CN113113650A - Special high-enhancement composite membrane containing fluorine proton or ion exchange membrane - Google Patents

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

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CN113113650A
CN113113650A CN202110337002.XA CN202110337002A CN113113650A CN 113113650 A CN113113650 A CN 113113650A CN 202110337002 A CN202110337002 A CN 202110337002A CN 113113650 A CN113113650 A CN 113113650A
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film
fluorine
microporous
membrane
ion exchange
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CN113113650B (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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Priority to CN202110337002.XA priority Critical patent/CN113113650B/en
Publication of CN113113650A publication Critical patent/CN113113650A/en
Priority to CA3213093A priority patent/CA3213093A1/en
Priority to JP2023559744A priority patent/JP2024515480A/en
Priority to CN202180096477.2A priority patent/CN117242608A/en
Priority to AU2021438644A priority patent/AU2021438644A1/en
Priority to KR1020237033275A priority patent/KR20230152725A/en
Priority to EP21934675.6A priority patent/EP4318693A1/en
Priority to PCT/CN2021/138855 priority patent/WO2022206039A1/en
Priority to BR112023019970A priority patent/BR112023019970A2/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 special high-enhancement composite membrane containing 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 special release film, the special release film is attached to the bottommost layer of the composite film, and the component of the special release film is engineering plastic containing bisphenol A as a main component or engineering plastic 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

Special high-enhancement composite membrane containing fluorine 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 from various industries because they have advantages of high energy conversion rate, environmental friendliness, low-temperature start, low noise, and the like, 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 used proton exchange membranes are still the earliest commercialized Nafion series membranes (>25 μm thick) of the U.S. DuPont corporation, which are mainly obtained by melt extrusion, calendering and stretching. The Gore-Select series of recent Gore-Select membranes from Gore usa have been made by ultra-thin (<25 μm thick) single layer microporous PTFE reinforced membranes, mainly by cast coating single layer microporous PTFE reinforced membranes (see us patent No. 5547551, 5599614), and a few domestic companies have been 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 perfluorinated sulfonic acid resin membrane has basic performances of excellent proton conductivity, low gas permeability, good mechanical property and dimensional stability, small contact resistance with a catalytic layer and the like, 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: tape 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, and the used film manufacturing method adopts release paper, so that the flock pollution caused by the release paper is easy to generate during the 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 compressive 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 an insulating release film of polycarbonate, 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 is complicated in process and easy to release during casting process to cause film surface contamination due to the release agent.
For example, the fluoropolymer microfibers are not continuous phase and can not be connected to form a film as disclosed in patents CN200710013624.7, US7259208, CN101350415B, CN101780376B, CN104018181A, CN101320818B, CN201546122U, CN103187549A, and CN 1298890C.
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 easy to be polluted by a release agent and is difficult to produce continuously.
In order to achieve the technical purpose, the following technical scheme is adopted in the application:
the composite membrane of the special high-enhancement type fluorine-containing proton or ion exchange membrane 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 weight ratio of the microporous reinforced membrane to the fluorine-containing proton or ion exchange resin is 10: 90-30: 70; 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 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%.
Preferably, the microporous reinforced membrane is 2 to 50 layers.
Preferably, the microporous reinforced membrane is 2-30 layers.
Preferably, the polymer obtained by polymerization or copolymerization of bisphenol A is one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin or mixed copolymer thereof; the polymer obtained by polymerization or copolymerization of the hexafluoro dimethyl bisphenol A is one of polycarbonate, polyphenyl ether, polysulfone resin, polyepoxy resin or mixed copolymer thereof.
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 form 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 one of silver, platinum or palladium, or a platinum/carbon composite, and the metal oxide powder includes one of zirconium dioxide or cerium dioxide.
Preferably, the total amount of the composite film 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.
