CN113113650B - High-enhancement composite membrane containing fluorine proton or ion exchange membrane - Google Patents

High-enhancement composite membrane containing fluorine proton or ion exchange membrane Download PDF

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CN113113650B
CN113113650B CN202110337002.XA CN202110337002A CN113113650B CN 113113650 B CN113113650 B CN 113113650B CN 202110337002 A CN202110337002 A CN 202110337002A CN 113113650 B CN113113650 B CN 113113650B
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film
microporous
fluorine
membrane
ion exchange
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CN113113650A (en
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吴慧生
杨颖�
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Shanghai Hancheng Industrial Co.,Ltd.
Shanghai Hanpu New Material Technology Co ltd
Shanghai Hanxun New Energy Technology Co ltd
Zhejiang Hancheng New Energy Co ltd
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Shanghai Hanpu New Material Technology Co ltd
Zhejiang Hancheng Technology Co ltd
Zhejiang Hancheng New Energy Co ltd
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Publication of CN113113650A publication Critical patent/CN113113650A/en
Priority to AU2021438644A priority patent/AU2021438644A1/en
Priority to EP21934675.6A priority patent/EP4318693A1/en
Priority to JP2023559744A priority patent/JP2024515480A/en
Priority to KR1020237033275A priority patent/KR20230152725A/en
Priority to CN202180096477.2A priority patent/CN117242608A/en
Priority to CA3213093A priority patent/CA3213093A1/en
Priority to BR112023019970A priority patent/BR112023019970A2/en
Priority to PCT/CN2021/138855 priority patent/WO2022206039A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • 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
    • 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

Abstract

The invention discloses a high-enhancement composite membrane containing a fluorine proton or ion exchange membrane, which is characterized by comprising at least two layers of microporous enhancement membranes, wherein the two sides of each layer of microporous enhancement membrane are filled with fluorine-containing proton or ion exchange resin, and the weight ratio of the microporous enhancement membranes to the fluorine-containing proton or ion exchange resin is 5: 95-40: 60; preferably, the composite film further comprises a release film, the release film is attached to the bottommost layer of the composite film, and the components of the release film are engineering plastics containing bisphenol A as a main component or engineering plastics containing hexafluorodimethyl bisphenol A as a main component; wherein the engineering plastic containing bisphenol A as the main component is a polymer obtained by polymerizing or copolymerizing bisphenol A, and the weight ratio of the polymer is more than 50 percent; the engineering plastic containing the hexafluorodimethyl bisphenol A as the main component is a polymer obtained by polymerization or copolymerization of the hexafluorodimethyl bisphenol A, and the weight ratio of the engineering plastic is more than 50%.

Description

Composite membrane of high-enhancement type fluorine-containing proton or ion exchange membrane
Technical Field
The invention relates to a special high-enhancement composite membrane containing a fluorine proton or ion exchange membrane.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs), which are high-efficiency power generation devices capable of directly converting fuel and chemical energy into electric energy, have attracted much attention in various industries because they have the advantages of high energy conversion rate, environmental friendliness, low-temperature start, low noise, and the like, as compared to conventional cells. The core component is a proton exchange membrane which is positioned at the most central position of the fuel cell and provides a channel for transferring protons generated by a cathode to an anode. The currently most commercially available proton exchange membranes are the first commercialized Nafion-series membranes (>25 μm thick) containing fluorosulfonic acid from Dupont, USA, which are mainly obtained by melt extrusion, calendering and stretching. The Gore-Select series of recent U.S. Gore corporation was made by tape casting a single layer microporous PTFE reinforced membrane, which was ultra thin (<25 microns thick), primarily made by tape casting (see U.S. patent No. 5547551, 5599614), and a few domestic companies were imitating.
The molecular structure of the fluorine-containing sulfonic acid resin is composed of a fluorocarbon main chain and a branched chain with a sulfonic group at the tail end, the polarizability of the main chain of a fluorocarbon bond is small, hydrophilic sulfonic acid or carboxylic acid groups on the branched chain can adsorb water molecules, and a micro-phase separation structure is formed inside a membrane due to the strong polarity difference between the hydrophobic main chain and the hydrophilic branched chain, and plays an important role in the mechanical property and the transmission property of the membrane. Therefore, the fluorosulfonic acid-containing resin film has basic properties such as excellent proton conductivity, low gas permeability, good mechanical properties and dimensional stability, and small contact resistance with a catalytic layer, and meets the application conditions of being used as a proton exchange membrane. The method for preparing the proton exchange membrane by adopting the sulfonic acid resin solution is more, for example: casting, dipping, spraying, and the like. At present, the preparation process of proton exchange membranes and various reinforced composite proton exchange membranes is complex, and continuous production is difficult to realize.
Patent ZL201010104002.7 discloses a method for preparing proton exchange membrane, which comprises blending sulfonated polyether ether ketone and sulfonated polyether sulfone to form a membrane solution, pouring the membrane solution into a mold to evaporate the solvent to form a membrane, and then carrying out vacuum drying and acid treatment to obtain the proton exchange membrane.
Patent ZL200710011141.3 discloses a novel proton exchange membrane forming process, which uses a single-layer expanded polytetrafluoroethylene microporous membrane as a base membrane, and the single-layer expanded polytetrafluoroethylene microporous membrane is firstly immersed into a low-concentration resin solution and then repeatedly immersed into a high-concentration resin solution for many times until reaching a proper membrane thickness.
Patent ZL201710251603.2 discloses a fluorine-containing chlorine-containing conductive polymer double-sided filled composite film, but the used film manufacturing method adopts release paper, and flock pollution caused by the release paper is easy to generate during production of high-quality films.
The release film refers to a film having a surface with separability, and the release film is not sticky or slightly sticky after being contacted with a specific material under limited conditions. In general, in order to increase the release force of the plastic film, the plastic film is subjected to corona or plasma treatment, followed by or coated with a release agent for surface modification, most commonly, a silicon-containing release agent or a fluorine-containing release agent is coated on the surface layer of the plastic film, so that the plastic film can show extremely light and stable release force for various organic glues. At present, silicone release paper (film) is commonly used in the market, silicone is used as a release agent, and the biggest defect is that the silicone remains on the surface of a product during stripping.
The polycarbonate insulating release film is also a common release film, and comprises 2, 2' -bis (4-hydroxyphenyl) propane polycarbonate, commonly known as polycarbonate, which is a high molecular polymer containing a carbonate group formed by condensation polymerization of bisphenol A in a molecular chain. The thermoplastic engineering plastic is an amorphous, odorless, nontoxic and highly transparent colorless or yellowish thermoplastic engineering plastic, has excellent physical and mechanical properties, particularly excellent impact resistance, and high tensile strength, bending strength and compression strength; small creep property and stable size. And thus is widely used in various fields. However, the polycarbonate insulating release film can work only by adding other additives or coating a release agent.
CN105440641A discloses a polycarbonate insulating release film, which requires the addition of other additives, and these additives are easily released during the casting process to cause the film surface contamination.
CN1840324A discloses a method for manufacturing a release film, which has a complicated process and requires a release agent to be coated, and the release agent is easily released during the casting process to cause the pollution of the film surface.
In addition, as disclosed in patents CN200710013624.7, US7259208, CN101350415B, CN101780376B, CN104018181A, CN101320818B, CN201546122U, CN103187549A, and CN1298890C, the fluoropolymer microfibers are not continuous phase and cannot be connected to form a film.
With the development of low carbon and green economy, the requirements or the application of a fluorine-containing proton exchange membrane or ion exchange membrane and a release film matched with the fluorine-containing proton exchange membrane or ion exchange membrane are higher and higher, the release film is required to have the effects of isolation and filling in actual use and also has the protection effect, and the release agent does not pollute the casting coating and has the effects of heat dissipation and the like; the requirements on the cleanliness, mechanical strength and service life of fluorine-containing proton exchange membranes or ion exchange membranes become more and more important.
