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

Abstract

To provide a composite membrane of a special highly-enhanced fluorine-containing proton or ion exchange membrane, a composite membrane electrode, and a fluorine-containing chlor-alkali battery membrane which are not contaminated by a release agent, and have heat resistance, improved tensile strength, and improved dimensional stability, and also to provide a preparation method of the membranes which reduces production cost and uses no release agent.SOLUTION: A composite membrane of a special highly-enhanced fluorine-containing proton or ion exchange membrane comprises at least two microporous enhancement membranes, wherein both sides of each microporous enhancement membrane are filled with a fluorine-containing proton or ion exchange resin, the composite membrane has tensile strength in both directions >40 MPa, room-temperature ionic conductivity >0.007 S / cm, and extremely low air permeability, and it is measured using a Gurley permeability tester that the time required for 100 ml of air to penetrate through the composite membrane is >5 minutes.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane, a composite membrane electrode, a special highly reinforced fluorine-chlorine-containing alkaline battery membrane, a special release membrane, and methods for producing them. [Background technology]

[0002] Proton exchange membrane fuel cells (PEMFCs), a highly efficient power generation device that directly converts fuel and chemical energy into electrical energy, have attracted attention in various industries due to their advantages over conventional batteries, including higher energy conversion efficiency, environmental friendliness, low-temperature start-up, and low noise. Their core component is the proton exchange membrane (PEMFC), located at the center of the fuel cell, which provides the channel for transporting protons generated at the cathode to the anode. The most widely available PEMFCs are still DuPont's perfluorosulfonic acid Nafion series membranes (thickness >25 μm), which were first commercialized and are primarily obtained by melt extrusion, rolling, and tensile drawing. In recent years, Gore's Gore-Select membrane series, which utilizes ultrathin (thickness <25 μm) single-layer microporous PTFE-reinforced membranes, primarily cast-coated (see U.S. Patent Nos. US 5,547,551A and US 5,599,614A), has been imitated by a small number of companies in China.

[0003] Fluorine-containing sulfonic acid resins have a molecular structure consisting of a fluorocarbon main chain with low main chain polarizability and hydrophilic sulfonic acid or carboxylic acid groups on the side chains capable of adsorbing water molecules, and side chains with terminal sulfonic acid groups. The strong difference in polarity between the hydrophobic main chain and the hydrophilic side chains forms a microphase-separated structure within the membrane, which plays an important role in its mechanical and transport properties. Therefore, perfluorosulfonic acid resin membranes have basic properties such as excellent proton conductivity, low gas permeability, good mechanical properties and dimensional stability, and low contact resistance with the catalyst layer, satisfying the requirements for use as proton exchange membranes. There are many methods for producing proton exchange membranes from sulfonic acid resin solutions, including casting, dipping, and spraying. Currently, the manufacturing processes for proton exchange membranes and various reinforced composite proton exchange membranes are complex, and continuous production is difficult.

[0004] Patent CN101771159B (patent number ZL201010104002.7) discloses a method for producing a proton exchange membrane, in which a sulfonated polyether ether ketone and a sulfonated polyether sulfone are blended to form a membrane solution, the membrane solution is poured into a mold, the solvent is evaporated to form a membrane, and then vacuum drying and acid treatment are performed to obtain a proton exchange membrane. However, the production of the product membrane is carried out in units, resulting in low production efficiency and high costs.

[0005] Patent CN100513460 (patent number ZL200710011141.3) discloses a novel method for forming a proton exchange membrane, using a single-layer expanded polytetrafluoroethylene microporous membrane as a base membrane, which is first immersed in a low-concentration resin solution, and then repeatedly immersed in a high-concentration resin solution multiple times until an appropriate membrane thickness is achieved. This method has a complicated manufacturing process, low efficiency, and high production and use costs for fuel cells, limiting the commercialization of fuel cells.

[0006] Patent CN106968110B (ZL201710251603.2) discloses a fluorine-chlorine-containing conductive polymer double-sided filled composite film, but the film production method uses release paper, which is prone to dandruff contamination caused by the release paper when producing high-quality film.

[0007] A release film is a film with a release surface that exhibits little or no tackiness after contact with a specific material under specific conditions. To increase the release force of a plastic film, the plastic film is typically treated with corona or plasma, followed by a surface modification treatment involving the application of a release agent. Most commonly, a silicon- or fluorine-containing release agent is applied to the surface of the film material, resulting in a very light and stable release force for various organic adhesives. Silicone release paper (film) is currently commonly found on the market, and all of these use silicone as a release agent. The biggest drawback is that silicone may remain on the product surface upon removal.

[0008] Polycarbonate insulating release film is another common type of release film. It is made from 2,2'-bis(4-hydroxyphenyl)propane polycarbonate, commonly known as polycarbonate. It is a high-molecular polymer containing carbonate groups formed by condensation polymerization of bisphenol A in the molecular chain. It is an amorphous, odorless, non-toxic, highly transparent, colorless or pale yellow thermoplastic engineering plastic with excellent physical and mechanical properties, particularly impact resistance, high tensile strength, flexural strength, and compressive strength, low creep, and dimensional stability. Therefore, it is widely used in a variety of fields. However, polycarbonate insulating release film functions better when other additives are added or a release agent is applied.

[0009] Patent CN105440641A discloses a polycarbonate insulating release film that requires the addition of other additives, which are easily released during the casting process and contaminate the film surface.

[0010] Patent CN1840324A discloses a method for producing a release film that is complicated, requires the application of a release agent, and is prone to contaminating the film surface during the casting process.

[0011] In addition, unlike the techniques disclosed in Patent CN100588676C (Patent No. 200710013624.7), US7259208B, CN101350415B, CN101780376B, CN104018181A, CN101320818B, CN201546122U, CN103187549A, CN1298890C, etc., the fluorine-containing polymer microfibers are not a continuous phase and cannot be connected to form a film.

