
Improving the water-retaining agent of the water holding capacity of PEM, and or,
To improve the porous matrix backing material of the mechanical strength of CCM.
For above-mentioned improvement, it is pointed out that:
1. in this improvement, be related to three kinds of addible components altogether, these components can individually add it is a kind of, two kinds or Three kinds.Namely based on various purposes, and select to add the combination of different component or component.
2. free radical quencher, water-retaining agent, porous matrix backing material, the addition opportunity of these three components are as follows: polymerizeing It is added in object slurry preparation process；The amount of addition are as follows: the 0.1%~10% of polymer quality；The type of addition is CeO2, cerium from Son, platinum black, platinum carbon.
3. if free radical quencher, water-retaining agent, two or three in porous matrix backing material is added, from each other Respective normal function will not be interfered.
4. porous matrix backing material may is that porous PTFE, ePTFE (expanded PTFE, e-PTFE second Alkene), the porous polymer films branch such as porous PEEK (polyetheretherketone, abbreviation PEEK, Chinese name: polyether-ether-ketone) Timbering material.
As improvement to above-mentioned technical proposal, in step c, perfluorinated sulfonic resin (PFSA) solution is the aqueous solution of PFSA Or the mixed liquor of water-alcohol solution or multi-solvents.It should further be noted that: " multi-solvents " herein include organic solvent, in addition Alcohol is also one kind of organic solvent；Water-alcohol solution, alcohol can be one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, butanol； " multi-solvents ", several alcohols are contained in solvent the inside, such as have the mixed liquor of methanol, ethyl alcohol and isopropanol.
The present invention also provides the preparation methods of fuel cell membrane electrode, include the following steps:
A) prepare the gas-diffusion electrode with a thickness of 30~300 microns, which includes that thickness is respectively 1 ~50 microns of the first catalyst layer；
B) coating of perfluorinated sulfonic resin (PFSA) solution is directly carried out on the first catalyst layer of gas-diffusion electrode； Dry (preferably drying, dry one kind for drying mode) processing；The proton exchange with a thickness of 5~200 microns is prepared Film (PEM)；
C) catalyst pulp is overlying on to the outer surface of the PEM membrane after drying by certain way；It is dried, obtains thickness The second catalyst layer that degree is 1~50 micron；It is subsequently heat-treated；Obtain the finished product trilamellar membrane electrode CCM of notacoria support.Also It may be noted that the heat treatment operation in step c is necessary step.
As improvement to above-mentioned technical proposal, being dried is specially drying operation.Such as use baking oven or drying box It is operated.
As improvement to above-mentioned technical proposal, the preparation method of fuel cell membrane electrode of the invention, further include just like Lower step:
D) gas diffusion layers are bonded, by centainly operate the trilamellar membrane electrode CCM for obtaining gas diffusion layers and step c into Row bonding；Seven layer membrane electrodes are prepared.
As improvement to above-mentioned technical proposal, certain operation in step d, specifically: marginal point glue laminating, i.e., along The uniform dispensing of the periphery of gas diffusion layers (can manually dispensing, dispensing behaviour can also be carried out using the equipment such as dispenser Make), then by gas diffusion layers gluing on the second catalyst layer；Or；Gas diffusion layer surface is sprayed into one layer of glue It being bonded, the glue sprayed is perfluorosulfonic acid ion polymer solution, it sprays thickness and is preferably less than equal to 1 micron,.
As improvement to above-mentioned technical proposal, the heat treatment is that hot place is carried out in 120~250 degree Celsius ranges Reason.
As improvement to above-mentioned technical proposal, catalyst pulp used in step c is a certain proportion of catalyst Powder and perfluor sulfoacid resin solution, the solvent of this catalyst pulp are the mixing of aqueous solution, water-alcohol solution or multi-solvents Liquid；Catalyst fines are to contain carbon carrier noble metal or base metal and its alloy.More preferably, the noble metal is Pt Or Pd.
It may also be noted that in step c, the catalyst slurry used in the first catalyst layer, the second catalyst layer Expect be same, may not be same.If only being needed specifically, 1. using same catalyst pulp in step c Prepare a kind of catalyst pulp of coating；2. needing to prepare two kinds if using two kinds of catalyst pulps in step c Catalyst pulp simultaneously separates storage, and should mark, mark or label, so that two kinds of catalyst pulps differentiate, then According to scheduled design, two kinds of catalyst pulps are respectively coated in the outer surface of PEM membrane, be respectively formed the first catalyst layer, Second catalyst layer.
As improvement to above-mentioned technical proposal, also added with the antioxidative freedom to improve PEM in step c Base quencher.It can also further expand to remove free radical or reducing the object of free radical quantity or absorption free radical Matter.
As improvement to above-mentioned technical proposal, also added with the water conservation to improve the water holding capacity of PEM in step c Agent.
As improvement to above-mentioned technical proposal, the porous base to improve the mechanical strength of CCM is also added in step c Body backing material.
As improvement to above-mentioned technical proposal, in step c, perfluorinated sulfonic resin (PFSA) solution is the aqueous solution of PFSA Or the mixed liquor of water-alcohol solution or multi-solvents.
The present invention also provides a kind of preparation methods of fuel cell membrane electrode, are used to prepare seven layer membrane electrodes, specifically include Following steps:
A) prepare two parts of gas diffusion layers, gas diffusion layers with a thickness of 30~260 microns.
B) coating of catalyst pulp is carried out on the surface of the microporous layers of first part of gas diffusion layers, drying obtains thickness For 1~50 micron of the first catalyst layer；First catalyst layer is first electrode.
C) coating that perfluorinated sulfonic resin (PFSA) solution is carried out in Catalytic Layer, is dried, and heat treatment obtains with a thickness of 5 ~200 microns of proton exchange membrane (PEM).