Disclosure of Invention
Because the technical problems exist in the prior art, the application aims to provide the special high-enhancement composite membrane containing the fluorine proton or ion exchange membrane so as to solve the problems that the preparation process of the exchange membrane in the prior art is complex, is easily polluted by a release agent and is difficult to continuously produce.
In order to achieve the technical purpose, the following technical scheme is adopted in the application:
a special high-enhancement composite membrane containing fluorine proton or ion exchange membrane is characterized by comprising at least two layers of microporous enhancement membranes, wherein two sides of each layer of microporous enhancement membrane are filled with fluorine-containing proton or ion exchange resin, and the weight ratio of the microporous enhancement membrane to the fluorine-containing proton or ion exchange resin is 5: 95-40: 60; the special release film is attached to the bottommost layer of the composite film, and the components of the special release film are engineering plastics containing bisphenol A as a main component or engineering plastics containing hexafluorodimethyl bisphenol A as a main component; wherein the engineering plastic containing bisphenol A as the main component is a polymer obtained by polymerizing or copolymerizing bisphenol A, and the weight ratio of the polymer is more than 50 percent; the engineering plastic containing the hexafluoro dimethyl bisphenol A as the main component is a polymer obtained by polymerization or copolymerization of the hexafluoro dimethyl bisphenol A, and the weight ratio of the engineering plastic is more than 50 percent.
Preferably, the weight ratio of the microporous reinforced membrane to the fluorine-containing proton or ion exchange resin is 10: 90-30: 70.
Preferably, the microporous reinforced membrane is 2 to 50 layers.
Preferably, the microporous reinforced membrane is 2-30 layers.
Preferably, the polymer obtained by polymerizing or copolymerizing bisphenol A is polycarbonate, polyphenylene ether, polysulfone resin, polyepoxy resin, or a mixture of at least two of the polycarbonate, the polyphenylene ether, the polysulfone resin, and the polyepoxy resin; the polymer obtained by polymerizing or copolymerizing the hexafluorodimethyl bisphenol A is polycarbonate, polyphenyl ether, polysulfone resin and polyepoxy resin, or a mixture of at least two of the polycarbonate, the polyphenyl ether, the polysulfone resin and the polyepoxy resin.
Preferably, the dry weight of the microporous reinforced membrane is 0.5-30 g/m, the open porosity is 40-95%, the thickness is 0.5-30 microns, and the tensile strength is more than 40MPa in both directions.
Preferably, the preparation method of the microporous reinforced membrane comprises the following steps: adopting hot melting spinning, wet phase change method, temperature difference phase change method, dry solvent method, electrostatic spinning method or ultra-high speed centrifugal spinning method to spin, etc., uniformly collecting nanometer or micron-sized fiber to form a random net-shaped microporous structure, and forming a microporous film after heat setting, wherein the resin is thermoplastic fluorine-containing or chlorine-containing resin, carbon fiber precursor or resin capable of being derived to generate carbon fiber; and extruding the microporous film in a paste shape and stretching the microporous film in two directions.
Preferably, one or more of metal nano powder, metal oxide nano powder, carbon powder, graphite powder, graphene and rare metal powder are mixed into the solution of the fluorine-containing proton exchange resin or ion exchange resin, and the total weight of the metal nano powder, the metal oxide nano powder, the carbon powder, the graphite powder, the graphene and the rare metal powder is not more than 80% of the dry weight of the fluorine-containing proton exchange resin or ion exchange resin.
Preferably, the metal nano powder includes silver, platinum or palladium, and the metal oxide powder includes zirconium dioxide or cerium dioxide.
Preferably, the total amount of the composite membrane is 2 to 500 g/m.
Due to the adoption of the technical scheme, the special high-enhancement type fluorine-containing proton or ion exchange membrane composite membrane is free from the trouble of pollution of a release agent, can be subjected to heat treatment for multiple times, and can resist heat of at least 100 ℃; the multilayer microporous reinforced membrane can cover bubble loss possibly formed by a single coating membrane, the yield can be greatly improved, the improvement on the tensile strength of the composite membrane can be increased, the size stability of the composite membrane is improved, the composite membrane is very important for the service life, high-speed continuous production can be realized, the requirement of commercial large-scale batch production is met, and the cleanliness and the stability of the prepared product membrane are high.
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Detailed Description
The present invention will be further described below, and it should be noted that the present embodiment is based on the technical solution, and a detailed implementation manner and a specific operation process are provided, but the protection scope of the present invention is not limited to the present embodiment.
(1) The composite membrane of the special high-enhancement type fluorine-containing proton or ion exchange membrane at least comprises two layers of microporous enhancement membranes, wherein both surfaces of each layer of microporous enhancement membrane (continuous phase) are filled with fluorine-containing proton exchange resin or ion exchange resin; (2) the lower surface of the composite membrane of the special high-enhancement type fluorine-containing proton or ion exchange membrane is attached with a special release membrane.
The fluorine-containing proton exchange resin or ion exchange resin can be a commercial product, such as Nafion, 3M or Suwei products of Dupont Mus, and can also be prepared by referring to a preparation method of the fluorine-containing chlorine-containing conductive polymer resin disclosed by ZL 201710251598.5.
The reinforced composite membrane at least comprises two layers of microporous reinforced membranes, wherein the two sides of each layer of the microporous reinforced membranes are filled with fluorine-containing proton exchange resin or ion exchange resin, and the integral manufacturing method comprises the following steps:
[ microporous reinforced membrane preparation method ] the preparation process and material of microporous reinforced membranes can be selected from the following two categories:
(1) the method comprises the following steps of adopting a hot melting spinning method, a wet phase change method, a temperature difference phase change method, a dry solvent method, an electrostatic spinning method or an ultrahigh speed centrifugal spinning method to carry out spinning and other processes, uniformly collecting nano or micron fibers to form a random net-shaped microporous structure, and forming a microporous film after heat setting, wherein the preferred resin is a hot melting fluorine-containing or chlorine-containing resin, a carbon fiber precursor or a resin which can be derived to generate carbon fibers, such as Polyacrylonitrile (PAN) or a copolymer thereof, polyimide, polyamide (nylon), Polyester (PET), aramid, polyether ketone (PEEK) and the like.
(2) The microporous reinforced film can be obtained by adopting paste extrusion and bidirectional stretching.
Microporous reinforced films having tensile strength (according to ASTM D882 test method) (TD, MD) of >40MPa, preferably >50MPa, most preferably >80MPa, and porosity of 40% to 95%. The microporous membrane is a reticular microporous structure, the reticular microporous structure can form a continuous phase microporous reinforced membrane after heat setting, the dry weight of the microporous reinforced membrane is about 0.5-30 g/sq m, preferably 1-10 g/sq m, the open porosity is about 40-95%, preferably 50-90%, the thickness is 0.5-30 microns, preferably 1-15 microns.
Coating fluorine-containing proton exchange resin or ion exchange resin solution on a release film which does not contain a release agent and can resist drying at 100 ℃ in a casting manner, covering at least two layers of microporous reinforced films, and filling the fluorine-containing proton exchange resin solution or ion exchange resin solution into pores on two sides of the microporous reinforced films as completely as possible by a multi-casting coating or soaking method, wherein the acid equivalent number (meq/g) of sulfonic acid or carboxylic acid of the fluorine-containing proton exchange resin or ion exchange resin is 400-1500, preferably 500-1100, and more preferably 600-950; drying the composite material to remove the solvent, and preparing the special high-enhancement composite membrane containing the fluorine proton or ion exchange membrane
The high-strength composite membrane at least comprises two layers of microporous reinforcement membranes, wherein each layer of double surfaces of each microporous reinforcement membrane is filled with fluorine-containing proton exchange resin or ion exchange resin, the weight ratio of the microporous reinforcement membrane to the fluorine-containing proton exchange resin or ion exchange resin is (5:95) - (40:60), preferably (10:90) - (30:70), the total weight of the reinforced composite membrane is 2-500 g/sq, preferably 5-300 g/sq, most preferably 5-200 g/sq, the thickness of the reinforced composite membrane is 1-300 microns, preferably 2-200 microns, most preferably 3-100 microns, the tensile strength (according to ASTM D882 test method) (TD, MD) of the reinforced composite membrane is more than 40MPa in both directions, preferably more than 50MPa, most preferably more than 80MPa in both directions, and the normal temperature proton/ion (Ionic Conductivity, GB/T20042.3-2009) of the reinforced composite membrane is part 3 of a proton exchange membrane fuel cell Method) >0.007(S/cm), preferably >0.013(S/cm), more preferably >0.018(S/cm) and the air permeability of the reinforced composite membrane is extremely low, the time required for 100 ml of air to penetrate through the composite membrane, measured with a Gurley permeameter, being >5 minutes, preferably >15 minutes.