[0012] With the development of a low-carbon, clean economy, the requirements and applications for fluorine-containing proton exchange membranes or ion exchange membranes and their counterpart release membranes are increasing. In practical use, release membranes must not only have isolation and filling functions, but also protective functions, prevent the release agent from contaminating the cast coating, and dissipate heat. Therefore, the requirements for the cleanliness, mechanical strength, and service life of fluorine-containing proton exchange membranes or ion exchange membranes are becoming increasingly important. Summary of the Invention [Problem to be solved by the invention]

[0013] The present invention has been made in view of the above-mentioned problems of the prior art. An object of the present invention is to provide a special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane, a composite membrane electrode, or a special highly reinforced fluorine-chlorine-containing membrane for alkaline batteries, in order to solve the problems of the prior art, such as the complicated production process of the exchange membrane, the susceptibility to contamination by release agents, and the difficulty of continuous production. [Means for solving the problem]

[0014] In order to achieve the above technical object, the present invention employs the following technical aspects.

[0015] <First embodiment of the present invention> In a first aspect of the present invention, there is provided a special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane comprising at least two micropore-reinforced membrane layers, each of which is filled on both sides with a fluorine-containing proton or ion exchange resin, with the weight ratio of the micropore-reinforced membrane to the fluorine-containing proton or ion exchange resin being 5:95 to 40:60. The thickness of the composite membrane is 1 to 300 μm. The composite membrane has a tensile strength of >40 MPa in both directions, a room-temperature ionic conductivity of >0.007 S / cm, and extremely low air permeability, with the time required for 100 ml of air to permeate the composite membrane being >5 minutes as measured using a Gurley air permeometer.

[0016] Preferably, the weight ratio of the micropore-reinforced membrane to the fluorine-containing proton or ion exchange resin is 10:90 to 30:70, and the composite membrane further includes a special release film attached to the bottom layer. The component of the special release film is selected from engineering plastics containing bisphenol A as a main component or engineering plastics containing hexafluorodimethylbisphenol A as a main component, provided that the engineering plastics containing bisphenol A as a main component are polymers obtained by polymerizing or copolymerizing bisphenol A and the weight ratio thereof exceeds 50%, and the engineering plastics containing hexafluorodimethylphenol A as a main component are polymers obtained by polymerizing or copolymerizing hexafluorodimethylphenol A and the weight ratio thereof exceeds 50%.

[0017] The micropore-reinforced membrane preferably has 2 to 50 layers.

[0018] The micropore-reinforced membrane preferably has 2 to 30 layers.

[0019] Preferably, the polymer obtained by polymerizing or copolymerizing bisphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof, and the polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof.

[0020] Preferably, the microporous reinforced membrane has a dry weight of 0.5 to 30 g / m 2 The open porosity is 40% to 95%, the thickness is 0.5 to 30 μm, and the tensile strength is >40 MPa in both directions.

[0021] Preferably, the method for producing the micropore-reinforced membrane comprises a process of spinning, such as melt spinning, wet spinning, wet phase change method, temperature difference phase change method, dry solvent method, electrostatic spinning, or ultra-high speed centrifugal spinning, to uniformly converge nano- or micro-sized fibers to form a random network micropore structure, which is then heat-set to form a microporous film, and the resin used is a thermoplastic fluorine-containing or chlorine-containing resin, a carbon fiber precursor, or a resin that can be derived from carbon fiber; the microporous film is extruded into a paste form and then biaxially stretched.

[0022] Preferably, the solution of the fluorine-containing proton exchange resin or ion exchange resin is mixed with one or more of metal nanopowder, metal oxide nanopowder, carbon powder, graphite powder, graphene, and rare metal powder, and the total weight thereof does not exceed 80% of the dry weight of the fluorine-containing proton exchange resin or ion exchange resin.

[0023] Preferably, the metal nanopowder comprises one of silver, platinum or palladium, or a platinum / carbon composite, and the metal oxide powder comprises one of zirconia or ceria.

[0024] Preferably, the total amount of the composite film is 2 to 500 g / m 2 is.

[0025] <Second embodiment of the present invention> In a second aspect of the present invention, there is provided a special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane for use in a battery separator, which comprises at least two micropore-reinforced membrane layers, both sides of each micropore-reinforced membrane being filled with a fluorine-containing proton or ion exchange resin, and the weight ratio of the micropore-reinforced membrane to the fluorine-containing proton or ion exchange resin is 5:95 to 40:60. The weight ratio of the micropore-reinforced membrane to the fluorine-containing proton or ion exchange resin is 10:90 to 30:70, and the special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane electrode has a total weight of 2 to 500 g / m 2 The composite membrane electrode of the special highly reinforced fluorine-containing proton or ion exchange membrane has a tensile strength of >40 MPa in both directions, an ionic conductivity at room temperature of >0.007 S / cm, and an extremely low air permeability, such that the time required for 100 ml of air to permeate the composite membrane electrode is >5 minutes as measured with a Gurley air permeability meter.

[0026] Preferably, the composite film includes a special release film attached to the bottom layer, and the components of the special release film are selected from engineering plastics containing bisphenol A as a main component or engineering plastics containing hexafluorodimethylbisphenol A as a main component, with the proviso that the engineering plastics containing bisphenol A as a main component are polymers obtained by polymerizing or copolymerizing bisphenol A and occupying a weight ratio of more than 50%, and the engineering plastics containing hexafluorodimethylphenol A as a main component are polymers obtained by polymerizing or copolymerizing hexafluorodimethylphenol A and occupying a weight ratio of more than 50%.

[0027] Preferably, the weight ratio of the microporous reinforced membrane to the fluorine-containing proton or ion exchange resin is 10:90 to 30:70.

[0028] Preferably, the microporous reinforced membrane has 2 to 50 layers.

[0029] Preferably, the microporous reinforced membrane has 2 to 30 layers.

[0030] Preferably, the polymer obtained by polymerizing or copolymerizing bisphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof, and the polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof.

[0031] Preferably, the microporous reinforced membrane has a dry weight of 0.5 to 30 g / m 2 The open porosity is 40% to 95%, the thickness is 0.5 to 30 μm, and the tensile strength is >40 MPa in both directions.

