WO2020237755A1 - Liant contenant du fluor, électrode à membrane et procédés pour leur préparation - Google Patents

Liant contenant du fluor, électrode à membrane et procédés pour leur préparation Download PDF

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Publication number
WO2020237755A1
WO2020237755A1 PCT/CN2019/092127 CN2019092127W WO2020237755A1 WO 2020237755 A1 WO2020237755 A1 WO 2020237755A1 CN 2019092127 W CN2019092127 W CN 2019092127W WO 2020237755 A1 WO2020237755 A1 WO 2020237755A1
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Prior art keywords
fluorine
adhesive
support material
catalyst
primer
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PCT/CN2019/092127
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English (en)
Chinese (zh)
Inventor
叶思宇
邹渝泉
唐军柯
杨云松
孙宁
吴力杰
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Sinohykey Technology Co Ltd
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Sinohykey Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • 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
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8668—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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 invention relates to a fluorine-containing binder (binder) used for a membrane electrode of a fuel cell, a membrane electrode using the binder, and a method for preparing the membrane electrode, belonging to the field of binders and membrane electrodes of fuel cells.
  • binder fluorine-containing binder
  • Some materials have low surface energy or high crystallinity or non-polar characteristics, making it difficult to use ordinary adhesives for bonding, which affects their use, such as fluorine-containing polymer materials.
  • the existing methods for improving the bonding performance of difficult-to-stick materials are roughly divided into two types: surface treatment of the difficult-to-stick materials and the use of new adhesives.
  • surface treatment of difficult-to-stick materials can improve the bonding performance of difficult-to-stick materials to a certain extent, the production process is more complicated, especially in some special industries, such as fuel cell membrane electrode manufacturing industry, material surface treatment Will increase the process and prolong the production time.
  • the existing methods for improving the bonding performance of difficult-to-stick materials are roughly divided into two types: surface treatment of the difficult-to-stick materials and the use of new adhesives.
  • One of the most commonly used surface treatment methods is to coat a layer of primer on the surface of the difficult-to-stick material, and then use an adhesive to bond it after the primer is completely dried.
  • this method is also very limited in improving the bonding performance of difficult-to-stick materials, especially in some special industries, such as the fuel cell membrane electrode manufacturing industry. The effect of increasing the bonding performance produced by this method does not make people satisfaction.
  • CCM Catalyst Coated Membrane
  • a (frame-shaped) support material with a central hole the commonly used adhesives include acrylic and epoxy Or polyolefin polymers.
  • the CCM is composed of a catalyst layer and a film.
  • the film is generally a perfluorosulfonic acid resin film
  • the support material is generally polyethylene terephthalate (PET), polyimide (PI), and poly 1,6-naphthalene Hydrocarbon polymers such as ethylene formate (PEN), polyphenylene sulfide (PPS), polyether ketone (PEK) and polycarbonate (PC).
  • the perfluorosulfonic acid resin membrane is a high molecular polymer with fluorine atoms in the main chain and side chains. Since the bond energy of the CF bond is as high as 485kJ ⁇ mol/L, it is the largest bond energy of all covalent bonds.
  • the bonding strength between the edge of the CCM (Catalyst Coated Membrane) and the (frame-shaped) support material with a central hole needs to be further improved.
  • the purpose of the present invention is a fluorine-containing binder (binder), and also provide a membrane electrode with improved bonding strength for fuel cell membranes, and the preparation of membranes Electrode method.
  • a fluorine-containing polyacrylate block copolymer binder having the general formula (I) is provided:
  • m:n 0.3-3:1, preferably 0.5-2:1, more preferably 0.7-1.6:1, more preferably 0.8-1.2:1.
  • the number average molecular weight (Mn) of the binder is 5 ⁇ 10 3 to 6 ⁇ 10 4 , preferably 2 ⁇ 10 4 to 5 ⁇ 10 4 , and more preferably 3 ⁇ 10 4 to 4.8 ⁇ 10 4 .