Optionally, one or more of metal nano powder, metal oxide nano powder, carbon powder, graphite powder, graphene, rare metal powder and the like can be mixed in the fluorine-containing proton exchange resin or ion exchange resin solution and the fluorine-containing proton exchange resin or ion exchange resin solution, and the mixture can be filled into the pores on the two sides of the microporous film.
The total weight of the metal nano powder, the metal oxide powder, the carbon powder, the graphite powder, the graphene, the rare metal powder and the like is not more than 80 percent of the dry weight of the fluorine-containing proton exchange resin or the ion exchange resin. The rare metal nanopowders include, but are not limited to, silver, platinum or palladium, or a platinum/carbon composite. The metal oxide powder includes, but is not limited to, zirconium dioxide, or cerium dioxide.
The obtained composite membrane of the special high-enhancement type fluorine-containing proton or ion exchange membrane at least comprises two layers of microporous enhancement membranes, wherein the two sides of each layer of the microporous enhancement membranes are filled with fluorine-containing proton exchange resin or ion exchange resin, the total weight of the enhanced composite membrane is 2-500 g/m, preferably 5-300 g/m, and most preferably 5-200 g/m, the thickness (see ASTM D756) of the enhanced composite membrane is 1-300 micrometers, preferably 2-200 micrometers, and most preferably 3-100 micrometers, the tensile strength (see ASTM D882 test method) (TD, MD) of the high-enhancement composite membrane is more than 40MPa in both directions, preferably more than 50MPa, and most preferably more than 80MPa, and the normal-temperature proton/ion Conductivity (Ionic Conductivity, see GB/T20042.3-2009, part 3 of a proton exchange membrane fuel cell) of the high-enhancement composite membrane is more than 0.007(S/cm), preferably >0.013(S/cm), more preferably >0.018(S/cm), and the air permeability of the highly reinforced composite membrane is extremely low, the time required to let 100 ml of air penetrate the composite membrane, measured with a Gurley permeameter, being >5 minutes, preferably >15 minutes.
Example 1: (Release film without Release agent)
(1A) Melt-extruding and biaxially stretching a polycarbonate resin obtained by condensation polymerization of bisphenol a (without adding any auxiliary agent or release agent) to obtain transparent films (used directly without corona) with the thicknesses of about 300 microns, 150 microns and 25 microns;
(1B) melt-extruding and biaxially stretching a carbonate resin (without adding any auxiliary agent or parting agent) obtained by polycondensation of hexafluorodimethyl bisphenol A to obtain a transparent film (used as is, without corona) with the thickness of about 300 microns, 150 microns and 25 microns;
(1C) a release film with a thickness similar to the above is prepared by using polyphenylene oxide p-bisphenol a type epoxy resin (EHPPO type, without adding any auxiliary agent or release agent, used directly, without corona), and the resin preparation process refers to: the hyperbranched polyphenylene oxide is used for low dielectric modification of bisphenol A epoxy resin, such as Lujiangyong, Menyan, He Li Fan, Qiteng, Li Xiaoyu, Wang Hai, Beijing university of chemical industry institute of Material science and engineering institute of carbon fiber and functional polymer education department, Beijing 100029, and the abstract is that a reaction type end epoxy group hyperbranched polyphenylene oxide (EHPPO) is prepared, added into bisphenol A epoxy resin for modification and cured by an anhydride curing agent, and the thermal property, the mechanical property and the dielectric property of a cured sample are represented. In addition, a comparative modification study is carried out by using hyperbranched polyphenylene oxide (CHPPO) with the same molecular main chain structure and non-reactive benzyl end group. The results show that the two different modifying agents have respective advantages in the modification effect on the bisphenol A epoxy resin, wherein the epoxy resin obtained by using EHPPO modification has more excellent thermal property and tensile strength, and the epoxy resin modified by CHPPO has relatively lower dielectric constant.
Example 2: (formulation of proton exchange resin solution or ion exchange resin solution or mixture solution)
S1 (containing weight ratio: about 20% [ tetrafluoroethylene copolymer with CF2 ═ CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the acid equivalent number (meq/g) of which is about 830 ]; 40% ethanol; 40% water);
s2 (containing about 20% [ tetrafluoroethylene and CF2 ═ CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the number of acid equivalents (meq/g) of which is about 790 ], 40% ethanol, 40% water, by weight);
l1 (containing about 20% by weight of a copolymer of tetrafluoroethylene and a fluorine-containing proton exchange resin CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H, the acid equivalent number (meq/g) of which is about 1000; 40% n-propanol; 40% water);
l2 (containing about 20% by weight of a copolymer of tetrafluoroethylene and CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin, the number of acid equivalents (meq/g) of which is about 950; 40% ethanol; 40% water);
l3 (containing 20% by weight of a copolymer of tetrafluoroethylene and CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin, the number of acid equivalents (meq/g) of which is about 1100; 40% of n-propanol; 40% of water);
l4 (containing about 10% by weight of platinum black powder; 10% [ copolymer of tetrafluoroethylene with CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin, the number of acid equivalents (meq/g) of which is about 1100 ]; 40% n-propanol; 40% water);
l5 (containing ZrO2 zirconium dioxide nanopowder in a weight ratio of about 15% [ tetrafluoroethylene and CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the acid equivalent number (meq/g) of which is about 1100 ]; 40% n-propanol; 40% water);
LC6 (containing ZrO2 zirconium dioxide nanopowder in a weight ratio of about 15% [ tetrafluoroethylene copolymer with a fluorine-containing proton exchange resin CF2 ═ CF-O-CF2CF2CF2-COOH, the acid equivalent number (meq/g) of which is about 1000 ]; 40% n-propanol; 40% water);
LC7 (containing weight ratios: about 20% [ tetrafluoroethylene and CF2 ═ CF-O-CF2CFCF3-OCF2CF2-COOH fluorine-containing proton exchange resin copolymer, the number of acid equivalents (meq/g) of which is about 950 ]; 40% n-propanol; 40% water);
l8 (containing about 10% by weight of platinum/carbon black powder; 10% [ tetrafluoroethylene copolymer with CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin, the number of acid equivalents (meq/g) of which is about 1100 ]; 40% n-propanol; 40% water);
example 3: (for comparison)
(Release film 1A, a microporous reinforcing film 10 μm thick)
Coating a proton exchange resin solution S1 (containing about 20% (weight ratio: tetrafluoroethylene to CF2 ═ CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the acid equivalent number (meq/g) of which is about 830); 40% ethanol, 40% water) on a release film 1A with the thickness of about 25 microns, then coating a microporous polytetrafluoroethylene reinforced film with the thickness of about 10 microns, drying the film by a blower, then coating the same proton exchange resin solution on the microporous polytetrafluoroethylene reinforced film, drying the film by a blower, finally placing the film in an oven at 120 ℃, taking out the film for cooling after baking for 5 minutes, wherein the fluorine-containing proton exchange film can be smoothly uncovered from the release film 1A, no residue is seen on the release film, the thickness of the uncovered fluorine-containing proton exchange film is flat and about 16-18 microns, the density is about 2.20, the acid equivalent number (meq/g) of the composite film is about 1000, the tensile strength TD, MD is 40-50 MPa, the normal temperature proton/ion Conductivity (Ionic Conductivity) >0.012(S/cm), and the time required for 100 ml of air to permeate the composite film is measured by a Gurley air permeameter and calculated to be >15 minutes.