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 micropore enhancement membranes, and both surfaces of each layer of micropore 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 carrying out spinning by adopting a hot-melt spinning method, a wet-process phase change method, a temperature difference phase change method, a dry solvent method, an electrostatic spinning method or an ultrahigh-speed centrifugal spinning method and the like, uniformly collecting nano or micron-scale fibers to form a random reticular microporous structure, and forming a microporous film after heat setting, wherein the used resin is preferably hot-melt fluorine-containing or chlorine-containing resin, a carbon fiber precursor or resin capable of being derived to generate carbon fibers, such as Polyacrylonitrile (PAN) or a copolymer thereof, polyimide, polyamide (nylon), Polyester (PET), aramid fiber, 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 reinforcing membranes, wherein each layer of the microporous reinforcing membranes is filled with fluorine-containing proton exchange resin or ion exchange resin on the two sides, the weight ratio of the microporous reinforcing membranes 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 on both sides, preferably more than 50MPa, most preferably more than 80MPa on both sides, and the normal temperature proton/ion Conductivity (Ionic Conductivity, GB/T20042.3-2009 proton exchange membrane fuel cell part 3: proton exchange membrane test 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 this composite membrane, measured with a Gurley permeameter, being calculated to be >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 nano 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 precious metal nanopowder includes, but is 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/sq m, preferably 5-300 g/sq m, most preferably 5-200 g/sq m, the thickness (see ASTM D756) of the enhanced composite membrane is 1-300 μm, preferably 2-200 μm, most preferably 3-100 μm, 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, most preferably more than 80MPa, and the normal-temperature proton/ion Conductivity (Ionic Conductivity, see GB/T20042.3-2009, part 3 of 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 a transparent film (used directly without corona) with the thickness of about 300 microns, 150 microns and 25 microns;
(1B) melt-extruding and biaxially stretching a carbonate resin (without adding any auxiliary agent or release agent) obtained by condensation polymerization of hexafluorodimethyl bisphenol A to obtain a transparent film (directly used 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, the hyperbranched polyphenylene oxide (CHPPO) with the same molecular main chain structure and the non-reactive benzyl end group is used for carrying out comparative modification research. 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 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 830% ], 40% ethanol, 40% water, by weight);
s2 (containing about 20% [ tetrafluoroethylene and CF2 ═ CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the acid equivalent number (meq/g) of which is about 790 ], 40% ethanol, 40% water, by weight);
l1 (containing about 20% [ tetrafluoroethylene and CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the number of acid equivalents (meq/g) of which is about 1000 ]; 40% n-propanol; 40% water) by weight;
l2 (containing about 20% [ tetrafluoroethylene and CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the number of acid equivalents (meq/g) of which is about 950 ]; 40% ethanol; 40% water) by weight;
l3 (containing 20% by weight [ 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);
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 nano-powder by weight; about 15% [ tetrafluoroethylene copolymer with CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin, the number of acid equivalents (meq/g) thereof being about 1100 ]; 40% n-propanol; 40% water);
LC6 (containing about 5% by weight ZrO2 zirconium dioxide nanopowder; about 15% [ tetrafluoroethylene and CF2 ═ CF-O-CF2CF2CF2-COOH fluorine-containing proton exchange resin copolymer, the number of acid equivalents (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 platinum/carbon black powder at a weight ratio of about 10%; 10% [ tetrafluoroethylene copolymer with a CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin, having an acid equivalent number (meq/g) of 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% [ tetrafluoroethylene-CF 2 ═ CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer with an acid equivalent number (meq/g) of about 830 ]; 40% ethanol; 40% water) on a release film 1A with a thickness of about 25 microns, then coating a microporous polytetrafluoroethylene reinforced film with a thickness of about 10 microns, drying the film by a blower, then coating the microporous polytetrafluoroethylene reinforced film with the same proton exchange resin solution, 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 smooth and about 16 to 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 5 micron thick microporous reinforced 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 again, 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 on the release membrane visually, 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 tensile strength of the membrane is unexpectedly found to be superior to that of the method adopting the microporous reinforced membrane with the thickness of 10 micrometers in the example 3, the normal temperature proton/ion Conductivity (Ionic Conductivity) is more than 0.012(S/cm), and the Gurley air permeability apparatus is used for measuring and calculating the time required by 100 milliliters of air to permeate the composite membrane to be more 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% [ tetrafluoroethylene to CF2 ═ CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer with an acid equivalent number (meq/g) of about 830 ]; 40% ethanol; 40% water) on a release film 1A with a thickness of about 25 microns, followed by coating a thinner microporous polytetrafluoroethylene reinforced film (continuous phase) with a thickness of about 3 microns, and blowing dry with 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) is coated, the thickness is about-3 microns, 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 at 120 ℃, the microporous polytetrafluoroethylene reinforced film is baked for 5 minutes and then taken out for cooling, the fluorine-containing proton exchange film can be smoothly uncovered from the release film 1A, no residue is on the release film by visual inspection, the thickness of the uncovered fluorine-containing proton exchange film is about 16-18 microns, the density is about 2.18, the acid equivalent number (meq/g) of the composite film is about 1040, the tensile strength TD and MD are all 80-90 MPa, and the strength is unexpectedly found to be better than that the microporous reinforced film with a single layer of 10 microns in the embodiment 3, normal temperature proton/ion Conductivity (Ionic Conductivity) >0.012(S/cm), the time required for 100 ml of air to permeate through the composite film was calculated to be >15 minutes as measured by a Gurley air permeameter.