D) in the proton exchange membrane obtained through step c, then the coating of one layer of catalyst pulp is carried out, forms the second catalysis Oxidant layer (coating is respectively coated in two surfaces of proton exchange membrane twice), obtains interlayer and connects excellent second electrode, be catalyzed Layer drying is with a thickness of 1~50 micron；First electrode, the polarity of second electrode are on the contrary, when first electrode is anode or cathode, the Two electrodes can only opposite polarity another electrode.
E) another gas diffusion layers are bonded with the second catalyst layer using certain applying method；Preferably, the fitting Method is marginal point glue laminating, is bonded or, gas diffusion layer surface is sprayed one layer of glue, and the glue sprayed is perfluor sulphur Acid ion polymer solution sprays thickness less than or equal to 1 micron.
As improvement to above-mentioned technical proposal, it is heat-treated in 120~250 degrees Celsius of (DEG C) ranges.
As improvement to above-mentioned technical proposal, the gas diffusion layers are commercial gas diffusion layer (by open channel It is commercially available and obtain)；Or；It is prepared by certain method, specific preparation method is: 1, to carbon fiber paper or carbon cloth Carry out hydrophobic material impregnation sintering and carbonization treatment；2, the coating of microporous layers is carried out later, and gas diffusion layers are prepared.
As improvement to above-mentioned technical proposal, step b, catalyst pulp used in step d is a certain proportion of Catalyst fines and perfluor sulfoacid resin solution, the solvent of this catalyst pulp are aqueous solution, water-alcohol solution or multi-solvents Mixed liquor；Catalyst fines are to contain carbon carrier noble metal or base metal and its alloy.More preferably, the noble metal For Pt or Pd.
As improvement to above-mentioned technical proposal, also added with the antioxidative freedom to improve PEM in step c Base quencher.
As improvement to above-mentioned technical proposal, also added with the water conservation to improve the water holding capacity of PEM in step c Agent.
As improvement to above-mentioned technical proposal, the porous base to improve the mechanical strength of CCM is also added in step c Body backing material.
As improvement to above-mentioned technical proposal, in step c, perfluorinated sulfonic resin (PFSA) solution is the aqueous solution of PFSA Or the mixed liquor of water-alcohol solution or multi-solvents.
As improvement to above-mentioned technical proposal, the perfluorinated sulfonic resin polymer can by any conduction cation or Conducts anions or the conducting polymer for conducting electronics replace, such as: such as sulfonated polyether-ether-ketone, the cations such as sulfonated polyether sulfone are led Anion conducting polymers such as electric polymer and quaternized polyphenylene oxide, Quaternized polybenzimidazoles or polyimidazole etc..It also needs to refer to Out: (any conduction cation or conducts anions conduct electronics for perfluorinated sulfonic resin polymer and its substitute Conducting polymer), it is necessary to play the role of glue, preferably can also play proton conducting, but be not required.
The present invention also provides a kind of preparation method of fuel cell membrane electrode, seven layer membrane electrodes are used to prepare, including as follows Step:
A) select 20~200 microns thick of conductive gas permeable material for the substrate of coating；
B) hydrophobic treatment is carried out to substrate；
C) coating of microporous layers is carried out on the substrate after hydrophobic treatment；
D) coating that catalyst pulp is carried out on the surface of microporous layers, is dried (also can choose other drying modes), Form the first catalyst layer with a thickness of 1~50 micron；First catalyst layer is as first electrode；
E) coating of perfluorinated sulfonic resin, drying (also can choose other drying modes), heat are carried out in Catalytic Layer Processing obtains with a thickness of 5~200 microns of thick proton exchange membrane (PEM)；
F) coating for carrying out one layer of catalyst pulp again in proton exchange membrane, obtains interlayer and connects another excellent Electrode (second electrode), drying, obtains the second catalyst layer with a thickness of 1~50 micron；First electrode, second electrode are polarity Two opposite electrodes；
G) another gas diffusion layers are bonded with the second catalyst layer using certain applying method；Preferably, the fitting Method is marginal point glue laminating, is bonded or, gas diffusion layer surface is sprayed one layer of glue, and the glue sprayed is perfluor sulphur Acid ion polymer solution sprays thickness less than or equal to 1 micron of (≤).In step G, device used is sprayed are as follows: spray Rifle or spraying equipment.
For above-mentioned preparation method, it is also stated that: 1. the method for preparing membrane electrode of other parts of the present invention is Using notacoria as cloth base material is applied, notacoria is general thin polymer film, and the technical program can not have to notacoria, directly use gas The characteristics of body diffused layer carries out the preparation of 7 layer membrane electrodes to replace notacoria, this is this preparation method, with other preparation methods Distinctive points；2. be located at proton exchange membrane two sides the first catalyst layer, the second catalyst layer, play two electrodes (anode and Cathode) function, be electrically connected by the first catalyst layer, the second catalyst layer and the external world.3. " gas is expanded in step g Scattered layer surface sprays one layer of glue ", one layer of glue can also be sprayed on the second catalyst layer, to substitute in gas diffusion layers On spray the operation of glue, but this mode of operation is not the mode of suggestion；One layer of glue is sprayed in gas diffusion layer surface The mode of water is best mode.4. " spraying one layer of glue " in step g, refers to spraying to be formed on the surface of gas diffusion layers One layer of glue layer, sprays in operation actual, can be by once spraying or the operation that sprays for several times forms the glue layer. 5. the glue in step g, the first function is gluing effect；Second function is can be with proton conducting, but is not required.
As improvement to above-mentioned technical proposal, the substrate is selected from carbon cloth or carbon fiber paper.