Example 4: (Release film 1A, two-layer 5 μm-thick microporous reinforcing film)
Coating a proton exchange resin solution S1 (containing about 20% (weight ratio: tetrafluoroethylene to CF2 ═ CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the number of acid equivalents (meq/g) of which is about 830); 40% ethanol; 40% water) on a release film 1A with a thickness of about 25 microns, then coating a thin microporous polytetrafluoroethylene reinforced film (continuous phase) with a thickness of about-5 microns, blow-drying with a blower, then coating the same proton exchange resin solution on the microporous polytetrafluoroethylene reinforced film, then coating the same thin microporous polytetrafluoroethylene reinforced film (continuous phase) with a thickness of about-5 microns, blow-drying with a blower, then coating the same proton exchange resin solution on the microporous polytetrafluoroethylene reinforced film, blow-drying with a blower, finally placing in an oven at 120 ℃, taking out and cooling after 5 minutes, the fluorine-containing proton exchange membrane can be smoothly stripped from the release membrane 1A, no residue is left on the release membrane by visual observation, the thickness of the stripped fluorine-containing proton exchange membrane is about 16-18 micrometers, the density is about 2.19, the acid equivalent number (meq/g) of the composite membrane is about 1020, the tensile strength TD and MD are both 60-70 MPa, the fact that the tensile strength of the membrane is superior to that of the method of adopting a single-layer 10-micrometer-thick microporous reinforced membrane in example 3 is unexpectedly found, the normal-temperature proton/ion Conductivity is greater than 0.012(S/cm), and the Gurley air permeameter is used for measuring and calculating the time required by 100 milliliters of air to permeate through the composite membrane is greater than 15 minutes.
Example 5: (Release film 1A, three-layer 3 micron thick microporous reinforced film)
Coating a proton exchange resin solution S1 (containing about 20% by weight of a copolymer of tetrafluoroethylene and CF2 ═ CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin, the acid equivalent number (meq/g) of which is about 830; 40% ethanol; 40% water) on a release film 1A having a thickness of about 25 μm, and then coating a thinner microporous polytetrafluoroethylene reinforced film (continuous phase) having a thickness of about 3 μm, and blowing a blower; then coating the same proton exchange resin solution on the microporous polytetrafluoroethylene reinforced film, then coating a thinner microporous polytetrafluoroethylene reinforced film (continuous phase) with the thickness of about-3 microns, and drying by using a blower; then, the microporous polytetrafluoroethylene reinforced film is coated with the same proton exchange resin solution, a thinner microporous polytetrafluoroethylene reinforced film (continuous phase) with the thickness of about-3 microns is coated, the microporous polytetrafluoroethylene reinforced film is dried by a blower, then the microporous polytetrafluoroethylene reinforced film is coated with the same proton exchange resin solution, the microporous polytetrafluoroethylene reinforced film is dried by the blower, finally the microporous polytetrafluoroethylene reinforced film is placed in an oven for 120 ℃ and is taken out for cooling after being baked for 5 minutes, the fluorine-containing proton exchange film can be smoothly uncovered from the release film 1A, no residue is left on the release film visually, the thickness of the uncovered fluorine-containing proton exchange film is flat and is about 16-18 microns, the density is about 2.18, the acid equivalent number (meq/g) of the composite film is about 80-90 MPa, the tensile strength TD and MD are all 80-90 MPa, the strength is unexpectedly found to be better than that the method adopting the microporous reinforced film with the thickness of a single layer of 10 microns in the embodiment 3, and the normal temperature proton/ion Conductivity (Ionic Conductivity) is more than 0.1040 (S/cm), the time required for 100 ml of air to permeate the composite film was calculated to be >15 minutes as measured by a Gurley permeameter.
Example 6 (Release film 1B, two-layer microporous reinforcing film)
Coating a proton exchange resin solution S2 (containing about 20% by weight of a copolymer of tetrafluoroethylene and CF2 ═ CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin, the acid equivalent number (meq/g) of which is about 790; 40% ethanol; 40% water) on a release film 1B with a thickness of about 25 micrometers, then coating a thinner microporous polytetrafluoroethylene reinforced film (continuous phase) with a thickness of about 2 micrometers, and blowing a blower; then, coating the same proton exchange resin solution on the microporous polytetrafluoroethylene reinforced film, then coating a thinner microporous polytetrafluoroethylene reinforced film (continuous phase) with the thickness of about-2 microns, and drying by using a blower; and then coating the microporous polytetrafluoroethylene reinforced film with the same proton exchange resin solution, drying by using a blower, finally placing the microporous polytetrafluoroethylene reinforced film in an oven at 120 ℃, baking for 5 minutes, taking out the microporous polytetrafluoroethylene reinforced film for cooling, wherein the fluorine-containing proton exchange film can be smoothly uncovered from the release film 1B, no residue is on the release film visually, the thickness of the uncovered fluorine-containing proton exchange film is flat and is about 8-9 micrometers, the density is about 2.20, the acid equivalent number (meq/g) of the composite film is about 1010, the tensile strength TD and MD are both greater than 100MPa, and the normal-temperature proton/ion Conductivity (Ionic Conductivity) is greater than 0.013(S/cm), and the time required for 100 milliliters of air to permeate the composite film is measured by a Gurley air permeability instrument and is greater than 15 minutes.
Example 7 (Release film 1C, two-layer microporous reinforcing film)
Coating a proton exchange resin solution S1 (containing about 20% [ tetrafluoroethylene to CF2 ═ CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the acid equivalent number (meq/g) of which is about 830 ]; 40% ethanol; 40% water) on a release film 1C about 25 microns thick, followed by coating a thinner microporous polytetrafluoroethylene reinforced film (continuous phase) about 1 micron thick, and blowing dry with a blower; then coating the same proton exchange resin solution on the microporous polytetrafluoroethylene reinforced film, then coating a thin microporous polytetrafluoroethylene reinforced film (continuous phase) with the thickness of about 1 micron, and drying by using a blower; then, coating the same proton exchange resin solution on the microporous polytetrafluoroethylene reinforced film, drying the microporous polytetrafluoroethylene reinforced film by using a blower, finally placing the microporous polytetrafluoroethylene reinforced film in an oven at 120 ℃, baking the microporous polytetrafluoroethylene reinforced film for 5 minutes, taking the microporous polytetrafluoroethylene reinforced film out, cooling the microporous polytetrafluoroethylene reinforced film, smoothly uncovering the fluorine-containing proton exchange film from the release film 1C, and visually observing no residue on the release film, wherein the thickness of the uncovered fluorine-containing proton exchange film is flat and is about 5-6 micrometers, the density is about 2.20, the acid equivalent number (meq/g) of the composite film is about 990, the tensile strength TD and MD are both greater than 120MPa, and the normal-temperature proton/ion Conductivity (Ionic Conductivity) is greater than 0.015(S/cm), and the time required for 100 milliliters of air to permeate the composite film is measured by using a Gurley air permeameter and is greater than 15 minutes.