  • Dissolve CH 2 CH-COOCH 2 Rf monomer in an organic solvent (for example, aromatic hydrocarbons, such as benzene or toluene) to obtain a monomer with a concentration of 20-60wt% (preferably 25-50wt%, such as 30wt% or 40wt%)
  • an organic solvent for example, aromatic hydrocarbons, such as benzene or toluene
  • the structure of the Rf group is CF 3 (CF 2 ) k (CH 2 ) l , k is an integer from 0 to 12 (preferably 1 to 5, such as 2 to 3), and l is 0 or 1, and the structure of the R group Is CH 3 (CH 2 ) x , and x is an integer of 0-12 (preferably 1-5, such as 2-3).
  • the above-mentioned catalytic system includes cuprous bromide and pentamethyldiethylenetriamine, and the above-mentioned initiator is ethyl 2-bromoisobutyrate.
  • the two monomers used in the above method are prepared by the following method: the alcohol compound RfCH 2 -OH or R-OH is dissolved in an organic solvent to form 15-60wt% (preferably 20-50wt%, such as 30wt% Or 40wt%) concentration of alcohol solution, and then add (for example, 0.1-10wt%, based on the mass of alcohol) radical polymerization inhibitor; add triethylamine as a catalyst (used to complex the generated hydrogen chloride), the resulting The reaction system (for example, with an ice water bath) is cooled (for example, cooled to below 10°C), and the acrylic chloride monomer is added dropwise under stirring.
  • the alcohol compound RfCH 2 -OH or R-OH is dissolved in an organic solvent to form 15-60wt% (preferably 20-50wt%, such as 30wt% Or 40wt%) concentration of alcohol solution, and then add (for example, 0.1-10wt%, based on the mass of alcohol) radical polymerization inhibitor; add triethylamine as
  • the method includes the following steps:
  • acrylate monomer Dissolve alcohol containing RfCH 2 group or R group (ie alcohol RfCH 2 -OH or R-OH) in an organic solvent, and prepare an alcohol solution with a concentration of 15-60% by weight, Add a polymerization inhibitor to the alcohol-containing solution.
  • the amount of the polymerization inhibitor is 0.1-10% by weight of the alcohol containing the RfCH2 group or the R group; then the catalyst triethylamine is added to complex the hydrogen chloride produced, with ice Cool the reaction system to below 10°C in a water bath, add acrylic chloride monomer dropwise under stirring, observe the temperature and control the dropping rate so that the temperature is not higher than 50°C; after the monomer is added dropwise, continue stirring at room temperature for 0.5-2 After hours, the reaction product was poured into 1 to 3 times the volume of deionized water and washed, and the organic layer and the water layer were separated using a separatory funnel.
  • the catalytic system includes cuprous bromide and pentamethyldiethylenetriamine, the initiator is ethyl 2-bromoisobutyrate, and the acrylate monomer containing RfCH 2 group: ethyl 2-bromoisobutyrate: penta
  • the ratio of methyldiethylenetriamine: cuprous bromide is: 40:0.8-1.2:1.6-2.4:0.8-1.2, preferably 40:1:2:1;
  • the solvent is a non-polar aromatic hydrocarbon solvent, The solvent is subjected to water removal treatment; the molar ratio of the triethylamine to the alcohol containing the RfCH 2 group or the R group is 1.01:1 to 1.2:1, and the acrylic chloride monomer and the RfCH 2 group-containing alcohol
  • the molar ratio of the alcohol of the group or the R group is 1.01:1 to 1.2:1; the molar ratio of the monomer containing the RfCH 2 group and the R group used in the step (2) is 0.8
  • the above-mentioned binder can be directly used to bond membrane electrodes; or, the binder can be formulated into an adhesive mixture (ie, the first fluorine-containing adhesive described below) And the latter is directly used for bonding membrane electrodes.
  • the adhesive mixture is prepared by mixing 65 to 95 parts by weight of the above-mentioned binder, and 1 to 5 parts by weight of an initiator (for example, an inorganic or organic peroxide initiator, such as benzoyl peroxide or two Tert-butyl), 1 to 5 parts by weight of curing agent (for example, aromatic amines, such as m-phenylenediamine or p-phenylenediamine), 3 to 25 parts by weight of toughening agent dissolved in the second organic solvent Forming.
  • an initiator for example, an inorganic or organic peroxide initiator, such as benzoyl peroxide or two Tert-butyl
  • curing agent for example, aromatic amines, such as m-phenylenediamine or p-phenylenediamine
  • toughening agent dissolved in the second organic solvent Forming.