As improvement to above-mentioned technical proposal, the process of the hydrophobic treatment are as follows: by carbon fiber paper hydrophobic material such as PTFE, white carbon black dispersion liquid impregnate and sintering processes.It should further be noted that: the actual conditions for 1. impregnating, being sintered: leaching Stain is that full wet type impregnates under room temperature, and sintering temperature is 300~400 degrees Celsius；2. the equipment that dipping, sintering respectively use: dipping Pond, baking oven；3. during the sintering process, can also use atmosphere, the atmosphere is air；More preferably, atmosphere is selected as cleaning Air, such as by air be filtered dedusting (removal solid particle polluter in air) and or dehumidification operation after be re-used as gas Atmosphere uses.
As improvement to above-mentioned technical proposal, step d, catalyst pulp used in step f is a certain proportion of Catalyst fines and perfluor sulfoacid resin solution, the solvent of this catalyst pulp are aqueous solution, water-alcohol solution or multi-solvents Mixed liquor.It should further be noted that: 1. it is catalyzed the preparation process of slurry are as follows: step 1, catalyst is sufficiently soaked with a small amount of water； Step 2, perfluor sulfoacid resin solution is slowly added to be dispersed；Step 3, water is added or catalyst pulp is configured to by alcohol The catalyst pulp of 1%~20% mass concentration；Step 4, by ultrasonic disperse or microjet homogenizer or ball mill or Catalyst pulp is uniformly dispersed by the combination of several dispersing modes of person.2. in water-alcohol solution, used alcohol be monohydric alcohol or Polyalcohol, preferably dihydric alcohol in polyalcohol, such as propylene glycol.
As improvement to above-mentioned technical proposal, catalyst fines be containing carbon carrier noble metal or base metal and its Alloy, wherein the noble metal is Pt or Pd.More specifically: 1. the particle size range of the catalyst fines is 10~200nm； 2. noble metal (Pt, Pd) needs to complete the catalysis of hydroxide and hydrogen reduction；3. base metal includes iron, cobalt, nickel etc.；4. closing Gold includes Pt/Co alloy, Pt/Ni alloy etc..
As improvement to above-mentioned technical proposal, also added with the antioxidative freedom to improve PEM in step e Base quencher.
As improvement to above-mentioned technical proposal, also added with the water conservation to improve the water holding capacity of PEM in step e Agent.
As improvement to above-mentioned technical proposal, the porous base to improve the mechanical strength of CCM is also added in step e Body backing material.
As improvement to above-mentioned technical proposal, in step e, perfluorinated sulfonic resin (PFSA) solution is the aqueous solution of PFSA Or the mixed liquor of water-alcohol solution or multi-solvents.
As improvement to above-mentioned technical proposal, the perfluorinated sulfonic resin polymer can by any conduction cation or Conducts anions or the conducting polymer for conducting electronics replace.Further, the perfluorinated sulfonic resin polymer can be by sun Ion exchange resin and anion exchange resin replace.
The present invention also provides a kind of proton exchange film fuel battery system, the fuel cell system is using above-mentioned film electricity Pole structure.
It may also be noted that the technical solution in the application is there is also some alternative solutions, these alternative solutions are also fallen Enter within the protection scope of the application:
A) the slot coated mode in scheme described above can be replaced with spraying, silk-screen printing, intaglio printing.
B) foregoing invention can add the inoxidizability of free radical quencher raising PEM during preparing PEM, water-retaining agent mentions The water holding capacity and porous matrix backing material of high PEM improves the mechanical strength of CCM.
C) above-mentioned perfluorinated sulfonic resin polymer can be replaced by any conduction cation or conducts anions or conduction The conducting polymer of electronics.
D) coating process of above-mentioned proton exchange membrane, which can be decomposed into multilayer and prepare, reaches target thickness, it may be assumed that by perfluor sulphur Acid resin solution is by multiple coating (coating) in catalyst layer surface, and coating operation can form certain thickness each time Proton exchange membrane, total proton exchange film thickness can be made to be located at prespecified section model by multiple thickness superposition Within enclosing.
The beneficial effects of the present invention are:
1. 3 layers of CCM in the present invention, can be prepared if first structure layer is common plastics notacoria.If the first knot Structure layer is gas diffusion layers, and preparation-obtained is 5 layers or 7 layer MEAs.Advantage of the invention is that perfluorinated sulfonic resin PFSA directly forms proton exchange membrane (PEM) in catalysis layer surface, compared to transfer printing, has the advantage that 1. due to straight It connects and forms PEM membrane in catalyst layer surface, reduce the resistance of the transmitting proton between catalyst layer and proton exchange membrane interface, by It needs for catalyst layer to be bonded with PEM in transfer printing, so mass transfer contact area is less than or equal to two layers of projected area；And this hair It is bright directly directly to form PEM membrane in catalyst layer surface, due to the roughness properties of catalyst layer surface, so mass transfer contact area Greater than the projected area of two layers of contact surface, so the resistance of transmitting proton is reduced, so that fuel cell be made outwardly to do work Efficiency relative increase, thus more energy saving；2. the Water transport ability between catalyst layer and proton exchange membrane is enhanced, in battery work Proton exchange membrane can be preferably soaked during work；3. proton exchange membrane preparation process is merged into the preparation process into membrane electrode, Preparation process is simplified, manufacturing cycle is shortened, this is because transfer printing needs first to prepare catalyst layer on notacoria again, using Catalyst layer is bonded by the mode of transfer fitting with PEM, this just needs two steps to operate, so the entire manufacturing cycle of transfer printing Just longer than preparation method of the invention, the present invention is simple compared to the preparation process that proton exchange membrane is coated directly is bought, Continuously.