[0032] Preferably, the method for producing the micropore-reinforced membrane comprises a process of spinning, such as melt spinning, wet spinning, wet phase change method, temperature difference phase change method, dry solvent method, electrostatic spinning, or ultra-high speed centrifugal spinning, to uniformly converge nano- or micro-sized fibers to form a random network micropore structure, which is then heat-set to form a microporous film, and the resin used is a thermoplastic fluorine-containing or chlorine-containing resin, a carbon fiber precursor, or a resin that can be derived from carbon fiber; the microporous film is extruded into a paste form and then biaxially stretched.

[0033] Preferably, the solution of the fluorine-containing proton exchange resin or ion exchange resin is mixed with one or more of metal nanopowder, metal oxide nanopowder, carbon powder, graphite powder, graphene, and rare metal powder, and the total weight thereof does not exceed 80% of the dry weight of the fluorine-containing proton exchange resin or ion exchange resin.

[0034] Preferably, the metal nanopowder comprises one of silver, platinum or palladium, or a platinum / carbon composite, and the metal oxide powder comprises one of zirconia or ceria.

[0035] Preferably, the microporous reinforced membrane has 2 to 20 layers.

[0036] <Third aspect of the present invention> In a third aspect of the present invention, there is provided a special highly reinforced fluorine-chlorine-containing alkaline battery membrane comprising at least two micropore-reinforced membranes, both sides of each of which are filled with a fluorine-containing proton exchange resin or ion exchange resin, and the weight ratio of the micropore-reinforced membrane to the fluorine-containing proton exchange resin or ion exchange resin is 5:95 to 40:60. The highly reinforced fluorine-chlorine-containing alkaline battery membrane has a total weight of 20 to 500 g / m. 2 The highly reinforced fluorine-chlorine containing alkaline battery membrane has a tensile strength of >40 MPa in both directions, a room temperature ionic conductivity of >0.007 S / cm, and an air permeability of the highly reinforced fluorine-chlorine containing alkaline battery membrane, as measured by a Gurley air permeability meter, such that the time required for 100 ml of air to permeate the composite membrane is >5 minutes.

[0037] Preferably, the weight ratio of the microporous reinforced membrane to the fluorine-containing proton or ion exchange resin is 10:90 to 30:70.

[0038] Preferably, the microporous reinforced membrane has 2 to 50 layers.

[0039] Preferably, the microporous reinforced membrane has 2 to 30 layers.

[0040] Preferably, the plastic further comprises a special release film that does not contain a release agent, and the components of the special release film are selected from engineering plastics containing bisphenol A as a main component or engineering plastics containing hexafluorodimethylbisphenol A as a main component, with the proviso that the engineering plastics containing bisphenol A as a main component are polymers obtained by polymerizing or copolymerizing bisphenol A and occupying a weight ratio of more than 50%, and the engineering plastics containing hexafluorodimethylphenol A as a main component are polymers obtained by polymerizing or copolymerizing hexafluorodimethylphenol A and occupying a weight ratio of more than 50%.

[0041] Preferably, the polymer obtained by polymerizing or copolymerizing bisphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof, and the polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof.

[0042] Preferably, the microporous reinforced membrane has a dry weight of 0.5 to 30 g / m 2 The open porosity is 40% to 95%, the thickness is 0.5 to 30 μm, and the tensile strength is >40 MPa in both directions.

[0043] Preferably, the manufacturing method and material of the microporous reinforced membrane are selected from the following:

[0044] (1) Spinning processes such as melt spinning, wet spinning, wet phase change method, temperature difference phase change method, dry solvent method, electrospinning method, or ultra-high speed centrifugal spinning method are carried out to uniformly converge nano- or μm-sized fibers into a random mesh-like microporous structure, which is then heat-set to form a microporous film, and the resin used is a thermoplastic fluorine-containing or chlorine-containing resin, a carbon fiber precursor, or a resin that can be derived into carbon fiber.

[0045] (2) The microporous film is extruded into a paste form and biaxially stretched to obtain a stretched microporous polytetrafluoroethylene membrane, a microporous polyolefin membrane, or a modified polyolefin membrane.

[0046] Preferably, the solution of the fluorine-containing proton exchange resin or ion exchange resin is mixed with one or more of metal nanopowder, metal oxide nanopowder, carbon powder, graphite powder, graphene, and rare metal powder, and the total weight thereof does not exceed 80% of the dry weight of the fluorine-containing proton exchange resin or ion exchange resin.

[0047] Preferably, the acid equivalent of the fluorine-containing proton exchange resin or ion exchange resin is 400 to 1500, and selectable fluorine-containing proton exchange resins or ion exchange resins include fluorine-containing sulfonic acid resins and fluorine-containing carboxylic acid resins, and the perfluorocarboxylic acid resin:perfluorosulfonic acid resin is filled in the special highly reinforced fluorine-chlorine-containing alkaline battery membrane at a dry weight ratio of 1:9 to 5:5.

[0048] <Fourth embodiment of the present invention> In a fourth aspect of the present invention, there is provided a method for producing a special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane according to the first aspect of the present invention, a composite membrane electrode according to the second aspect, or a fluorine-chlorine-containing alkaline battery membrane according to the third aspect, comprising the following steps:

[0049] Step 1: Cast-coat one side of the special release film with a fluorine-containing proton exchange resin solution or a fluorine-containing ion exchange resin solution and allow it to absorb.

[0050] Step 2: A micropore-reinforced membrane is coated with the resin solution, and the resin solution coated on the release film and the coated micropore-reinforced membrane are thoroughly blended together to obtain a composite membrane.

[0051] Step 3: The composite membrane obtained in step 2 is dried.

[0052] Step 4: A resin solution is further cast-coated on the upper surface of the micropore-reinforced membrane of the composite membrane, and the cast-coated resin solution and the coated micropore-reinforced membrane are thoroughly blended together to obtain a composite membrane.

[0053] Step 5: The composite membrane obtained in step 4 is dried.