  • the preparation method of the membrane electrode includes: coating a binder or an adhesive mixture on the surface of a frame-shaped support material, attaching the CCM to the frame-shaped support material, heating to 80-150°C, and curing for 5-300s.
  • binder and primer can also be used in combination to bond the membrane electrode, as described below.
  • a method for improving the bonding strength between a frame shape support material and a catalyst-coated perfluorinated ion exchange resin membrane includes the following steps:
  • the first fluorine-containing adhesive is applied on the surface of the primer layer so as to be between the primer layer and the first adhesive coating Forming a fusion layer or a transition layer or an overlapping layer (ie, an intermediate layer);
  • primer layer and the first fluorine-containing adhesive layer be completely cured (for example, by heating them to 80-150°C and holding them for 5 to 300s), so that the edges of the catalyst-coated perfluorinated ion exchange resin membrane and the frame shape The supporting materials are glued together.
  • the primer includes or mainly consists of the following components: a fluoropolymer resin or a fluoro-modified polymer resin as a binder, a toughening agent (preferably a fluorine-containing rubber additive) and The first solvent.
  • a fluoropolymer resin or a fluoro-modified polymer resin as a binder
  • a toughening agent preferably a fluorine-containing rubber additive
  • the first fluorine-containing adhesive is selected from fluorine-containing polyacrylate adhesives, fluorine-containing epoxy resin adhesives, fluorine-containing polyurethane adhesives, fluorine-containing silicone adhesives, and fluorine-containing silicone adhesives.
  • fluorine-containing polyacrylate adhesives fluorine-containing epoxy resin adhesives
  • fluorine-containing polyurethane adhesives fluorine-containing silicone adhesives
  • fluorine-containing silicone adhesives fluorine-containing silicone adhesives.
  • One or more of polyimide adhesive and fluorine-containing polyolefin adhesive preferably polyurethane-fluorinated epoxy acrylate adhesive or polyvinylidene fluoride adhesive; preferably, the first fluorine-containing adhesive
  • the adhesive contains a second solvent.
  • the first solvent and the second solvent may be the same or different.
  • the primer and the first fluorine-containing adhesive are both thermosetting.
  • the first type of fluorine-containing adhesive includes a thermal curing type in which chain extension and/or crosslinking reaction occurs under heating or a thermal curing type in which a solvent contained therein is cured by volatilization under heating.
  • the primer is a heat curing type in which the solvent contained therein is cured by volatilization under heating.
  • the first fluorine-containing adhesive is a thermal curing type in which chain extension and/or crosslinking reactions occur under heating.
  • a membrane electrode for a fuel cell comprising: a frame-shaped support material having a central hole, and a catalyst-coated perfluorinated ion that completely covers the central hole of the frame-shaped support material Exchange resin membrane, a sheet-like cathode gas diffusion component bonded on one surface of a catalyst-coated perfluoroion exchange resin membrane, and a sheet bonded to the other surface of a catalyst-coated perfluoroion exchange resin membrane
  • the anode gas diffusion assembly is characterized in that between the frame-shaped support material and the catalyst-coated perfluorinated ion exchange resin membrane, there is a cured primer layer adhered to the frame-shaped support material and the perfluorinated ion exchange resin film.
  • a method for preparing the above-mentioned membrane electrode including the following steps:
  • the first fluorine-containing adhesive is applied on the surface of the primer layer so as to be between the primer layer and the first adhesive coating Forming a fusion layer or a transition layer or an overlapping layer (ie, an intermediate layer);
  • primer layer and the first fluorine-containing adhesive layer be completely cured (for example, by heating them to 80-150°C and holding them for 5 to 300s), so that the edges of the catalyst-coated perfluorinated ion exchange resin membrane and the frame shape The supporting materials are glued together;
  • the second adhesive and the third adhesive can be the same or different.
  • the primer includes or mainly consists of the following components: a fluoropolymer resin or a fluoro-modified polymer resin as a binder, a toughening agent (preferably a fluorine-containing rubber additive) and The first solvent.
  • a fluoropolymer resin or a fluoro-modified polymer resin as a binder
  • a toughening agent preferably a fluorine-containing rubber additive
  • the first fluorine-containing adhesive is selected from fluorine-containing polyacrylate adhesives, fluorine-containing epoxy resin adhesives, fluorine-containing polyurethane adhesives, fluorine-containing silicone adhesives, and fluorine-containing silicone adhesives.