2. advantage of the invention also resides in: for catalyst layer of the invention after lyosoption, deformation quantity is smaller, grasps in coating It not will lead to the case where Catalytic Layer and proton exchange membrane are removed from notacoria appearance during making, the support energy of notacoria can be continued reliance on Power carries out remaining painting work, is easily achieved whole operation.
3. advantage of the invention finally also reside in preparation method of the invention (especially step 3 and step 4) compared to Conventional transfer method, which prepares CCM, can be obtained connection between closer catalyst layer and proton exchange membrane, that is, increase catalyst layer, Bonding strength between proton exchange membrane；To weaken due in cell operation because of the object of Catalytic Layer and proton exchange membrane The decaying in battery performance and service life caused by reason removing.Traditional transfer printing due to needing for catalyst layer to be bonded with PEM, and It is substantially less than of the invention that fitting operation, which is formed by bonding strength,.The present invention turns by catalyst layer direct formation of film at surface Print method by the way of fitting (such as dispensing laminating type), so, the area of connecting portion of the invention is much larger than conventional transfer The area of the connecting portion of method, so, membrane electrode prepared by the present invention, bonding strength is significantly better than traditional transfer printing.
4. the key technology point of the application:
A) PFSA polymer solution is directly coated with catalyst layer (or referred to as Catalytic Layer) surface, due to catalyst layer The roughness properties on surface, the ion that the geometrical contact area raising interlayer of catalyst layer and proton exchange membrane can be improved in the present invention are led Logical ability；When proton shuttle catalyst layer, proton exchange membrane, mass transfer contact area of the invention is larger.This is because Catalytic Layer Proton conduction between proton exchange membrane is decided by that the area connected between two layers, the joint face of straight line are less than rough surface Joint face.
B) coating that perfluorinated sulfonic resin is carried out in Catalytic Layer can effectively improve the layer between Catalytic Layer and proton exchange membrane Between binding force (gluing of perfluorinated sulfonic resin, adhesive effect), improve the service life；
C) PEMFC microporous layers and catalysis in the process of running can effectively be prevented by being directly coated on Catalytic Layer on microporous layers The separation of layer effectively raises the electronic conduction ability between two layers and the uniformity of gas dispersion；
D) PEMFC microporous layers and catalysis in the process of running can effectively be prevented by being directly coated on Catalytic Layer on microporous layers The separation of layer, has prevented the water generated in battery and has been detained in two interlayers and hinders gas transport to Catalytic Layer；Prevent the delay of water The reason of: microporous layers and catalysis interlayer closely contact so that the water generated will not be trapped in because of between two layers there are gap In gap；The reason of hindering gas transport to catalyst layer: gas is passed through if will affect gas if two interlayers generate moisture film Diffusion layer reaches inside Catalytic Layer；
E) the invention overcomes one side coating method or double spread method is prepared in the method for CCM, in the direct coating catalytic of PEM The phenomenon that PEM caused by agent slurry is removed from notacoria realizes stable preparation CCM and simplifies CCM preparation process；Directly exist The upper painting catalyst slurry of PEM has certain swelling to PEM since the catalyst pulp of coating includes certain water and alcohol Property, it mismatches so that forming size between PEM and notacoria and causes to remove；And the present invention uses and coats perfluor in catalyst layer surface Sulfonate resin (PFSA) solution, for catalyst layer after lyosoption (aqueous and alcohol), deformation quantity is smaller, just overcomes existing The problem of PEM is removed from notacoria；
F) preparation process of proton exchange membrane (PEM) is directly incorporated in the preparation flow of trilamellar membrane electrode (CCM), is saved Cost；
G) preparation process of gas diffusion layers (GDL) can be dissolved into the preparation flow of seven layer membrane electrodes, is further saved It makes an appointment and cost.
Detailed description of the invention
Fig. 1 is the schematic diagram of an embodiment of the prior art, i.e. the preparation of a kind of MEA that refers to of specification background technology part Method, i.e., traditional gas-diffusion electrode (GDE) the preparation method；
Fig. 2 is seven layer membrane electrode structural schematic diagrams of the invention；
Fig. 3 is the schematic diagram of the embodiment of the present invention one；
Fig. 4 is the schematic diagram of the embodiment of the present invention two；
Fig. 5 is the schematic diagram of the embodiment of the present invention three；
Fig. 6 is the schematic diagram of the embodiment of the present invention four；
Fig. 7 is the schematic diagram of an embodiment of film electrode structure of the invention；
Fig. 8 is the flow diagram of a preparation method of the invention, for showing committed step of the invention；
Fig. 9 is the flow diagram of another preparation method of the present invention, for showing.
Appended drawing reference:
Carbon fibre paper layer, 10；Microporous layers, 20；First catalyst layer, 30；Proton exchange membrane, 40；Second catalyst layer, 50；Gas-diffusion electrode, 60；Gas diffusion layers, 70；
Notacoria, 11.
The embodiments will be further described with reference to the accompanying drawings for the realization, the function and the advantages of the object of the present invention.
Specific embodiment
Fig. 1 is please referred to Fig. 9.The invention discloses a kind of preparation methods of fuel cell membrane electrode.It specifically includes as follows Step:
A) with the smooth thin polymer film in surface or corresponding release film (such as: PEFE, FEP, PET, PI, PEEK, PSU film) etc. start, be dusted and destatic processing；
B) coating of catalyst pulp is carried out to notacoria 11, drying obtains Catalytic Layer；
C) it carries out the coating of proton exchange membrane 30 again in Catalytic Layer, dries, and be heat-treated；
D) it carries out the coating of one layer of catalyst again on the outside of proton exchange membrane, dries, heat treatment；Obtain trilamellar membrane electrode CCM。
Due to be catalyzed layer surface roughness properties, this method can be improved Catalytic Layer and proton exchange membrane geometrical contact area, The ion ducting capacity of interlayer is improved, and the inter-layer bonding force between Catalytic Layer and proton exchange membrane can be effectively improved, moreover it is possible to be improved The membrane electrode service life.