[0054] Preferably, the resin solution is further coated on the micropore-reinforced membrane of the composite membrane obtained in step 2, and the resin solution is thoroughly mixed and filled with both the upper and lower surfaces of the micropore-reinforced membrane to form a composite membrane, and then all materials are dried together.

[0055] Preferably, the void volume of the microporous reinforced membrane filled with the fluorine-containing proton exchange resin solution or the fluorine-containing ion exchange resin solution is at least 60% to 90%.

[0056] Preferably, the void volume of the microporous reinforced membrane filled with the fluorine-containing proton exchange resin solution or the fluorine-containing ion exchange resin solution is at least 80%.

[0057] Preferably, the dry weight ratio of the micropore-reinforced membrane to the fluorine-containing proton exchange resin or ion exchange resin is 5:95 to 40:60.

[0058] Preferably, the dry weight ratio of the micropore-reinforced membrane to the fluorine-containing proton exchange resin or ion exchange resin is 10:90 to 30:70.

[0059] Preferably, the components of the special release film are selected from engineering plastics containing bisphenol A as a main component or engineering plastics containing hexafluorodimethylbisphenol A as a main component, provided that the engineering plastics containing bisphenol A as a main component are polymers obtained by polymerizing or copolymerizing bisphenol A and the weight ratio thereof exceeds 50%, and the engineering plastics containing hexafluorodimethylphenol A as a main component are polymers obtained by polymerizing or copolymerizing hexafluorodimethylphenol A and the weight ratio thereof exceeds 50%.

[0060] Preferably, the polymer obtained by polymerizing or copolymerizing bisphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof, and the polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof.

[0061] Preferably, the fluorine-containing proton exchange resin solution or the fluorine-containing ion exchange resin solution is mixed with one or more of metal nanopowder, metal oxide nanopowder, carbon powder, graphite powder, graphene, and rare metal powder, and the total weight thereof does not exceed 80% of the dry weight of the fluorine-containing proton exchange resin or ion exchange resin.

[0062] <Fifth embodiment of the present invention> In a fifth aspect of the present invention, there is provided a special release film containing no release agent for use in producing a battery separator by a cast coating method, the components of which are selected from engineering plastics containing bisphenol A as a main component and engineering plastics containing hexafluorodimethylbisphenol A as a main component, with the proviso that the engineering plastic containing bisphenol A as a main component is a polymer obtained by polymerizing or copolymerizing bisphenol A and occupies more than 50% by weight, and the engineering plastic containing hexafluorodimethylphenol A as a main component is a polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A and occupies more than 50% by weight.

[0063] Preferably, the polymer obtained by polymerizing or copolymerizing bisphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof, and the polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof.

[0064] Preferably, the special release film containing no release agent has a thickness of 10 to 500 μm, a width of at least 100 mm, and is heat-resistant up to 100° C. without deformation.

[0065] Preferably, the thickness of the special resin film not containing a release agent is 25 to 300 μm.

[0066] In addition, the special release film containing no release agent is used to manufacture battery separators by cast coating.

[0067] By adopting the above technical features, the special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane, composite membrane electrode, and fluorine-chlorine-containing alkaline battery membrane of the present invention can be heat-treated several times without being contaminated by release agents and have heat resistance of at least 100°C. The multi-layer microporous reinforced membrane can hide defects of bubbles that may occur from a single coating membrane, greatly improving productivity, greatly improving the tensile strength of the composite membrane, composite membrane electrode, and fluorine-chlorine-containing alkaline battery membrane, and improving the dimensional stability of the composite membrane, composite membrane electrode, and fluorine-chlorine-containing alkaline battery membrane, which is extremely important for service life, enabling high-speed continuous production, meeting the requirements of commercial mass production, and the resulting membrane products have high cleanliness and stability.

[0068] The methods for producing the composite membrane, composite membrane electrode, and fluorine-chlorine-containing alkaline battery membrane of the present invention are simple, reduce production costs, and more importantly, avoid the problem of the release film containing a small amount of free release agent, thereby significantly improving the yield of the final product. The special release film of the present invention, which does not contain a release agent, can have release function without corona treatment or release agent coating, can be used in continuous production, simplify the production process, and reduce production costs.

[0069] <Mode for Carrying Out the Invention> The present invention will be further described below. Note that, although the present examples are based on the technical aspects of the present invention and show detailed embodiments and specific operating procedures, the scope of protection of the present invention is not limited to these examples.

[0070] (1) A composite membrane, composite membrane electrode, or fluorine-chlorine-containing alkaline battery membrane of a special highly reinforced fluorine-containing proton or ion exchange membrane includes at least two layers of micropore-reinforced membrane, and both sides of the micropore-reinforced membrane (continuous phase) of each layer are filled with a fluorine-containing proton exchange resin or ion exchange resin. (2) A special release film is attached to the underside of the composite membrane, composite membrane electrode, or fluorine-chlorine-containing alkaline battery membrane of a special highly reinforced fluorine-containing proton or ion exchange membrane.

[0071] The fluorine-containing proton exchange resin or ion exchange resin may be a commercially available product, for example, from Nafion, 3M, or Solvay, or may be prepared by referring to the method for preparing a fluorine-containing or chlorine-containing conductive polymer resin disclosed in Patent CN106947027B (Patent No. ZL201710251598.5).

[0072] The reinforced composite membrane, composite membrane electrode, or fluorine-chlorine-containing alkaline battery membrane comprises at least two microporous reinforced membrane layers, each of which is filled with a fluorine-containing proton exchange resin or ion exchange resin on both sides, and the overall manufacturing method includes the following steps:

[0073] <Method of manufacturing a micropore-reinforced membrane> Processes and materials for producing the microporous reinforced membrane The manufacturing processes and materials can be selected from the following two groups.