Example 8 (Release film 1A, five-layer microporous reinforcing film, inner and outer layers of PTFE, middle layer of polypropylene)
Casting and coating a proton exchange resin solution S1 (containing 20 weight percent of copolymer of tetrafluoroethylene and CF2 ═ CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin and the acid equivalent number (meq/g) of about 830; 40% ethanol; 40% water) on a release film 1A with the thickness of about 150 micrometers, then coating a thin microporous polytetrafluoroethylene reinforced film with the thickness of about-3 micrometers, and drying by using a blower; then, coating the same proton exchange resin solution on the microporous polytetrafluoroethylene reinforced film, then coating a thin microporous polypropylene reinforced film with the thickness of about-4 microns, and drying by using a blower; then, coating the same proton exchange resin solution on the microporous polypropylene reinforced film, then coating a thin microporous polypropylene reinforced film with the thickness of about 4 microns, and drying by using a blower; then, coating the same proton exchange resin solution on the microporous polypropylene reinforced film, then coating a thin microporous polypropylene reinforced film with the thickness of about 4 microns, and drying by using a blower; then coating the same proton exchange resin solution on the microporous polypropylene reinforced film, then coating a thinner microporous polytetrafluoroethylene reinforced film with the thickness of about-3 microns, drying the microporous polypropylene reinforced film by using a blower, then coating the same proton exchange resin solution on the microporous polytetrafluoroethylene reinforced film, drying the microporous polypropylene reinforced film by using the blower, finally placing the microporous polypropylene reinforced film in an oven at 120 ℃, taking out the microporous polypropylene reinforced film for cooling after baking for 5 minutes, wherein the fluorine-containing proton exchange film can be smoothly released from the release film 1A, no residue is observed on the release film, the thickness of the released fluorine-containing proton exchange film is flat and about 28-30 microns, the density is about 2.1, the acid equivalent number (meq/g) of the composite film is about 1050, the tensile strength TD and MD are both greater than 70MPa, and the normal-temperature proton/ion Conductivity (Ionic Conductivity) is greater than 0.011(S/cm), and the time required for 100 ml of air to permeate the composite film is measured by a Gurley air permeameter and calculated to be greater than 15 minutes.
Example 9 (Release film 1A, ten microporous reinforced films, inner and outer layers of PTFE, and middle eight layers of polyacrylonitrile PAN)
Coating a proton exchange resin solution L1 (containing about 20% by weight of a copolymer of tetrafluoroethylene and CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin, the acid equivalent number (meq/g) of which is about 1000; 40% of n-propanol; 40% of water) on a release film 1A with the thickness of about 150 microns by casting, then coating a thin microporous polytetrafluoroethylene reinforced film with the thickness of about-3 microns, and drying by a blower; then coating a proton exchange resin solution L2 (containing weight ratio of about 20% [ copolymer of tetrafluoroethylene and CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin, the acid equivalent number (meq/g) of which is about 950 ]; 40% ethanol and 40% water) on the microporous polytetrafluoroethylene reinforced film, then coating a thin microporous polyacrylonitrile PAN reinforced film, the thickness of which is about 3-4 micrometers, and drying by a blower; then, coating the same proton exchange resin solution L2 on the microporous polyacrylonitrile PAN reinforced film, immediately coating a thin microporous polyacrylonitrile PAN reinforced film with the thickness of about 3-4 microns, and drying by using a blower; then, coating the same proton exchange resin solution L2 on the microporous polyacrylonitrile PAN reinforced film, then coating a thin microporous polyacrylonitrile PAN reinforced film with the thickness of about 3-4 microns, and drying by using a blower; then, coating the same proton exchange resin solution L2 on the microporous polyacrylonitrile PAN reinforced film, then coating a thin microporous polyacrylonitrile PAN reinforced film with the thickness of about 3-4 microns, and drying by using a blower; then, coating the same proton exchange resin solution L2 on the microporous polyacrylonitrile PAN reinforced film, then coating a thin microporous polyacrylonitrile PAN reinforced film with the thickness of about 3-4 microns, and drying by using a blower; then, coating the same proton exchange resin solution L2 on the microporous polyacrylonitrile PAN reinforced film, immediately coating a thin microporous polyacrylonitrile PAN reinforced film with the thickness of about 3-4 microns, and drying by using a blower; then, coating the same proton exchange resin solution L2 on the microporous polyacrylonitrile PAN reinforced film, then coating a thin microporous polyacrylonitrile PAN reinforced film with the thickness of about 3-4 microns, and drying by using a blower; then, coating the same proton exchange resin solution L2 on the microporous polyacrylonitrile PAN reinforced film, immediately coating a thin microporous polyacrylonitrile PAN reinforced film with the thickness of about 3-4 microns, and drying by using a blower; then, coating the same proton exchange resin solution L2 on the microporous polyacrylonitrile PAN reinforced film, then coating a thinner microporous polytetrafluoroethylene reinforced film with the thickness of about-3 microns, drying the microporous polyacrylonitrile PAN reinforced film by using a blower, then coating the proton exchange resin solution L1 on the microporous polytetrafluoroethylene reinforced film, drying the microporous polyacrylonitrile PAN reinforced film by using the blower, finally placing the microporous polyacrylonitrile PAN reinforced film in an oven at 130 ℃, baking the microporous polyacrylonitrile PAN reinforced film for 10 minutes, taking the microporous polyacrylonitrile PAN reinforced film out, cooling the microporous polyacrylonitrile PAN reinforced film, smoothly uncovering the fluorine-containing proton exchange film from the release film 1A, visually observing no residue on the release film, flattening the thickness of the uncovered fluorine-containing proton exchange film to about 58-60 microns, the density of the fluorine-containing proton exchange film to about 2.1, the tensile strength TD and MD of the fluorine-containing proton exchange film to be greater than 50MPa, and measuring the time required for 100 ml of air to permeate the composite film to be greater than 15 minutes by using a Gurley air permeameter.
Example 10 (Release film 1B, fifteen layers of microporous reinforcing films, all of expanded polytetrafluoroethylene)
Proton exchange membrane electrode with platinum black on both sides:
the ultrafine powder of metal platinum is black, so called "platinum black", and has an apparent density of 15.8 to 17.6, a specific surface area: 40-60 square meters per gram, particle size: <10 nm. The platinum black powder and a proton exchange resin solution L4 (containing 10% of platinum black powder by weight, 10% of tetrafluoroethylene-CF 2-CF 2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer with acid equivalent number (meq/g) of about 1100), 40% of n-propanol and 40% of water are cast and coated on a release film 1B with the thickness of about 150 microns, and then a thin microporous polytetrafluoroethylene reinforced film with the thickness of about-3 microns is coated on the release film, and the release film is dried by a blower; then coating a proton exchange resin solution L1 (containing weight ratio: about 20% [ tetrafluoroethylene to CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the acid equivalent number (meq/g) of which is about 1000 ]; 40% n-propanol; 40% water) on the microporous polytetrafluoroethylene reinforced film, then coating a thinner microporous polytetrafluoroethylene reinforced film, the thickness of which is about 3 microns, and drying by a blower; then coating a proton exchange resin solution L2 (containing weight ratio of about 20% [ tetrafluoroethylene to CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the acid equivalent number (meq/g) of which is about 950 ]; 40% ethanol and 40% water) on the microporous polytetrafluoroethylene reinforced film, then coating a thinner microporous polytetrafluoroethylene reinforced film with the thickness of about-3 microns, and drying by a blower; [ the following process was then repeated 10 times: coating the microporous polytetrafluoroethylene reinforced film with the same proton exchange resin solution L2, then coating a thin microporous polytetrafluoroethylene reinforced film with the thickness of about-3 microns, and drying by a blower; then coating proton exchange resin solution L1 on the microporous polytetrafluoroethylene reinforced film, then coating a thin microporous polytetrafluoroethylene reinforced film with the thickness of about-3 microns, and drying by a blower; finally, coating a proton exchange resin solution L4 containing platinum black on the microporous polytetrafluoroethylene reinforced film, drying the microporous polytetrafluoroethylene reinforced film by using a blower, finally placing the microporous polytetrafluoroethylene reinforced film in an oven at 130 ℃, baking the microporous polytetrafluoroethylene reinforced film for 10 minutes, taking out the microporous polytetrafluoroethylene reinforced film, cooling the microporous polytetrafluoroethylene reinforced film, smoothly uncovering the fluorine-containing proton exchange film containing platinum black on both sides from the release film 1B, observing no residue on the release film, flattening the thickness of the uncovered fluorine-containing proton exchange film containing platinum black on both sides to be 87-90 micrometers, ensuring the density to be 2.2, ensuring the tensile strength TD and MD to be more than 50MPa, ensuring the normal-temperature proton/ion Conductivity (Ionic Conductivity) to be more than 0.008(S/cm), and measuring and calculating the time required for 100 milliliters of air to penetrate through the composite film to be more than 15 minutes by using a Gurley air permeameter.