The invention is extended to since with Catalytic Layer gas diffusion layers on this basis, i.e., from traditional gas diffusion Electrode (GDE) starts for notacoria.The preparation method of the fuel cell membrane electrode, specifically comprises the following steps:
A) coating of proton exchange membrane, drying are carried out on the catalyst layer of gas diffusion layers, and are heat-treated；
B) it carries out the coating of one layer of catalyst pulp again on the outside of proton exchange membrane, dries, heat treatment；
C) above-mentioned prepared product and existing gas diffusion layers are subjected to laminating process, obtain complete 7 layer membrane electrode.
Gas diffusion layers (GDL) is dissolved into entire preparation flow by such method, can simply, be effectively prepared 7 Layer membrane electrode.
It further extends, the invention discloses a kind of preparation methods of fuel cell membrane electrode.It specifically includes as follows Step:
A) carbon fiber paper 10 with PTFE or white carbon black dispersion liquid is subjected to hydrophobic treatment as substrate, after drying by carbon black, The materials such as carbon nanotube are coated on substrate surface, and drying obtains gas diffusion layers；
B) catalyst pulp coating is carried out on the surface of gas diffusion layers 70, drying obtains the first catalyst layer；
C) the gas diffusion layers catalyst side to above-mentioned coated with catalyst layer carries out the coating of proton exchange membrane, dries, And it is heat-treated；
D) it carries out the coating of one layer of catalyst again on the outside of proton exchange membrane, dries, heat treatment；Obtain the second catalyst Layer；
E) above-mentioned prepared product laminating process is carried out with existing gas diffusion layers (to paste gas diffusion layers respectively Close on the surface of the first catalyst layer, the second catalyst layer), obtain complete 7 layer membrane electrode (as shown in Figure 2).
The process for preparing gas diffusion layers can be dissolved among the seven layer membrane electrode preparation methods of the invention by such method, The small membrane electrode of good contact mass transfer resistance, whole between available gas diffusion layers and Catalytic Layer, Catalytic Layer and proton exchange membrane A process can greatly simplify the preparation process of membrane electrode.
Embodiment one
Referring to Fig. 3, a kind of preparation method of fuel cell membrane electrode, includes the following steps:
A) step 1: dedusting destatics.It is specific as follows, select 25~150 micron thickness notacoria (BL), as PEFE, FEP, PET, PI film etc. the processing such as is dusted and destatics to notacoria surface as the basis material of this embodiment；
B) step 2: the coating of catalyst pulp.So-called Catalytic Layer coating refers to the coating of the first catalyst layer 20. Concrete operations are as follows: catalyst pulp being coated on notacoria substrate by slot coated, and is dried, wherein being catalyzed Agent slurry is a certain proportion of catalyst fines and perfluor sulfoacid resin solution, and the solvent of this catalyst pulp is aqueous solution, water The mixed liquor of alcoholic solution or multi-solvents, Catalytic Layer drying with a thickness of 1~50 micron, catalyst can for the Pt containing carbon carrier, The noble metals such as Pd or base metal and its alloy；
C) step 3: polymer preparation.It is catalyzed the preparation process of slurry are as follows: step 1, a small amount of water of catalyst is sufficiently moistened It is wet；Step 2, perfluor sulfoacid resin solution is slowly added to be dispersed；Step 3, water is added or alcohol configures catalyst pulp At the catalyst pulp of 1%~20% mass concentration；Step 4, pass through ultrasonic disperse or microjet homogenizer or ball mill Or catalyst pulp is uniformly dispersed by the combination of several dispersing modes.The formula and preparation method of perfluor sulfoacid resin solution: PFSA solution, to be diluted to certain polymer with water or alcohols on the basis of the PFSA polymer solution being commercially available Ratio is dispersed with stirring at room temperature.The viscosity of PFSA solution can be changed by way of ultrasound and heating, viscosity control range is 50 ~5000cps is adjustable；For the formula and preparation method of glue referring to PFSA solution formula and preparation method, the two is identical.
D) step 4: Catalytic Layer coating.Catalytic Layer coating herein refers to the coating of the second catalyst layer.Concrete operations It is as follows: perfluorinated sulfonic resin (PFSA) solution is directly coated to the surface of Catalytic Layer, 60~120 degrees Celsius of drying (baking oven or Oven, the roll-to-roll preferred partition baking oven of coating), 10~100 microns of PEM membrane is prepared, wherein PFSA solution is PFSA's The mixed liquor of aqueous solution, water-alcohol solution or multi-solvents, the method can effectively improve the interlayer between Catalytic Layer and proton exchange membrane Binding force improves the service life, and the roughness properties due to being catalyzed layer surface, and the several of Catalytic Layer and proton exchange membrane can be improved in this method What contact area improves the ion ducting capacity of interlayer, then and the preparation process of proton exchange membrane is incorporated membrane electrode by the method Preparation flow greatly reduces operating cost；
E) step 5: the outer surface side of PEM after the drying carries out the coating of a step catalyst pulp again, dries, catalysis Layer drying with a thickness of 1~50 micron, and be heat-treated in 120~250 degree Celsius ranges to get to have notacoria support at Product trilamellar membrane electrode CCM.
It is also pointed out that: the drying operation occurred in the present invention can be carried out with baking oven or oven.