[0074] (1) This method involves melt spinning, wet spinning, wet phase change, temperature difference phase change, dry solvent spinning, electrospinning, and ultra-high speed centrifugal spinning. This process uniformly converges nano- or μm-sized fibers into a random, mesh-like microporous structure, which is then thermally fixed to form a microporous film. The resins used are preferably heat-meltable fluorine- or chlorine-containing resins, carbon fiber precursors, or resins that can be derived into carbon fibers, such as polyacrylonitrile (PAN) or its copolymers, polyimide, polyamide (nylon), polyester (PET), aramid, and polyether ketone (PEEK). (2) Paste extrusion and biaxial stretching can produce microporous reinforced membranes (e.g., stretched microporous polytetrafluoroethylene membranes, microporous polyolefin membranes (polyethylene, polypropylene, etc.), and modified polyolefin membranes).

[0075] The microporous reinforced membrane has a tensile strength (TD, MD) (see ASTM D882 test method) of >40 MPa in both directions, preferably >50 MPa, and most preferably >80 MPa, and an open porosity of 40% to 95%. The microporous reinforced membrane has a mesh-like microporous structure, which can form a continuous phase microporous reinforced membrane after heat setting, and the microporous reinforced membrane has a dry weight of 0.5 to 30 g / m. 2 , preferably 1 to 10 g / m 2 The open porosity is 40 to 95%, preferably 50 to 90%, and the thickness is 0.5 to 30 μm, preferably 1 to 15 μm.

[0076] <Method of manufacturing a highly reinforced composite membrane, a composite membrane electrode, or a special highly reinforced fluorine-chlorine-containing alkaline battery membrane> A fluorine-containing proton exchange resin or ion exchange resin solution may be cast-coated onto the release film, which is free of the release agent and can withstand drying at least at 100°C, to form at least two layers of a microporous reinforced membrane. The fluorine-containing proton exchange resin or ion exchange resin solution is filled as completely as possible into the pores on both sides of the microporous reinforced membrane by multiple cast coating or immersion processes. The fluorine-containing proton exchange resin or ion exchange resin has a sulfonic acid or carboxylic acid acid equivalent (meq / g) of 400 to 1500, preferably 500 to 1100, and more preferably 600 to 950. The solvent is then removed from the composite material by drying to produce a special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane, composite membrane electrode, or special highly reinforced fluorine-chlorine-containing alkaline battery membrane.

[0077] The method for producing the specially reinforced fluorine-containing composite membrane or membrane electrode of the present invention includes the following steps:

[0078] Step 1: Cast-coat one side of a release film that does not contain a special release agent with a fluorine-containing proton exchange resin solution or a fluorine-containing ion exchange resin solution and allow it to soak in.

[0079] Step 2: A micropore-reinforced membrane is coated with the coated resin solution, and the resin solution coated on the release film and the coated micropore-reinforced membrane are allowed to fully blend together to obtain a composite membrane.

[0080] Step 3: The composite membrane obtained in step 2 is dried.

[0081] Step 4: The resin solution is cast-coated on the upper surface of the microporous reinforced membrane of the composite membrane, and then dried twice to obtain a finished product.

[0082] However, the components of the special release film will be described in detail later.

[0083] The method for producing a special reinforced fluorine-containing composite membrane or film electrode of the present invention is simple, reduces production costs, and more importantly, avoids the problem of the release membrane containing a trace amount of free release agent, significantly improving the yield of the final product. After drying, more than 60%, preferably more than 80%, and most preferably more than 90% of the void volume on both sides of the microporous reinforced membrane is filled with the fluorine-containing proton exchange resin. The dry weight ratio of the microporous reinforced membrane to the fluorine-containing proton exchange resin or ion exchange resin is (5:95) to (40:60), preferably (10:90) to (30:70), and the reinforced fluorine-containing composite membrane has a total weight of 3 to 60 g / m. 2 The thickness is 2 μm to 30 μm, the tensile strength (TD, MD) of the highly reinforced composite membrane is >40 MPa, preferably >50 MPa, and most preferably >80 MPa in both directions, the room temperature ionic conductivity of the reinforced composite membrane is >0.007 (S / cm), preferably >0.013 (S / cm), and more preferably >0.018 (S / cm), and the air permeability of the reinforced composite membrane is extremely low, and the time required for 100 ml of air to permeate through the composite membrane as measured with a Gurley air permeometer is >5 minutes, and preferably >15 minutes.

[0084] In addition, the resin solution is further coated on the micropore-reinforced membrane of the composite membrane obtained in step 2, and the resin solution is thoroughly mixed with both the upper and lower surfaces of the micropore-reinforced membrane to fill the membrane, forming a composite membrane, and then all materials are dried together.

[0085] Alternatively, step 2 is repeated after step 3 to coat N layers of microporous reinforced membranes, and the microporous reinforced membranes may be 2 to 50 layers, preferably 2 to 30 layers, of a highly reinforced fluorine-containing composite membrane, provided that the total dry weight ratio of the microporous reinforced membranes to the fluorine-containing proton exchange resin or ion exchange resin is (5:95) to (40:60). The highly reinforced fluorine-containing composite membrane comprises 2 to 50 layers of microporous reinforced membranes, preferably 2 to 30 layers of microporous reinforced membranes, and both sides of each layer of the microporous reinforced membrane are filled with the fluorine-containing proton exchange resin or ion exchange resin, and the total weight of the highly reinforced fluorine-containing composite membrane is 3 to 500 g / m. 2 , preferably 5 to 300 g / m 2 , and most preferably 10 to 250 g / m 2 The thickness is 2 μm to 250 μm, preferably 3 μm to 150 μm, and most preferably 5 μm to 130 μm. The tensile strength (TD, MD) of the highly reinforced fluorine-containing composite membrane is >40 MPa, preferably >50 MPa, and most preferably >80 MPa in both directions. The room temperature ionic conductivity of the highly reinforced fluorine-containing composite membrane is >0.007 (S / cm), preferably >0.013 (S / cm), and more preferably >0.018 (S / cm). The air permeability of the highly reinforced fluorine-containing composite membrane is very low, and the time required for 100 ml of air to permeate through the composite membrane is >5 minutes, preferably >15 minutes, as measured using a Gurley air permeability meter.