Example 6 (Release film 1B, two-layer microporous reinforcing film)
Coating a proton exchange resin solution S2 (containing about 20% [ tetrafluoroethylene-CF 2 ═ CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer with an acid equivalent number (meq/g) of about 790 ], 40% ethanol and 40% water by weight) 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 with an acid equivalent number (meq/g) of 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; 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 torn off from the release film 1C, no residue is left on the release film visually, the thickness of the torn-off fluorine-containing proton exchange film is flat and is about 5-6 microns, 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 ml of air to permeate the composite film is measured and calculated by using a Gurley air permeability instrument and is greater than 15 minutes.
Example 8 (Release film 1A, five-layer microporous reinforcing film, inner and outer layers of PTFE, and middle layer of Polypropylene)
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 with an acid equivalent number (meq/g) of about 830; 40% ethanol; 40% 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 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, immediately 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, immediately 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 20 weight percent of copolymer of tetrafluoroethylene and CF2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin and the acid equivalent number (meq/g) of which is about 950), 40 percent of ethanol and 40 percent of water on the microporous polytetrafluoroethylene reinforced film, immediately coating a thin microporous polyacrylonitrile PAN reinforced film with the thickness of about 3 to 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, 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, 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, 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, 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, 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, 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 microporous reinforced films, all 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.
Example 11 (Release film 1A, Twenty layers of microporous reinforced film, both 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 with an acid equivalent number (meq/g) of about 1000 ]; 40% n-propanol and 40% water), coating the mixture on a release film 1A with a thickness of about 150 microns by casting, then coating a thin microporous polytetrafluoroethylene reinforced film with a thickness of about-3 microns, and drying the film 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 acid equivalent number (meq/g) of about 950; 40 percent of n-propanol; 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; 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 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 a blower; [ the following process was then repeated 13 times: coating perfluorinated sulfonic 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-layer microporous reinforcing films, all of which are expanded polytetrafluoroethylene films previously filled with cerium oxide CeO2)
Enhancement type proton exchange membrane:
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) is cast and coated on a release film 1B with the thickness of about 300 microns, and then a thin microporous polytetrafluoroethylene reinforced film (the weight ratio of pre-filling cerium oxide CeO 2: polytetrafluoroethylene) is coated to 10% with the thickness of about 3 microns, and the film is dried by a blower; then, a perfluorinated sulfonic acid resin solution L2 (containing 20 weight percent of 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) is coated on the microporous polytetrafluoroethylene reinforced film, 40 percent of ethanol and 40 percent of water are coated on the microporous polytetrafluoroethylene reinforced film, and the microporous polytetrafluoroethylene reinforced film (containing 10 percent of CeO2) is coated on the microporous polytetrafluoroethylene reinforced film, the thickness of the microporous polytetrafluoroethylene reinforced film is about 3 microns, and the microporous polytetrafluoroethylene reinforced film is dried 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% by weight of zirconium dioxide ZrO 2; 15% [ tetrafluoroethylene-CF 2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the acid equivalent number (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 thinner microporous polytetrafluoroethylene reinforced film [ the weight ratio of pre-filling (cerium dioxide CeO 2: polytetrafluoroethylene) to 10% ] is coated on the release film 1A with the thickness of about 3 microns, and the release film is dried by a blower; then, a perfluorinated sulfonic acid resin solution L2 (containing 20 weight percent of 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) is coated on the microporous polytetrafluoroethylene reinforced film, 40 percent of ethanol and 40 percent of water are coated on the microporous polytetrafluoroethylene reinforced film, and the microporous polytetrafluoroethylene reinforced film (containing 10 percent of CeO2) is coated on the microporous polytetrafluoroethylene reinforced film, the thickness of the microporous polytetrafluoroethylene reinforced film is about 3 microns, and the microporous polytetrafluoroethylene reinforced film is dried 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% of platinum/carbon black powder by weight, 10% [ tetrafluoroethylene-CF 2 ═ CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, the acid equivalent number (meq/g) of which is about 1100 ]; 40% of n-propanol, 40% of water) is cast and coated on a release film 1B with the thickness of about 150 microns, and then a thin microporous polytetrafluoroethylene reinforced film (containing 10% of cerium dioxide CeO2) with the thickness of about 3 microns is coated on the release film, and a blower is used for drying; 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 original film, without any release agent, one microporous reinforced film)