Embodiment two
Referring to Fig. 4, a kind of preparation method of fuel cell membrane electrode, includes the following steps:
A) step 1: polymer preparation.Part is prepared referring to the polymer of embodiment one kind.In addition, applying cloth base material can expand Exhibition is gas-diffusion electrode, and the thickness of gas diffusion layers electrode can be 30~300 microns；
B) step 2: Catalytic Layer coating.Specifically: perfluorinated sulfonic acid tree is directly carried out in the Catalytic Layer of gas-diffusion electrode The coating of rouge, drying heat treatment obtain with a thickness of 5~200 microns of thick proton exchange membrane, and the method can effectively improve Catalytic Layer Inter-layer bonding force between proton exchange membrane, due to being catalyzed the roughness properties of layer surface, Catalytic Layer is can be improved in this method and proton is handed over The geometrical contact area for changing film improves the ion ducting capacity of interlayer；Carry out the painting of one layer of catalyst again in proton exchange membrane It covers, obtains interlayer and connect another excellent electrode, with a thickness of 1~50 micron after catalyst layer drying；
C) step 3: gas diffusion layers fitting.Specifically: finally carrying out commercial gas diffusion layer or obtained by step 2 The fitting of gas diffusion layers, this method can be simple marginal point glue laminating, can also be that gas diffusion layer surface is sprayed one layer Glue is bonded, and the glue sprayed is preferably perfluorosulfonic acid ion polymer solution, and spraying thickness is preferably 1 micron or less.
The contact resistance that 7 layer membrane electrodes that this method is prepared greatly weaken each interlayer of membrane electrode improves mass transfer performances Can, good combination property, low in cost, simple and easy, suitable mass centralization produce, and have very big practical value.
Embodiment three
Referring to Fig. 5, a kind of preparation method of fuel cell membrane electrode, includes the following steps:
A) step 1: Catalytic Layer coating.Concrete operations are as follows: applying cloth base material can directly be preferably gas diffusion layers, gas The thickness of diffusion layer can be 30~260 microns；The coating of catalyst is carried out on the surface of microporous layers, Catalytic Layer is dried with a thickness of 1 ~50 microns, catalyst can be noble metals or the base metal and its alloy such as Pt, Pd containing carbon carrier, and Catalytic Layer is direct Coated on the separation that can effectively prevent PEMFC microporous layers and Catalytic Layer in the process of running on microporous layers, effectively raise The uniformity of electronic conduction ability and gas dispersion between two layers, and prevented the water generated in battery and be detained simultaneously in two interlayers Hinder gas transport to Catalytic Layer；This step forms the first catalyst layer.
B) step 2: polymer is prepared (referring to the polymer preparation part of embodiment one).Perfluorinated sulfonic acid is being prepared After resin, include the steps that as follows.In Catalytic Layer carry out perfluorinated sulfonic resin coating, drying heat treatment obtain with a thickness of 5~200 microns of thick proton exchange membrane, the method can effectively improve the inter-layer bonding force between Catalytic Layer and proton exchange membrane, by In the roughness properties of catalysis layer surface, the geometrical contact area that Catalytic Layer and proton exchange membrane can be improved in this method improve interlayer from Sub- ducting capacity.
C) step 3: Catalytic Layer coating.Specific step is as follows: carrying out the painting of one layer of catalyst again on proton exchange membrane upper layer It covers, obtains interlayer and connect another excellent electrode (general conventional method such as transfer printing can not obtain PEM and catalysis Very strong interface is connected between layer by layer, and the preparation method of the application may be implemented), Catalytic Layer is dried with a thickness of 1~50 micron；This Step forms the second catalyst layer.
D) step 4: gas diffusion layers fitting.Specific step is as follows: finally carrying out commercial gas diffusion layer or by step 2 The fitting of obtained gas diffusion layers, this method can be simple marginal point glue laminating, can also be to spray gas diffusion layer surface It covers one layer of glue to be bonded, the glue sprayed is preferably perfluorosulfonic acid ion polymer solution, and spraying thickness is preferably 1 micron Below.
The contact resistance that 7 layer membrane electrodes that this method is prepared greatly weaken each interlayer of membrane electrode improves mass transfer performances Can, good combination property, low in cost, simple and easy, suitable mass centralization produce, and have very big practical value.
Example IV
Referring to Fig. 6, a kind of preparation method of fuel cell membrane electrode, includes the following steps:
A) step 1: hydrophobic treatment.It is specific as follows: carbon cloth or carbon paper that the substrate of coating is 20~200 microns etc. Conductive gas permeable material, preferably carbon fiber paper.Hydrophobic treatment is carried out on carbon paper, the process of hydrophobic treatment is by carbon paper hydrophobic Material such as solution of PTFE, white carbon black etc. impregnate and sintering processes, and hydrophobic material quality accounting is 10%~50%, hydrophobic Processing can drain ventilative ability in raising PEMFC in operating with environment and maintain the electronic conduction of basis material substantially Ability.
B) step 2: microporous layers coating.It is specific as follows: the mostly empty of carbon black or carbon fiber etc. is carried out to the carbon paper of hydrophobic treatment The coating of layer, with a thickness of 10~60 microns after coating drying, microporous layers 20 can further by by the gas of gas diffusion layers into Row subdivision pressure improves the dispersed homogeneous degree of gas, improves the efficiency that water excludes, and can provide Catalytic Layer and proton exchange membrane Physical buffer protection.
C) step 3: Catalytic Layer coating.It is specific as follows: to carry out the coating of catalyst on the surface of microporous layers, Catalytic Layer is dried Dry thickness is 1~50 micron, and catalyst can be noble metals or the base metals and its alloy such as Pt, Pd containing carbon carrier, will be urged Change layer and be directly coated on microporous layers the separation that can effectively prevent PEMFC microporous layers and Catalytic Layer in the process of running, effectively The electronic conduction ability improved between two layers and gas dispersion the uniformity, and the water for having prevented to generate in battery is at two layers Between be detained and hinder gas transport to Catalytic Layer；This step forms the first catalyst layer.