[0086] The dry weight ratio of the micropore-reinforced membrane to the fluorine-containing proton exchange resin or ion exchange resin is 10:90 to 30:70.

[0087] The fluorine-containing proton exchange resin or ion exchange resin has an acid equivalent (g / equivalent wt.) of 400 to 1500, preferably 600 to 1200. Examples of the fluorine-containing proton exchange resin or ion exchange resin include, but are not limited to, fluorine-containing sulfonic acid resins and fluorine-containing carboxylic acid resins. The fluorine-containing proton exchange resin solution or fluorine-containing ion exchange resin solution is mixed with one or more of metal nanopowder, metal oxide nanopowder, carbon powder, graphite powder, graphene, and rare metal powder, the total weight of which does not exceed 80% of the dry weight of the fluorine-containing proton exchange resin or ion exchange resin. Examples of the metal nanopowder include, but are not limited to, silver, platinum alloy, palladium, or platinum / carbon composite. Examples of the metal oxide powder include, but are not limited to, zirconia and ceria.

[0088] The advantage of the material of the present invention is that such a release film does not contain any applied release agents, thereby eliminating the risk of release agents contaminating the finished membrane electrode. By casting the multilayer microporous reinforced membrane multiple times, the air bubble defects that may be formed by a single applied layer can be hidden and significantly reduced, greatly improving the yield. Unexpectedly, the multilayer microporous composite membrane also contributes to improving the tensile strength of the composite membrane, improving the dimensional stability of the composite membrane, which is extremely important for its service life. It can achieve high-speed continuous production, meeting the requirements of commercial mass production, and the resulting finished membrane has high cleanliness and stability.

[0089] <Special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane, composite membrane electrode, special highly reinforced fluorine-chlorine-containing alkaline battery membrane> The highly reinforced composite membrane and composite membrane electrode of the present invention comprise at least two microporous reinforced membrane layers, each of which is filled with a fluorine-containing proton exchange resin or ion exchange resin on both sides, and the weight ratio of the microporous reinforced membrane to the fluorine-containing proton exchange resin or ion exchange resin is (5:95) to (40:60), preferably (10:90) to (30:70). The total weight of the reinforced composite membrane and composite membrane electrode is 2 to 500 g / m 2 , preferably 5 to 300 g / m2 , and most preferably 5 to 200 g / m 2 The thickness is 1 μm to 300 μm, preferably 2 μm to 200 μm, and most preferably 3 μm to 100 μm. The tensile strength (see ASTM D882 test method) (TD, MD) of the reinforced composite membrane or composite membrane electrode is >40 MPa, preferably >50 MPa, and most preferably >80 MPa in both directions. The room temperature proton / ion conductivity (Ionic Conductivity, GB / T20042.3-2009 Proton Exchange Membrane Fuel Cell Part 3: Test Methods for Proton Exchange Membranes) of the reinforced composite membrane is >0.007 (S / cm), preferably >0.013 (S / cm), and more preferably >0.018 (S / cm). The air permeability of the reinforced composite membrane or composite membrane electrode is extremely low, and the time required for 100 ml of air to permeate through the composite membrane or composite membrane electrode, as measured using a Gurley permeometer, is >5 minutes, preferably >15 minutes.

[0090] The special highly reinforced fluorine-chlorine-containing alkaline battery membrane according to the present invention comprises at least two microporous reinforced membranes, each of which is filled with a fluorine-containing proton exchange resin or ion exchange resin on both sides, the weight ratio of the microporous reinforced membrane to the fluorine-containing proton exchange resin or ion exchange resin being 5:95-40:60, and the total weight of the highly reinforced fluorine-chlorine-containing alkaline battery membrane is 20-500 g / m 2 The thickness is 10 μm to 260 μm, the tensile strength of the highly reinforced fluorine chlorine-containing alkaline battery membrane is greater than 40 MPa in both directions, the room temperature ionic conductivity of the highly reinforced fluorine chlorine-containing alkaline battery membrane is greater than 0.007 S / cm, and the air permeability of the highly reinforced fluorine chlorine-containing alkaline battery membrane is such that the time required for 100 ml of air to permeate the composite membrane, as measured by a Gurley air permeability meter, is greater than 5 minutes.

[0091] The fluorine-containing proton exchange resin or ion exchange resin solution may be mixed with one or more kinds of metal nanopowder, metal oxide nanopowder, carbon powder, graphite powder, graphene, rare metal powder, etc., and the mixture may be filled all at once into the pores on both sides of the microporous membrane.

[0092] The total weight of the metal nanopowder, metal oxide nanopowder, carbon powder, graphite powder, graphene, rare metal powder, etc. does not exceed 80% of the dry weight of the fluorine-containing proton exchange resin or ion exchange resin. The rare metal nanopowder includes, but is not limited to, silver, platinum, palladium, or platinum / carbon composite. The metal oxide powder includes, but is not limited to, zirconia and ceria.

[0093] In some embodiments of the present invention, the resulting special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane comprises at least two microporous reinforced membrane layers, each of which is filled with a fluorine-containing proton exchange resin or ion exchange resin on both sides, and the total weight of the reinforced composite membrane is 2 to 500 g / m 2 , preferably 5 to 300 g / m 2 , and most preferably 5 to 200 g / m 2 The thickness (see ASTM D756) of the highly reinforced composite membrane is 1 μm to 300 μm, preferably 2 μm to 200 μm, and most preferably 3 μm to 100 μm. The tensile strength (see ASTM D882 test method) (TD, MD) of the highly reinforced composite membrane is >40 MPa, preferably >50 MPa, and most preferably >80 MPa in both directions. The room temperature proton / ion conductivity (Ionic Conductivity, see GB / T20042.3-2009 Proton Exchange Membrane Fuel Cell Part 3: Proton Exchange Membrane Measurement Methods) of the highly reinforced composite membrane is >0.007 (S / cm), preferably >0.013 (S / cm), and more preferably >0.018 (S / cm). The highly reinforced composite membrane has extremely low air permeability, with the time required for 100 ml of air to permeate the composite membrane being >5 minutes, preferably >15 minutes, as measured using a Gurley air permeability meter.