Example 11 (Release film 1A, Twenty layers of microporous reinforced film, all expanded polytetrafluoroethylene)
Enhanced chlor-alkali battery separator:
mixing nano zirconium oxide powder into a perfluorocarboxylic acid resin solution to obtain LC6 (containing ZrO2 zirconium dioxide nano powder in a weight ratio of about 5%; 15% [ tetrafluoroethylene and CF2 ═ CF-O-CF2CF2CF2-COOH fluorine-containing proton exchange resin copolymer, the acid equivalent number (meq/g) of which is about 1000 ]; 40% n-propanol and 40% water), coating the mixture on a release film 1A with the thickness of about 150 microns by casting, then coating a thin microporous polytetrafluoroethylene reinforced film with the thickness of about-3 microns, and drying by a blower; then coating a perfluorocarboxylic acid resin solution LC7 (containing weight ratio of about 20% [ tetrafluoroethylene to CF2 ═ CF-O-CF2CFCF3-OCF2CF2-COOH fluorine-containing proton exchange resin copolymer with the acid equivalent number (meq/g) of about 950 ] on the microporous polytetrafluoroethylene reinforced film, 40% of n-propanol and 40% of water), then coating a thinner microporous polytetrafluoroethylene reinforced film with the thickness of about-3 micrometers, and drying by a blower; then coating a perfluorocarboxylic acid resin solution LC7 (containing 20 weight percent of copolymer of tetrafluoroethylene and CF2 ═ CF-O-CF2CFCF3-OCF2CF2-COOH fluorine-containing proton exchange resin with the acid equivalent number (meq/g) of about 950; 40 percent of ethanol; 40 percent of water) on the microporous polytetrafluoroethylene reinforced film, then coating a thinner microporous polytetrafluoroethylene reinforced film with the thickness of about 3 microns, and drying by a blower; [ the following process was then repeated 3 times: coating the same perfluorocarboxylic acid resin solution LC7 on the microporous polytetrafluoroethylene reinforced film, then coating a thin microporous polytetrafluoroethylene reinforced film with the thickness of about-3 microns, and drying by using a blower; [ the following process was then repeated 13 times: coating perfluorosulfonic acid resin solution L2 on the microporous polytetrafluoroethylene reinforced film, then coating a thin microporous polytetrafluoroethylene reinforced film with the thickness of about-3 microns, and drying by a blower; finally, coating perfluorinated sulfonic acid resin solution L5 containing nano zirconium dioxide powder on the microporous polytetrafluoroethylene reinforced film, drying the film by using a blower, finally placing the film in an oven at 130 ℃, baking the film for 10 minutes, taking out and cooling the film, wherein one surface of the film, which contains zirconium dioxide, contains perfluorocarboxylic acid resin, and the other surface of the film contains fluorosulfonic acid resin, the film can be smoothly peeled off from the release film 1A, no residue is left on the release film by visual inspection, the thickness of the peeled film is flat and about 115-120 micrometers, the density is about 2.2, the tensile strength TD and MD are both greater than 50MPa, the normal-temperature Ionic Conductivity is greater than 0.01(S/cm), and the time required for 100 ml of air to penetrate through the composite film is measured by a Gurley air permeameter and is greater than 15 minutes.
Example 12 (Release film 1B, thirty layers of microporous reinforcing films, all expanded polytetrafluoroethylene films previously filled with CeO2)
Enhancement type proton exchange membrane:
coating L3 (containing 20% by weight of copolymer of tetrafluoroethylene and CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin and having an acid equivalent number (meq/g) of about 1100; 40% of n-propanol; 40% of water) on a release film 1B with a thickness of about 300 microns by casting, then coating a thin microporous polytetrafluoroethylene reinforced film (CeO 2: polytetrafluoroethylene) -10% by weight of pre-filling) with a thickness of about 3 microns, and blowing the film by a blower; then, coating perfluorinated sulfonic acid resin solution L2 (containing weight ratio of about 20% [ tetrafluoroethylene to CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the acid equivalent number (meq/g) of which is about 950 ]; 40% ethanol and 40% water) on the microporous polytetrafluoroethylene reinforced film, then coating a thinner microporous polytetrafluoroethylene reinforced film (containing 10% CeO2) with the thickness of about 3 microns, and drying by a blower; then coating perfluorocarboxylic acid resin solution L2 on the microporous polytetrafluoroethylene reinforced film, then coating a thin microporous polytetrafluoroethylene reinforced film (containing 10% of cerium dioxide CeO2) with the thickness of about-3 microns, and drying by using a blower; [ the following process was then repeated 27 times: coating the same perfluorinated sulfonic acid resin solution L2 on the microporous polytetrafluoroethylene reinforced film, and then coating a thin microporous polytetrafluoroethylene reinforced film (containing 10% of cerium dioxide CeO2) with the thickness of about-3 microns, and drying by using a blower; and finally, coating a fluorine-containing sulfonic acid resin solution L3 on the microporous polytetrafluoroethylene reinforced film, drying the microporous polytetrafluoroethylene reinforced film by using a blower, finally placing the microporous polytetrafluoroethylene reinforced film in an oven at 130 ℃, baking the microporous polytetrafluoroethylene reinforced film for 10 minutes, taking out the microporous polytetrafluoroethylene reinforced film for cooling, wherein the reinforced composite film can be smoothly uncovered from the release film 1B, no residue is visually observed on the release film, the thickness of the uncovered reinforced fluorine-containing proton exchange film containing cerium dioxide is flat and about 175-180 micrometers, the density is about 2.2, the tensile strength TD and MD are both greater than 50MPa, the normal-temperature proton/ion Conductivity (Ionic Conductivity) is greater than 0.01(S/cm), and the time required for 100 ml of air to penetrate through the composite film is measured by using a Gurley air permeameter and calculated to be greater than 15 minutes.
Example 13 (Release film 1A, forty-five layer microporous reinforced films, both expanded polytetrafluoroethylene films Pre-filled with Ceria CeO2)
Enhancement type proton exchange membrane:
l5 (containing 5% of zirconium dioxide ZrO2 by weight, 15% [ tetrafluoroethylene-CF 2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the number of acid equivalents (meq/g) of which is about 1100 ]; 40% of n-propanol; 40% of water) is coated on a release film 1A with the thickness of about 300 microns in a casting manner, and then a thin microporous polytetrafluoroethylene reinforced film [ the weight ratio of which is pre-filled (cerium dioxide CeO 2: polytetrafluoroethylene) to 10% ] is coated on the release film 1A with the thickness of about 3 microns in a casting manner, and the release film is dried by a blower; then, coating perfluorinated sulfonic acid resin solution L2 (containing weight ratio of about 20% [ tetrafluoroethylene to CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the acid equivalent number (meq/g) of which is about 950 ]; 40% ethanol and 40% water) on the microporous polytetrafluoroethylene reinforced film, then coating a thinner microporous polytetrafluoroethylene reinforced film (containing 10% CeO2) with the thickness of about 3 microns, and drying by a blower; then coating perfluorocarboxylic acid resin solution L2 on the microporous polytetrafluoroethylene reinforced film, then coating a thin microporous polytetrafluoroethylene reinforced film (containing 10% of cerium dioxide CeO2) with the thickness of about-3 microns, and drying by using a blower; [ the following process was then repeated 37 times: coating the same perfluorinated sulfonic acid resin solution L2 on the microporous polytetrafluoroethylene reinforced film, and then coating a thin microporous polytetrafluoroethylene reinforced film (containing 10% of cerium dioxide CeO2) with the thickness of about-3 microns, and drying by using a blower; and finally, coating a fluorine-containing sulfonic acid resin solution L5 on the microporous polytetrafluoroethylene reinforced film, drying the microporous polytetrafluoroethylene reinforced film by using a blower, finally placing the microporous polytetrafluoroethylene reinforced film in an oven at 130 ℃, baking the microporous polytetrafluoroethylene reinforced film for 10 minutes, taking out the microporous polytetrafluoroethylene reinforced film for cooling, wherein the fluorine-containing sulfonic acid resin reinforced film with zirconium dioxide on both surfaces and cerium dioxide inside can be smoothly uncovered from the release film 1A, no residue is visually observed on the release film, the thickness of the uncovered reinforced fluorine-containing proton exchange film with cerium dioxide is flat and about 260-270 micrometers, the density is about 2.2, the tensile strength TD and MD are both greater than 50MPa, the normal-temperature proton/ion Conductivity (Ionic Conductivity) is greater than 0.01(S/cm), and the time required for 100 milliliters of air to penetrate through the composite film is measured by a Gurley air permeameter and calculated to be greater than 15 minutes.