D) step 4: polymer prepares (the polymer preparation part of reference implementation example one kind).Perfluor sulphur is being prepared After acid resin, include the steps that having as follows: carrying out the coating of perfluorinated sulfonic resin in Catalytic Layer and obtained after drying, heat treatment To the proton exchange membrane with a thickness of 5~200 microns, the method can effectively improve the Coating combination between Catalytic Layer and proton exchange membrane Power, due to being catalyzed the roughness properties of layer surface, Catalytic Layer is can be improved in this method and the geometrical contact area of proton exchange membrane improves layer Between ion ducting capacity.
E) step 5: Catalytic Layer coating.Specific step is as follows: carrying out the painting of one layer of catalyst again on proton exchange membrane upper layer It covers, obtains interlayer and connect another excellent electrode, Catalytic Layer is dried with a thickness of 1~50 micron；This step is prepared Two catalyst layers 50.
F) step 6: gas diffusion layers 70 are bonded.Specific step is as follows: finally carrying out commercial gas diffusion layer or by step The fitting of two obtained gas diffusion layers, this method can be simple marginal point glue laminating, can also be by gas diffusion layer surface It sprays one layer of glue to be bonded, the glue sprayed is preferably perfluorosulfonic acid ion polymer solution, and spraying thickness is preferably 1 micro- Meter or less.
The contact resistance that 7 layer membrane electrodes that this method is prepared greatly weaken each interlayer of membrane electrode improves mass transfer performances Can, good combination property, low in cost, simple and easy, suitable mass centralization produce, and have very big practical value.
Embodiment five
A kind of membrane-membrane electrode for fuel cell structure provided by the invention, comprising:
With a thickness of 25~300 microns of first structure layer；
The first catalyst layer on first structure layer；
Perfluorosulfonic acid proton exchange film on the first catalyst layer；
The second catalyst layer on perfluorosulfonic acid proton exchange film；
Wherein, first catalyst layer, the second catalyst layer thickness be respectively 1~50 micron；
After above each layer is compound, the trilamellar membrane electrode CCM of notacoria support is formed.
Further improve above-mentioned technical proposal: the first structure layer is notacoria, the film electrode structure specifically:
Without electrostatic and dustless notacoria, the notacoria with a thickness of 25~300 microns；
It is coated on the first catalyst layer of the drying on notacoria；
It is coated on the proton exchange membrane of the drying on the first catalyst layer；
It is coated on the second catalyst layer of the drying on the outside of proton exchange membrane；
Wherein, first catalyst layer, the second catalyst layer thickness be respectively 1~50 micron；
After above each layer is compound, the trilamellar membrane electrode CCM of notacoria support is formed.
As improvement to above-mentioned technical proposal, the proton exchange membrane is specifically perfluorosulfonic acid proton exchange film.
As improvement to above-mentioned technical proposal, the notacoria is specifically PEFE film, fep film, PET film, one in PI film Kind film.Notacoria herein is to select one kind from the film of above each material, is not related to change the property of listed film Into.
As the further improvement to inventive film electrode structure, the first structure layer is specially gas diffusion layers, The gas diffusion layers include two sublayers:
First sublayer, using hydrophobic material treated conductive gas permeable material substrate layer；
Second sublayer, the microporous layers for the conductive gas permeable material substrate layer surface being coated on；
The film electrode structure further includes having:
The first catalyst layer on microporous layers；
Perfluorosulfonic acid proton exchange film on the first catalyst layer；
The second catalyst layer on perfluorosulfonic acid proton exchange film；
Wherein, first catalyst layer, the second catalyst layer thickness be respectively 1~50 micron.
As the further improvement to inventive film electrode structure, membrane-membrane electrode for fuel cell structure of the invention, packet It includes:
Conductive gas permeable material substrate layer；
Set on the microporous layers of the conductive gas permeable material substrate layer；Microporous layers herein can also be referred to as porous layer；
The first catalyst layer on the microporous layers；
Proton exchange membrane (PEM) layer on first catalyst layer；
The second catalyst layer on the proton exchange membrane layer；
The gas diffusion layers (GDL) being glued on second catalyst layer；Wherein, gas diffusion layers and the second catalysis Oxidant layer forms gas-diffusion electrode 60；
After above each layer is compound, seven layer membrane electrode structures are formed.
As improvement to above-mentioned technical proposal, the conduction gas permeable material substrate layer is specially carbon cloth or carbon fiber Paper.
As improvement to above-mentioned technical proposal, the microporous layers are specially carbon black layer or carbon nanotube layer.
As improvement to above-mentioned technical proposal, the hydrophobic material is specially the solution of PTFE or white carbon black.
As improvement to above-mentioned technical proposal, the catalyst contained in first catalyst layer, the second catalyst layer, Tool
Body is the noble metal containing carbon carrier or base metal and its alloy.
More preferably, the noble metal is specially platinum (Pt) or palladium (Pd).
As the further improvement to above-mentioned technical proposal, first catalyst layer is anode catalyst layer, described Second catalyst layer is cathode catalyst layer.
Although the film electrode structure being prepared is similar with the membrane electrode general structure that conventional method obtains, compared to The bonding strength of traditional approach, each function interlayer of the membrane electrode of the invention will greatly enhance.Each function of the membrane electrode of the application It is close face contact between ergosphere, and face contact or part often local between each functional layer of existing membrane electrode Point contact, so, membrane electrode of the invention is also distinguished with existing membrane electrode from structure, and this difference is mainly phase The larger difference at the interface between adjacent functional layer.