[0094] In some embodiments of the present invention, the resulting special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane electrode comprises at least two microporous reinforced membrane layers, each of which is filled with a fluorine-containing proton or ion exchange resin on both sides, preferably 2 to 30 microporous reinforced membrane layers, most preferably 2 to 15 microporous reinforced membrane layers. The total weight of the reinforced composite membrane electrode is 3 to 80 g / m 2 and preferably 8 to 50 g / m 2 , and most preferably 10 to 30 g / m 2 The thickness (see ASTM D756) is 3 μm to 35 μm, preferably 5 μm to 25 μm, and most preferably 7 μm to 18 μm. The tensile strength (TD, MD) of the highly reinforced composite membrane electrode is >40 MPa in both directions, preferably >50 MPa, and most preferably >80 MPa. The room temperature ionic conductivity of the highly reinforced composite membrane electrode is >0.007 (S / cm), preferably >0.013 (S / cm), and more preferably >0.018 (S / cm). The air permeability of the highly reinforced composite membrane is very low, and the time required for 100 ml of air to permeate the composite membrane, as measured using a Gurley permeometer, is >5 minutes, preferably >15 minutes.

[0095] In another embodiment of the present invention, the special highly reinforced fluorine-containing proton or ion exchange membrane composite electrode comprises at least two layers of microporous reinforced membrane, preferably 2 to 45 layers of microporous reinforced membrane, most preferably 2 to 20 layers of microporous reinforced membrane, both sides of which are filled with a fluorine-containing proton exchange resin or ion exchange resin, the weight ratio of the microporous reinforced membrane to the fluorine-containing proton exchange resin or ion exchange resin is (5:95) to (40:60), preferably (10:90) to (30:70), and the total weight of this highly reinforced composite membrane electrode is 70 to 500 g / m 2 , preferably 80 to 300 g / m 2 , and most preferably 100 to 200 g / m 2The thickness is 30 μm to 300 μm, preferably 50 μm to 200 μm, and most preferably 60 μm to 120 μm. The tensile strength (TD, MD) of the highly reinforced composite membrane electrode is >40 MPa in both directions, preferably >50 MPa, and most preferably >80 MPa. The room temperature ionic conductivity of the highly reinforced composite membrane electrode is >0.007 (S / cm), preferably >0.013 (S / cm), and more preferably >0.018 (S / cm). The air permeability of the highly reinforced composite membrane electrode is very low, and the time required for 100 ml of air to permeate through the composite membrane, as measured using a Gurley permeometer, is >5 minutes, preferably >15 minutes.

[0096] In another embodiment of the present invention, the special reinforced fluorine-chlorine-containing alkaline battery membrane comprises three layers of micropore-reinforced membrane, each of which is filled with a fluorine-containing proton exchange resin or ion exchange resin on both sides, and the weight ratio of the micropore-reinforced membrane to the fluorine-containing proton exchange resin or ion exchange resin is (5:95) to (40:60), preferably (10:90) to (30:70), and the total weight of the highly reinforced fluorine-chlorine-containing alkaline battery membrane is 2 to 500 g / m 2 , preferably 5 to 300 g / m 2 , and most preferably 5 to 200 g / m 2 The thickness of the microporous reinforced membrane is 1 μm to 300 μm, preferably 2 μm to 200 μm, and most preferably 3 μm to 100 μm. The tensile strength (see ASTM D882 test method) of the highly reinforced fluorine-chlorine-containing membrane in both TD and MD directions is >40 MPa, preferably >50 MPa, and most preferably >80 MPa. The room temperature proton / ion conductivity (Ionic Conductivity, GB / T20042.3-2009 Proton Exchange Membrane Fuel Cell Part 3: Proton Exchange Membrane Measurement Method) of the reinforced composite membrane is >0.007 (S / cm), preferably >0.013 (S / cm), and more preferably >0.018 (S / cm). The air permeability of the reinforced composite membrane is extremely low, and the time required for 100 ml of air to permeate the composite membrane as measured using a Gurley air permeometer is >5 minutes, and preferably >15 minutes.

[0097] In yet another embodiment of the present invention, the special highly reinforced fluorine-chlorine-containing alkaline battery membrane comprises 3 to 30 micropore-reinforced membranes, and both sides of each micropore-reinforced membrane are filled with a fluorine-containing proton exchange resin or an ion exchange resin; the highly reinforced fluorine-chlorine-containing alkaline battery composite membrane has one side entirely coated with a perfluorocarboxylic acid resin and the other side entirely coated with a perfluorosulfonic acid resin; the total weight ratio of the micropore-reinforced membrane to the fluorine-containing proton exchange resin or the ion exchange resin is (5:95) to (40:60), preferably (10:90) to (30:70); and the total weight of the highly reinforced chlorine-alkali battery composite membrane is 20 to 450 g / m 2 , preferably 50 to 300 g / m 2 , and most preferably 100 to 250 g / m 2 The thickness of the highly reinforced fluorine-chlorine-containing alkaline battery composite membrane is 10 μm to 230 μm, preferably 25 μm to 150 μm, and most preferably 50 μm to 130 μm. The tensile strength (TD, MD) of the highly reinforced fluorine-chlorine-containing alkaline battery composite membrane is greater than 40 MPa, preferably greater than 50 MPa, and most preferably greater than 80 MPa. The room temperature ionic conductivity of the highly reinforced fluorine-chlorine-containing alkaline battery composite membrane is greater than 0.007 (S / cm), preferably greater than 0.013 (S / cm), and more preferably greater than 0.018 (S / cm). The air permeability of the reinforced fluorine-chlorine-containing alkaline battery composite membrane is extremely low, and the time required for 100 ml of air to permeate the composite membrane, as measured using a Gurley air permeability meter, is greater than 5 minutes, and preferably greater than 15 minutes.