  • fluorine-containing polyacrylate adhesives fluorine-containing epoxy resin adhesives, fluorine-containing polyurethane adhesives, fluorine-containing silicone adhesives, and fluorine-containing silicone adhesives.
  • polyimide-based adhesives and fluorine-containing polyolefin-based adhesives are preferably polyurethane-fluorinated epoxy acrylate adhesives or polyvinylidene fluoride adhesives.
  • the first fluorine-containing adhesive is a polyurethane-fluorinated epoxy acrylate adhesive or a polyvinylidene fluoride adhesive.
  • the first fluorine-containing adhesive contains a second organic solvent.
  • the first fluorine-containing adhesive is prepared by mixing 65 to 95 parts by weight of the above-mentioned binder and 1 to 5 parts by weight of an initiator (for example, an inorganic or organic peroxide type initiator, such as benzyl peroxide). Acyl or di-tert-butyl peroxide), 1 to 5 parts by weight of curing agent (for example, aromatic amines, such as m-phenylenediamine or p-phenylenediamine), and 3 to 25 parts by weight of toughening agent dissolved in the second Formed in a kind of organic solvent.
  • an initiator for example, an inorganic or organic peroxide type initiator, such as benzyl peroxide
  • Acyl or di-tert-butyl peroxide 1, 1 to 5 parts by weight of curing agent (for example, aromatic amines, such as m-phenylenediamine or p-phenylenediamine), and 3 to 25 parts by weight of toughening agent dissolved in
  • the primer, the first fluorine-containing adhesive, the second adhesive and the third adhesive are all thermosetting.
  • the first fluorine-containing adhesive, the second adhesive and the third adhesive mentioned above can be the same or different.
  • the second adhesive and the third adhesive may be the same or different and independently are epoxy resin adhesives
  • the polyolefin-based adhesive or polyacrylate-based adhesive is more preferably an epoxy resin-based adhesive or polyacrylate-based adhesive.
  • the primer includes a fluorine-modified polymer resin, a toughening agent, and an organic solvent (for example, methyl isobutyl ketone).
  • the fluorine-modified polymer resin is selected from vinyl fluoride-vinyl ether copolymers (for example, vinyl fluoride-perfluorovinyl perfluoro C2-C4 alkylene ether sulfonic acid copolymer), partial Difluoroethylene-vinyl ether copolymer (for example, vinylidene fluoride-perfluorovinyl perfluoro C2-C4 alkylene ether sulfonic acid copolymer), tetrafluoroethylene-vinyl perfluoroalkylene ether sulfonic acid copolymer (E.g.
  • tetrafluoroethylene-perfluorovinyl perfluoro C2-C4 alkylene ether sulfonic acid copolymer perfluoropropylene-vinylidene fluoride polymer, perfluoropropylene-perfluoroethylene-vinyl ether copolymer (For example, perfluoropropylene-perfluoroethylene-perfluorovinyl perfluoro C2-C4 alkylene ether sulfonic acid) one or more.
  • the number average molecular weight Mn (GPC) of these fluoro-modified polymer resins is generally between 40,000 and 60,000, for example, about 50,000.
  • the toughening agent is selected from carboxylated nitrile rubber, neoprene, chlorosulfonated polyethylene, ABS resin, or perfluoropropylene-vinylidene fluoride rubber and ethylene-vinyl acetate polymer according to 15-45: One or more of the mixture of 85-55 weight ratio.
  • the number average molecular weight Mn (GPC) of these polymers as toughening agents is generally between 40,000 and 60,000, for example, about 50,000.
  • the frame-shaped support material for example, polyester film
  • the frame-shaped support material has a hole punched out in the center.
  • the area of the center hole accounts for 50-96% of the area of the entire frame, preferably 70-95%, more preferably 80-92%, such as 80% or 88%.
  • the outline of the frame of the frame-shaped supporting material may be square, rectangular or circular.
  • the outline of the central hole can also be square, rectangular or circular.
  • the CCM (Catalyst Coated Membrane) used in this application and the (frame-shaped) support material with a central hole are all commercially available products.