Example 14 (Release film 1B, three-layer microporous reinforcing film)
A proton exchange resin solution L8 (containing about 10% by weight of platinum/carbon black powder; 10% [ tetrafluoroethylene and CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the acid equivalent number (meq/g) of which is about 1100 ] was cast on a release film 1B about 150 microns thick, 40% n-propanol, 40% water) was coated thereon, and then a thin microporous polytetrafluoroethylene reinforced film (containing 10% cerium dioxide CeO2) about 3 microns thick was coated thereon and blown dry by a blower; then coating proton exchange resin solution L2 on the microporous polytetrafluoroethylene reinforced film, then coating a thinner microporous polytetrafluoroethylene reinforced film (containing 10% cerium dioxide CeO2) with the thickness of about-3 microns, and drying by using a blower; then coating a proton exchange resin solution L2 on the microporous polytetrafluoroethylene reinforced film, then coating a thin microporous polytetrafluoroethylene reinforced film (containing 10% cerium dioxide CeO2) with the thickness of about-3 microns, drying by using a blower, then coating a proton exchange resin solution L8 on the microporous polytetrafluoroethylene reinforced film, drying by using a blower, finally placing the microporous polytetrafluoroethylene reinforced film in an oven at 120 ℃, baking for 5 minutes, taking out and cooling, wherein the fluorine-containing proton exchange membrane can be smoothly uncovered from the release membrane 1B, no residue is observed on the release membrane, the thickness of the uncovered fluorine-containing proton exchange membrane electrode is about-28 microns, the tensile strength TD and MD of the membrane are all 80-90 MPa, and the normal temperature proton/ion Conductivity (Ionic Conductivity) is more than 0.012(S/cm), and the time required for 100 ml of air to permeate the composite film is measured by a Gurley air permeability instrument and calculated to be more than 15 minutes. Is suitable for being used as a membrane electrode of a fuel cell.
Comparative example 1((PET raw film, without any release agent, one microporous reinforced film)
PET (CAS: 25038-59-9) original film, the surface of which does not contain any release agent. Coating a proton exchange resin solution S1 (containing 20 weight percent of tetrafluoroethylene-CF 2 weight percent of CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer with the acid equivalent number (meq/g) of about 830; 40% ethanol; 40% water) on a PET original film with the thickness of about 25 microns and without any release agent, coating the casting slurry with proper tiling property, then coating a microporous polytetrafluoroethylene reinforced film with the thickness of about 8-9 microns, drying by using a blower, then coating the same proton exchange resin solution on the microporous polytetrafluoroethylene reinforced film, drying by using the blower, finally placing the film in an oven for 120 degrees, taking out the film after baking for 5 minutes, cooling, and taking out the fluorine-containing proton exchange film which cannot be uncovered from the PET original film, wherein the foam water cannot be uncovered smoothly. Although PET is the most common release film material in the market, the PET release film is also an original film made of aromatic engineering plastics and does not contain any release agent, but the PET release film is not suitable for being applied to manufacturing a fluorine-containing proton exchange membrane, and the release films, such as 1A, 1B and 1C, extracted in the above embodiment of the invention can have the performance suitable for being applied successfully, and the result is unexpected.
Comparative example 2((PET original film without any release agent, corona made, one microporous reinforcing film)
PET original film (CAS: 25038-59-9) without any release agent on the surface, but corona. Coating a proton exchange resin solution S1 (containing 20 weight percent of tetrafluoroethylene-CF 2 weight percent of CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer with the acid equivalent number (meq/g) of about 830) and 40 percent of ethanol and 40 percent of water) on a corona PET original film with the thickness of about 25 microns, coating a microporous polytetrafluoroethylene reinforced film with the thickness of about 8-9 microns, drying by using a blower, coating the same proton exchange resin solution on the microporous polytetrafluoroethylene reinforced film, drying by using a blower, finally placing the film in an oven for 120 degrees, taking out the film after baking for 5 minutes, cooling, preventing the fluorine-containing proton exchange film from being uncovered from the corona PET original film and preventing foam water from being uncovered smoothly. Although PET is the most common release film material in the market, the PET film is also an original film made of aromatic engineering plastics and does not contain any release agent, but the PET film is not suitable for being applied to the release film for manufacturing the fluorine-containing proton exchange membrane, and the release films such as 1A, 1B and 1C provided by the above examples of the invention can have the performance suitable for being applied successfully, and the result is unexpected.
Comparative example 3(PET Release film silicon-containing Release agent, one layer of microporous reinforcing film)
The traditional release film is mostly made of PET (CAS: 25038-59-9), corona addition release agent, such as silicon-containing or fluorine-containing release agent. Coating a proton exchange resin solution S1 (containing about 20 weight percent of tetrafluoroethylene-CF 2 weight percent of CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer with the acid equivalent number (meq/g) of about 830) and 40 percent of ethanol and 40 percent of water) on a PET release film containing a silicon release agent with the thickness of about 25 micrometers, coating the casting slurry with poor tiling property and cohesion, then coating a microporous polytetrafluoroethylene reinforced film with the thickness of about 8-9 micrometers, drying by using a blower, then coating the same proton exchange resin solution on the microporous polytetrafluoroethylene reinforced film, drying by using the blower, finally placing the film in an oven at 120 ℃, taking out and cooling after baking for 5 minutes, successfully uncovering the fluorine-containing proton exchange film from the (PET/silicon) release film, enabling no residue to be seen on the release film, enabling the thickness of the uncovered fluorine-containing proton exchange film to be about 10-18 micrometers, the flatness is poor, residual silicon-containing pollutants exist on the surface of the membrane analyzed by infrared IR, and the release membrane is not suitable for manufacturing a high-quality proton exchange membrane.
Comparative example 4 ((fluorine-containing release agent of PET Release film, one layer of microporous reinforcing film)
Adopts a PET release film, the surface of which is provided with a fluorine-containing release agent. Coating a proton exchange resin solution S1 (containing 20 weight percent of tetrafluoroethylene-CF 2 ═ CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer with the acid equivalent number (meq/g) of about 830; 40% ethanol; 40% water) on a PET release film with a thickness of about 25 micrometers, coating the casting slurry with a flat spreading property, then coating a microporous polytetrafluoroethylene reinforced film with the thickness of about 8-9 micrometers, drying by a blower, then coating the same proton exchange resin solution on the microporous polytetrafluoroethylene reinforced film, drying by the blower, finally placing in an oven for 120 degrees, taking out for cooling after baking for 5 minutes, wherein the fluorine-containing proton exchange membrane cannot be uncovered from the PET/fluorine-containing release film, the foam water can be uncovered, the thickness of the fluorine-containing proton exchange membrane is about 13-16 micrometers, and the surface of the fluorine-containing proton exchange membrane is damaged in some places. The release film is not suitable for manufacturing a high-quality proton exchange membrane.
The above examples and comparative examples clearly show that the special release film without release agent used in the invention is used for manufacturing the special high-enhancement composite film containing fluorine proton or ion exchange membrane, and the performance of the composite film is superior to that of the composite film manufactured by the traditional release film containing release agent.
Various changes and modifications can be made by those skilled in the art based on the above technical solutions and concepts, and all such changes and modifications should be included in the protection scope of the present claims.