Embodiment six
Invention additionally discloses a kind of proton exchange film fuel battery system, the membrane electrode being prepared using above-described embodiment Structure.
The fuel cell system can be applied in automotive field, and such as the new energy vehicle comprising the fuel cell system is (such as New energy car, new energy bus etc.), due to using membrane electrode of the invention, jolting, shake etc. for vehicle is not allowed yet Membrane electrode easily is damaged, improves the job stability of fuel cell, applies fuel cell more complicated, severe Under operating condition.The fuel cell can be applied in unmanned plane field, supply electric energy for unmanned plane.
The fuel cell can be applied in robot field, provide electric energy for robot.For example, by fuel of the invention Battery applications are on industrial robot.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example Property, it is not considered as limiting the invention, those skilled in the art are not departing from the principle of the present invention and objective In the case where can make changes, modifications, alterations, and variations to the above described embodiments within the scope of the invention.

Claims (10)

1. a kind of preparation method of fuel cell membrane electrode, which comprises the steps of:
A) prepare with a thickness of 30~300 microns of gas diffusion layers, the gas diffusion layers include with a thickness of 1~50 micron the One catalyst layer；
B) coating of perfluorinated sulfonic resin (PFSA) solution is directly carried out on the first catalyst layer of gas-diffusion electrode；It is dry Processing；The proton exchange membrane (PEM) with a thickness of 5~200 microns is prepared；
C) catalyst pulp is overlying on to the outer surface of the PEM membrane after drying by certain way；Be dried, obtain with a thickness of 1~50 micron of the second catalyst layer；It is subsequently heat-treated；Obtain trilamellar membrane electrode CCM.
2. the preparation method of fuel cell membrane electrode according to claim 1, which is characterized in that further include having following step It is rapid:
D) gas diffusion layers are bonded, that is, by centainly operate the trilamellar membrane electrode CCM for obtaining gas diffusion layers and step c into Row bonding；Seven layer membrane electrodes are prepared.
3. the preparation method of fuel cell membrane electrode according to claim 2, is used to prepare seven layer membrane electrodes, feature exists In including the following steps:
A) prepare two parts of gas diffusion layers, gas diffusion layers with a thickness of 30~260 microns；
B) coating of catalyst pulp is carried out on the surface of the microporous layers of first part of gas diffusion layers, drying, obtain with a thickness of 1~ 50 microns of the first catalyst layer；
C) coating that perfluorinated sulfonic resin (PFSA) solution is carried out in Catalytic Layer, is dried, and heat treatment obtains with a thickness of 5~200 The proton exchange membrane (PEM) of micron；
D) in the proton exchange membrane obtained through step c, then the coating of one layer of catalyst pulp is carried out, forms the second catalyst Layer, Catalytic Layer are dried with a thickness of 1~50 micron；
E) another gas diffusion layers are bonded with the second catalyst layer using certain applying method；The applying method is marginal point Glue laminating is bonded or, gas diffusion layer surface is sprayed one layer of glue, and the glue sprayed is perfluorosulfonic acid ion polymer Solution sprays thickness less than or equal to 1 micron.
4. the preparation method of fuel cell membrane electrode according to claim 2, is used to prepare seven layer membrane electrodes, feature exists In including the following steps:
A) select 20~200 microns thick of conductive gas permeable material for the substrate of coating；
B) hydrophobic treatment is carried out to substrate；
C) coating of microporous layers is carried out on the substrate after hydrophobic treatment；
D) coating of catalyst pulp is carried out on the surface of microporous layers, drying forms the first catalyst with a thickness of 1~50 micron Layer；
E) coating of perfluorinated sulfonic resin is carried out in Catalytic Layer, drying, heat treatment obtain with a thickness of 5~200 microns of thick matter Proton exchange (PEM)；
F) coating for carrying out one layer of catalyst pulp again in proton exchange membrane obtains interlayer and connects another excellent electricity Pole, drying, obtains the second catalyst layer with a thickness of 1~50 micron；
G) another gas diffusion layers are bonded with the second catalyst layer using certain applying method；The applying method is marginal point Glue laminating is bonded or, gas diffusion layer surface is sprayed one layer of glue, and the glue sprayed is perfluorosulfonic acid ion polymer Solution sprays thickness less than or equal to 1 micron.
5. the preparation method of fuel cell membrane electrode according to claim 4, which is characterized in that the substrate is carbon fiber Cloth or carbon fiber paper.
6. the preparation method of fuel cell membrane electrode according to any one of claims 1 to 4, which is characterized in that 120~ It is heat-treated in 250 degree Celsius ranges.
7. the preparation method of fuel cell membrane electrode according to any one of claims 1 to 4, which is characterized in that used Catalyst pulp be a certain proportion of catalyst fines and perfluor sulfoacid resin solution, the solvent of this catalyst pulp is water-soluble The mixed liquor of liquid, water-alcohol solution or multi-solvents；Catalyst fines are containing carbon carrier noble metal or base metal and its to close Gold, wherein the noble metal is Pt or Pd.
8. the preparation method of fuel cell membrane electrode according to any one of claims 1 to 4, which is characterized in that perfluor sulphur Acid resin (PFSA) solution is the aqueous solution of PFSA or the mixed liquor of water-alcohol solution or multi-solvents.
9. the preparation method of fuel cell membrane electrode according to any one of claims 1 to 4, which is characterized in that described complete Perfluorosulfonic acid resin polymer can be replaced by the conducting polymer of any conduction cation or conducts anions or conduction electronics.
10. the preparation method of fuel cell membrane electrode according to any one of claims 1 to 4, which is characterized in that described complete Perfluorosulfonic acid resin polymer can be replaced by the conducting polymer of any conduction cation or conducts anions or conduction electronics.
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