  • the thickness of the primer layer is 1-10 ⁇ m, preferably 3-7 ⁇ m, more preferably 4-6 ⁇ m.
  • the thickness of the adhesive layer used in combination with the primer layer is 2 to 50 ⁇ m, preferably 5 to 40 ⁇ m, more preferably 8 to 35 ⁇ m, more preferably 15 to 30 ⁇ m, such as 20 or 25 ⁇ m.
  • the thickness of the fusion layer (or transition layer or overlap layer) between the primer layer and the adhesive layer is generally 0.5 to 3 ⁇ m, 0.7 to 2 ⁇ m.
  • the primer layer before the primer layer is completely cured or in the case where the primer layer is partially cured, the primer layer is in a partially dried and cured state or a partially wet state.
  • the first fluorine-containing adhesive is dot-coated (or sprayed) on the surface of the primer layer, and the solvent contained in the adhesive (that is, the second organic solvent) ) Can swell the primer and be self-volatile, so that the first fluorine-containing adhesive can gradually penetrate into the primer layer before the solvent is completely volatilized, forming a fusion layer or overlapping layer, and after the solvent is completely volatilized, The first fluorine-containing adhesive no longer enters the primer layer.
  • the mass fraction of the solvent (ie, the second organic solvent) contained in the first fluorine-containing adhesive is 5-50 wt%.
  • the boiling point of the solvent is generally 60 to 150°C, preferably 75 to 130°C, more preferably 90 to 120°C.
  • the fluorine-modified polymer resin used in the primer includes one or more of a solubilizing functional group, an adhesive functional group, a crosslinking curable functional group, and a rheological promoting functional group.
  • the present invention has the following beneficial technical effects:
  • the adhesive of the general formula (I) of the present invention includes a fluorine-containing block copolymer. Because the fluorine-containing block copolymer adhesive has phase separation, the fluorine-containing section will aggregate to form a fluoride-philic phase, while the hydrocarbon The part of the fluorine-containing hard-to-stick material will aggregate to form a hydrocarbon-philic phase, so that this kind of adhesive can have good adhesion to hydrocarbons and fluorine-containing hard-to-stick materials at the same time, even if no primer is used when bonding fluorine-containing hard-to-stick materials It can have better bonding performance, in which the size of the phase separation size can be adjusted according to the molecular weight of each segment of the polymer and the relative ratio of the molecular weight to achieve the best bonding effect.
  • the method of the present invention firstly performs primer treatment on the material to be bonded. Before the primer is completely cured, the first fluorine-containing adhesive is used to treat the surface of the primer so that the primer and the first fluorine-containing A fusion layer or overlapping layer between the primer and the first fluorine-containing adhesive is formed between the adhesives.
  • the first fluorine-containing adhesive and the primer in the overlapping layer are fused with each other Cured together, there is no clear interface, so the adhesion between the first fluorine-containing adhesive and the primer is improved, and the primer and the first fluorine-containing adhesive treat the bonding material "frame-shaped support material" and The other material to be bonded (CCM) has good bonding performance, thereby improving the bonding strength between the support material and the CCM.
  • the supporting material DuPont Teijin Films, 542, thermoplastic polyester film material
  • cathode gas diffusion components SGL, Sigracet GDL 25 BC
  • anode gas diffusion components SGL, Sigracet GDL 25 BC
  • the membrane (CCM) of perfluorinated ion exchange resin (such as Nafion resin) coated with platinum metal nanoparticles can also be described in CN106848355A, CN1992400 A, CN103682386 A, CN109088073 A, CN108075158 A, CN109860630 A and CN102544558 A. The method disclosed in.
  • the binder of this embodiment is applied to the fuel cell field, and the adhesive is used to bond the CCM and the supporting material in the membrane electrode of the fuel cell.
  • the preparation method of the binder (binder) includes the following steps:
  • the ratio is 42:1:2.1:1, and react at 60°C under argon atmosphere for 25 hours; after the polymerization reaction is completed, cool to room temperature under argon atmosphere, and then add monomers containing CH 3 groups, containing CH 3
  • the molar ratio of the monomer of the group to the monomer containing the CF 3 CH 2 group is 1:1, the temperature is raised to 60°C, and the reaction is continued for 25 hours under an argon atmosphere.