PET (CAS: 25038-59-9) original film, the surface does not contain any release agent. Coating a proton exchange resin solution S1 (containing 20 weight percent of tetrafluoroethylene-CF 2-CF-O-CF 2CF2-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 a microporous polytetrafluoroethylene reinforced film with proper spreading property, drying the film with the thickness of about 8-9 microns by using a blower, coating the same proton exchange resin solution on the microporous polytetrafluoroethylene reinforced film, drying the film 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 film, wherein the fluorine-containing proton exchange film cannot be uncovered from the PET original film, and the bubble 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-CF-O-CF 2CF2-SO3H fluorine-containing proton exchange resin copolymer with the equivalent acid number (meq/g) of about 830; 40% ethanol; 40% water) on a PET original film with the thickness of about 25 microns and provided with corona, 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 PET original film provided with the corona, 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 containing silicon Release agent, one 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-CF-O-CF 2CF2-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 containing a silicon release agent with the thickness of about 25 microns, coating the PET release film with poor spreading property and cohesion of casting slurry, 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 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, visually observing no residue on the release film, and uncovering the fluorine-containing proton exchange film with the thickness of about 10-18 microns, 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 microporous reinforcing film)
Adopts a PET release film, and the surface of the PET release film is provided with a fluorine-containing release agent. Coating a proton exchange resin solution S1 (containing about 20 weight percent of tetrafluoroethylene-CF 2-CF-O-CF 2CF2-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 containing a fluorine release agent 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, placing the film in an oven for 120 degrees, taking out the film for cooling after baking for 5 minutes, wherein the fluorine-containing proton exchange film cannot be uncovered from the PET/fluorine-containing release film, the bubble water can be barely uncovered, the thickness of the fluorine-containing proton exchange film is about 13-16 microns, and the surface of the film 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 special high-enhancement type fluorine-containing proton or ion exchange membrane 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; the thickness is 1-300 microns; the tensile strength of the composite membrane of the special 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 permeameter for more than 5 minutes.
2. The special high-reinforcement fluorine-containing proton or ion exchange membrane composite membrane according to claim 1, wherein the weight ratio of the microporous reinforcement membrane to the fluorine-containing proton or ion exchange resin is 10: 90-30: 70;
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 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%.
3. The special high-reinforcement fluorine-containing proton or ion exchange membrane composite membrane according to claim 1, wherein the microporous reinforcement membrane comprises 2-50 layers.
4. The special high-reinforcement fluorine-containing proton or ion exchange membrane composite membrane according to claim 3, wherein the microporous reinforcement membrane comprises 2-30 layers.
5. The special high-reinforcement fluorine-containing proton or ion exchange membrane composite membrane according to claim 2, wherein the polymer obtained by polymerization or copolymerization of bisphenol a is one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin or their mixed copolymer; the polymer obtained by polymerization or copolymerization of the hexafluoro dimethyl bisphenol A is one of polycarbonate, polyphenyl ether, polysulfone resin, polyepoxy resin or mixed copolymer thereof.
6. The special high-reinforcement fluorine-containing proton or ion exchange membrane composite membrane according to claim 1, wherein the dry weight of the microporous reinforcement membrane is 0.5-30 g/m, the open porosity is 40-95%, the thickness is 0.5-30 μm, and the tensile strength is more than 40MPa in both directions.
7. The special high-reinforcement fluorine-containing proton or ion exchange membrane composite membrane according to claim 6, wherein the preparation method of the microporous reinforcement 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 form and stretching the microporous film in two directions.
8. The special high-reinforcement fluorine-containing proton or ion exchange membrane composite membrane according to claim 1, wherein one or more of metal nano powder, metal oxide nano powder, carbon powder, graphite powder, graphene and rare metal powder is mixed into the solution of 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.
9. The special high-reinforcement fluorine-containing proton or ion exchange membrane composite membrane according to claim 8, wherein the metal nanopowder includes one of silver, platinum or palladium, or a platinum/carbon composite material, and the metal oxide powder includes one of zirconium dioxide or cerium dioxide.
10. The special high-reinforcement fluorine-containing proton or ion exchange membrane composite membrane according to claim 1, wherein the total amount of the composite membrane is 2-500 g/m.
CN202110337002.XA 2021-03-29 2021-03-29 High-enhancement composite membrane containing fluorine proton or ion exchange membrane Active CN113113650B (en)

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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
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
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
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
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
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.
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
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
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
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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