Claims (10)

1. The composite membrane of the high-enhancement type fluorine-containing proton or ion exchange membrane is characterized by comprising at least two layers of microporous enhancement membranes, wherein two sides of each layer of microporous enhancement membrane are filled with fluorine-containing proton or ion exchange resin, and the weight ratio of the microporous enhancement membrane to the fluorine-containing proton or ion exchange resin is 5: 95-40: 60; the thickness of the film is 1-300 micrometers; the tensile strength of the composite membrane of the high-enhancement type fluorine-containing proton or ion exchange membrane is more than 40MPa in both directions, the normal-temperature ionic conductivity of the composite membrane is more than 0.007S/cm, the air permeability is extremely low, and the time required for 100 ml of air to penetrate through the composite membrane electrode is calculated and calculated by a Gurley air permeability instrument for more than 5 minutes;
the release film is attached to the bottommost layer of the composite film, and the components of the release film are engineering plastics containing bisphenol A as a main component or engineering plastics containing hexafluorodimethyl bisphenol A as a main component; wherein the engineering plastic containing bisphenol A as the main component is a polymer obtained by polymerizing or copolymerizing bisphenol A, and the weight ratio of the polymer is more than 50 percent; the engineering plastic containing the hexafluoro dimethyl bisphenol A as the main component is a polymer obtained by polymerization or copolymerization of the hexafluoro dimethyl bisphenol A, and the weight ratio of the engineering plastic is more than 50 percent.
2. The composite membrane of the high-enhancement type fluorine-containing proton or ion exchange membrane according to claim 1, wherein the weight ratio of the microporous enhancement membrane to the fluorine-containing proton or ion exchange resin is 10: 90-30: 70.
3. The composite membrane of the high-enhancement type fluorine-containing proton or ion exchange membrane according to claim 1, wherein the microporous enhancement membrane comprises 2-50 layers.
4. The composite membrane of the high-enhancement type fluorine-containing proton or ion exchange membrane according to claim 3, wherein the microporous enhancement membrane comprises 2-30 layers.
5. The membrane according to claim 1, wherein the polymer obtained by polymerization or copolymerization of bisphenol A is polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixture of at least two of the polycarbonate, the polyphenylene oxide, the polysulfone resin, and the polyepoxy resin; the polymer obtained by polymerization or copolymerization of the hexafluoro dimethyl bisphenol A is polycarbonate, polyphenyl ether, polysulfone resin and polyepoxy resin, or a mixture of at least two of the polycarbonate, the polyphenyl ether, the polysulfone resin and the polyepoxy resin.
6. The composite membrane of the highly enhanced fluorine-containing proton or ion exchange membrane according to claim 1, wherein the dry weight of the microporous enhanced membrane is 0.5 to 30 g/m, the open porosity is 40 to 95 percent, the thickness is 0.5 to 30 microns, and the tensile strength is more than 40MPa in both directions.
7. The composite membrane of the high-enhancement type fluorine-containing proton or ion exchange membrane according to claim 6, wherein the preparation method of the microporous enhancement membrane is as follows:
adopting hot melt spinning, wet phase change method, temperature difference phase change method, dry solvent method, electrostatic spinning method or ultra-high speed centrifugal spinning method to carry out spinning process, uniformly collecting nano or micron fibers to form a random net-shaped microporous structure, and forming a microporous film after heat setting, wherein the resin is thermoplastic fluorine-containing or chlorine-containing resin and carbon fiber precursor; and extruding the microporous film in a paste shape and stretching the microporous film in two directions.
8. The composite membrane of the highly enhanced fluorine-containing proton or ion exchange membrane according to claim 1, wherein one or more of metal nano powder, metal oxide powder, carbon powder, graphite powder and graphene is mixed into the solution of the fluorine-containing proton exchange resin or ion exchange resin, and the total weight of the metal nano powder, the metal oxide powder, the carbon powder, the graphite powder and the graphene is not more than 80% of the dry weight of the fluorine-containing proton exchange resin or ion exchange resin.
9. The highly enhanced membrane comprising fluorine proton or ion exchange membrane as claimed in claim 8, wherein the metal nanopowder comprises silver, platinum or palladium, and the metal oxide powder comprises zirconium dioxide or cerium dioxide.
10. The composite membrane of the highly enhanced fluorine-containing proton or ion exchange membrane according to claim 1, wherein the total amount of the composite membrane is 2 to 500 g/m.
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CN202110337002.XA CN113113650B (en) 2021-03-29 2021-03-29 High-enhancement composite membrane containing fluorine proton or ion exchange membrane
EP21934675.6A EP4318693A1 (en) 2021-03-29 2021-12-16 Composite membrane of special highly-enhanced fluorine-containing proton or ion exchange membrane, composite membrane electrode, special highly-enhanced fluorine-containing chlor-alkali battery membrane, special release membrane, and preparation method therefor
AU2021438644A AU2021438644A1 (en) 2021-03-29 2021-12-16 Composite membrane of special highly-enhanced fluorine-containing proton or ion exchange membrane, composite membrane electrode, special highly-enhanced fluorine-containing chlor-alkali battery membrane, special release membrane, and preparation method therefor
JP2023559744A JP2024515480A (en) 2021-03-29 2021-12-16 Special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane, composite membrane electrode, special highly reinforced fluorine-chlorine-containing alkaline battery membrane, special release membrane, and methods for producing the same
KR1020237033275A KR20230152725A (en) 2021-03-29 2021-12-16 Special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane, composite membrane electrode, special highly reinforced fluorine-containing chlor-alkali cell membrane, special release membrane, and method for manufacturing the same.
CN202180096477.2A CN117242608A (en) 2021-03-29 2021-12-16 Composite membrane of special high-enhancement type fluorine-containing proton or ion exchange membrane, composite membrane electrode, special high-enhancement type fluorine-containing chlor-alkali battery membrane, special release membrane and preparation method thereof
CA3213093A CA3213093A1 (en) 2021-03-29 2021-12-16 Composite membrane of special highly-enhanced fluorine-containing proton or ion exchange membrane, composite membrane electrode, special highly-enhanced fluorine-containing chlor-alkali battery membrane, special release membrane, and preparation method therefor
BR112023019970A BR112023019970A2 (en) 2021-03-29 2021-12-16 COMPOSITE MEMBRANE, COMPOSITE MEMBRANE ELECTRODE OF SPECIAL HIGHLY ENHANCED FLUORINE-CONTAINING ION OR PROTON MEMBRANE, SPECIAL HIGHLY ENHANCED FLUORINE-CONTAINING CHLORINE AND ALKALI BATTERY MEMBRANE, SPECIAL RELEASE MEMBRANE AND METHOD OF PREPARATION THEREOF
PCT/CN2021/138855 WO2022206039A1 (en) 2021-03-29 2021-12-16 Composite membrane of special highly-enhanced fluorine-containing proton or ion exchange membrane, composite membrane electrode, special highly-enhanced fluorine-containing chlor-alkali battery membrane, special release membrane, and preparation method therefor
ZA2023/09062A ZA202309062B (en) 2021-03-29 2023-09-26 Composite membrane of special highly-enhanced fluorine-containing proton or ion exchange membrane, composite membrane electrode, special highly-enhanced fluorinecontaining chlor-alkali battery membrane, special release membrane, and preparation method therefor

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BR112023019970A2 (en) * 2021-03-29 2023-11-21 Shanghai Hyproof New Material Tech Co Ltd COMPOSITE MEMBRANE, COMPOSITE MEMBRANE ELECTRODE OF SPECIAL HIGHLY ENHANCED FLUORINE-CONTAINING ION OR PROTON MEMBRANE, SPECIAL HIGHLY ENHANCED FLUORINE-CONTAINING CHLORINE AND ALKALI BATTERY MEMBRANE, SPECIAL RELEASE MEMBRANE AND METHOD OF PREPARATION THEREOF
CN114665134A (en) * 2022-03-29 2022-06-24 中汽创智科技有限公司 Proton exchange membrane and preparation method and application thereof

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