  • the mixture is filtered to obtain the filtrate Two times the volume of the filtrate was used to precipitate polymer solids from the filtrate.
  • the precipitated polymer solids were washed with 220 mL of deionized water each time for a total of 2 washes.
  • the resulting polymer solids were dried under vacuum at 40°C for 24 hours.
  • the fluorine-containing block copolymer 1 was obtained.
  • the fluorinated block copolymer has the following structural formula:
  • the method when the binder (binder) of this embodiment is used for bonding CCM and support material includes the following steps: dissolving binder, initiator, curing agent and toughening agent in a solvent, and then coating After being placed on the surface of the support material, the CCM is attached to the support material, and the temperature is raised to cure.
  • the curing temperature of the adhesive is 80°C, and the curing time of the adhesive is 300s.
  • the mass percentages of binder, initiator, curing agent and toughening agent are: 65% of binder, 5% of initiator, 5% of curing agent, 25% of toughening agent; initiator is peroxide Benzoyl, curing agent is m-phenylenediamine, and toughening agent is carboxyl nitrile rubber (GPC number average molecular weight Mn is 52000).
  • the binder of this embodiment is applied to the fuel cell field, and the adhesive is used to bond the CCM and the supporting material in the membrane electrode of the fuel cell.
  • the preparation method of binder includes the following steps:
  • the temperature to control the dropping rate to make The temperature of the reaction system is not higher than 50°C; after the monomer is added dropwise, continue to stir at room temperature for 1 hour, then pour the reaction product into 2 times volume of deionized water to wash, use a separatory funnel to separate the organic layer and the water layer, After washing 4 times, the combined organic layer was dried overnight with MgSO 4 ; then the organic layer was recrystallized with toluene to obtain purified CF 3 (CF 2 ) 2 CH 2 group or CH 3 (CH 2 ) 2 group The monomer containing CF 3 (CF 2 ) 2 CH 2 group or CH 3 (CH 2 ) 2 group is stored in the refrigerator at low temperature;
  • the obtained filtrate is used to precipitate polymer solids from the filtrate with 4 times the volume of the filtrate.
  • the precipitated polymer solids are It was washed with 200 mL of deionized water for three times, and the obtained polymer solid was dried under vacuum at 50° C. for 24 hours to obtain fluorine-containing block copolymer 2.
  • the fluorinated block copolymer has the following structural formula:
  • Its number average molecular weight Mn measured by GPC method is 48,500.
  • the method when the binder (binder) of this embodiment is used for bonding CCM and support material includes the following steps: dissolving binder, initiator, curing agent and toughening agent in a solvent, and then coating After the surface of the support material, the CCM is attached to the support material, and the temperature is raised to cure.
  • the curing temperature of the adhesive is 110°C, and the curing time of the adhesive is 120s.
  • the mass percentages of binder, initiator, curing agent and toughening agent are: 70% of the binder, 5% of the initiator, 5% of the curing agent, and 20% of the toughening agent; the initiator is peroxide Benzoyl, curing agent is m-phenylenediamine, and toughening agent is carboxyl nitrile rubber (GPC number average molecular weight Mn is 52000).
  • the CCM is a self-made component, which is based on "Durability and degradation analysis of hydrocarbon ionomer membrane in polymer electrolyte fuel cells accelerated stress evaluation", ⁇ Journal of Power Sources>, 2017 Issue 367, pages 63-71 ( oF: Ryo Shimizu et 2.1 part) was prepared as described.
  • the membrane electrode preparation method includes the following steps:
  • the adhesive is it is formed by mixing 78wt% of the adhesive A synthesized in the above preparation example A and 22wt% of methyl isobutyl ketone solvent.
  • the CCM is attached to the frame-shaped support material. Before the solvent in the adhesive is completely volatilized, the solvent in the adhesive will swell the primer, and the adhesive will gradually penetrate into the primer layer to form an overlap with a thickness of 0.8 ⁇ m Layer, heat up to 80°C, keep for 120s, so that the primer and adhesive layer are completely cured;
  • an unpunched rectangular (15 ⁇ 10 cm) support material is also used to repeat the operations of steps (2) and (3) to obtain samples for testing.
  • Samples were taken from multiple batches of products, and the samples were measured according to the Chinese standard GB/T 2792-2014 "Test Method for Peeling Strength of Adhesive Tapes" to measure the bonding strength between the support material and CCM (refer to Adhesive Tapes and Anti-sticking Material method), and the test results are shown in Table 1 as the arithmetic average of the peel strength (N/cm).
  • the second adhesive is bisphenol A epoxy resin (E-51).
  • the wet coating thickness of the second adhesive is 3.5um.
  • the width is 10mm; after the application is finished, cover the sheet-shaped cathode gas diffusion assembly to the CCM, attach the two, and then turn over, and then attach the sheet-shaped anode gas diffusion assembly on the back side;
  • the third adhesive is the same as the second adhesive.
  • the wet coating of the adhesive has a thickness of 3.5um and a width of 10mm; after the application is completed, The sheet anode gas diffusion assembly covers the CCM;
  • the membrane electrode is fabricated by heating and curing, the heating temperature is 150°C, and the heating time is 120s.
  • Example 1 was repeated, except that in step (3), the fluorinated block copolymer 1 of Preparation Example 1 was used instead of adhesive A and perfluoropropylene-vinylidene fluoride polymer was used as the fluorine-modified polymer resin instead of tetrafluoroethylene.
  • a random copolymer of ethylene and CF 2 CF-O-CF 2 CF 2 -SO 3 H.
  • Example 1 was repeated, except that the polyphenylene sulfide support material was used instead of the PET support material and the fluorinated block copolymer 2 of Preparation Example 2 was used instead of the adhesive A in step (3). An overlapping layer with a thickness of 2.8 ⁇ m is formed.
  • the membrane electrode preparation method includes the following steps:
  • the adhesive is formed by mixing 70% by weight of the fluorinated block copolymer 1 synthesized in the above preparation example 1 and 30% by weight of methyl isobutyl ketone solvent.
  • the thickness of the wet coating of the adhesive is 20 ⁇ m.
  • the second adhesive is bisphenol A epoxy resin (E-51).
  • the wet coating thickness of the second adhesive is 3.5um.
  • the width is 10mm; after the application is completed, cover the sheet-shaped cathode gas diffusion assembly to the CCM, attach the two, and then turn over, and then attach the sheet-shaped anode gas diffusion assembly on the back side;
  • the third adhesive is the same as the second adhesive.
  • the wet coating of the adhesive has a thickness of 3.5um and a width of 10mm; after the application is completed, The sheet anode gas diffusion assembly covers the CCM;
  • the membrane electrode is fabricated by heating and curing, the heating temperature is 150°C, and the heating time is 120s.
  • Example 4 was repeated, except that the fluorinated block copolymer 2 of Preparation Example 2 was directly used to bond the support material and the CCM.
  • the peeling force between the two materials is much greater than that produced by using traditional adhesives.
  • the peeling force, and the peeling force of the product of the present invention is far greater than the requirements of the membrane electrode field for the peeling force of CCM and support material.
  • the bonding performance between CCM and the support material is high, without air leakage, and a toughening agent is used in the primer, which improves the toughness of the bonding structure and avoids the brittleness of the bonding structure caused by a wide range of temperature changes during use Cracking, piercing the membrane material, resulting in air leakage, further reducing the possibility of air leakage, improving the performance and life of the membrane electrode; on the other hand, after the CCM is bonded to the support material, continue to bond the cathode gas diffusion layer Later, when bonding the anode gas diffusion layer, there is still a reversal process.
  • the method for preparing membrane electrodes of the present invention is suitable for large-scale industrialization of membrane electrodes.

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Abstract

L'invention concerne un liant copolymère séquencé à base de polyacrylate contenant du fluor. L'invention concerne également un procédé pour améliorer la force de liaison d'une électrode à membrane par liaison de CCM (matériaux de contact cathodique) et d'un matériau de support à l'aide d'un apprêt et d'un adhésif pour former une couche de fusion entre une couche d'apprêt et un revêtement adhésif, et une électrode à membrane et un procédé pour sa préparation.
PCT/CN2019/092127 2019-05-30 2019-06-20 Liant contenant du fluor, électrode à membrane et procédés pour leur préparation Ceased WO2020237755A1 (fr)

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CN111785932B (zh) * 2020-09-07 2021-01-26 苏州清陶新能源科技有限公司 一种锂离子电池的正极制备方法
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