[0098] The total dry weight ratio of the perfluorocarboxylic acid resin filled in the special highly reinforced fluorine-chlorine-containing alkaline battery membrane is (1:9) to (5:5), preferably (2:8) to (4:6).

[0099] The special highly reinforced fluorine-chlorine-containing alkaline battery membrane of the present invention is free from the risk of contamination by release agents, can be subjected to multiple heat treatments, and has heat resistance of at least 100°C. The multi-layer microporous reinforced membrane can hide defects that may occur from a single coating membrane, greatly improving productivity. It also contributes to improving the tensile strength of the special high-strength fluorine-chlorine-containing alkaline battery membrane and improving its dimensional stability, which is crucial for its service life. It also enables high-speed continuous production, meets the requirements of commercial mass production, and the resulting membrane product has high cleanliness and stability.

[0100] <Release film without release agent> One objective of the present invention is to overcome the shortcomings of conventional production processes. Conventional release films contain trace amounts of free release agents, particularly silicon-containing release agents, which are easily adsorbed by cast coating materials, contaminating the final product and making cleaning difficult, which is a significant disadvantage in producing high-quality, clean proton exchange membranes. The present invention provides a release-agent-free release film (i.e., the membrane itself has inherent release properties and does not require corona or release agent application), which can be used for continuous production. A fluorine-containing proton exchange resin solution or ion exchange resin solution is cast onto such a release-agent-free release film and does not deform even when dried at least at 100°C, thereby producing high-quality fluorine-containing proton exchange membranes or fluorine-containing ion exchange membranes. Furthermore, by applying such a release-agent-free modified membrane to the surface through one or more cast coatings, and further coating the coating solution with a microporous reinforced membrane, the applied fluorine-containing sulfonic acid or carboxylic acid resin solution can be dried and repeatedly processed, thereby making mass production of fluorine-containing proton exchange membranes more convenient and further reducing production costs.

[0101] The present invention discloses a special release film that does not contain any coating release agent, does not require corona treatment, may have a thickness of 10 to 500 μm, preferably 25 to 300 μm, and is at least 100 mm in width, and can withstand heat of at least 100°C without deformation, preferably 120°C without deformation, and can be used to manufacture fluorine-containing proton exchange membranes or fluorine-containing ion exchange membranes, etc., and is applicable to battery separators. The battery separator manufacturing process involves cast-coating such a release film using a fluorine-containing proton exchange resin solution or fluorine-containing ion exchange resin solution with excellent film-forming properties, followed by drying to form a fixed film and winding it up into a roll.

[0102] The release film component is selected from (1) engineering plastics containing bisphenol A as the main component (weight ratio >50%): polymers obtained by polymerizing or copolymerizing with bisphenol A, such as polycarbonate, polyphenylene ether, polysulfone resin, polyepoxy resin, or mixed copolymers thereof, or (2) engineering plastics containing hexafluorodimethylbisphenol A as the main component (weight ratio >50%): polymers obtained by polymerizing or copolymerizing hexafluorodimethylbisphenol A, such as polycarbonate, polyphenylene ether, polysulfone resin, polyepoxy resin, or mixed copolymers thereof.

[0103] The membrane surface does not contain any additional coating release agent, does not require corona treatment, can be cast once or multiple times, and by coating a microporous reinforced membrane during the casting process, the strength of the composite membrane can be improved, and a proton exchange membrane or ion exchange membrane can be formed that is unexpectedly easy to peel off after casting and drying and is free of residual solvent or release agent contamination. The advantages of the material of the present invention are that such a release membrane does not contain a coated release agent, so there is no risk of the release agent contaminating the finished membrane, and by casting and coating multiple multi-layer microporous reinforced membranes multiple times, the bubble defects that may occur from a single coating can be hidden and greatly reduced, greatly improving productivity and enabling continuous production, meeting the requirements of commercial mass production, and the resulting finished membrane has high cleanliness and stability, and waste disposal is convenient.

[0104] When a battery separator is manufactured using a cast coating method with a special release film that does not contain a release agent, the manufacturing process can include: 1. applying a fluorine-containing proton exchange resin solution or a fluorine-containing ion exchange resin solution to one side of the special release film and allowing it to soak in; then coating a micropore-reinforced film with the applied resin solution, allowing the resin solution applied to the special release film and the coated micropore-reinforced film to soak in thoroughly; and 2. cast-coating the composite film (mounted on the special engineering plastic film) obtained in step 1 with a second resin solution onto the first layer of the coated micropore-reinforced film; then coating the second layer of the micropore-reinforced film with the second cast-coated resin solution, allowing the resin solution applied to the special release film to soak in thoroughly; then drying; so that after drying, the void volume on both sides of each layer of the micropore-reinforced film is filled with the fluorine-containing proton exchange resin. 3. Step 2 is repeated at least 0 to 48 times, preferably 0 to 28 times, and finally, a resin solution is applied to the coated microporous reinforced membrane layer, followed by drying, to obtain a highly reinforced proton exchange membrane, ion exchange membrane, or membrane electrode having at least two (2 to 50, preferably 2 to 30) microporous reinforced membrane layers. Example 1

[0105] (Release film containing no release agent) (1A) Carbonate resin obtained by polycondensation of bisphenol A (without adding any auxiliary or release agent) is melt-extruded and biaxially stretched to obtain transparent films with thicknesses of approximately 300 μm, 150 μm, and 25 μm (used as is without corona treatment).

[0106] (1B) Polycarbonate resin obtained by polycondensation of hexafluorodimethylphenol A (without adding any auxiliary or release agent) is melt-extruded and biaxially stretched to obtain transparent films with thicknesses of approximately 300 μm, 150 μm, and 25 μm (used as is without corona treatment).

[0107] (1C) A release film with the above thickness was produced, but the resin used was a polyphenylene ether-p-bisphenol A type epoxy resin (EHPPO type, used as is without adding any auxiliary or release agent, and without corona treatment). The resin production process was JPEG2025128245000001.jpg5170 Teng, Xiaoyu Li, and Haiqiao Wang, Key Laboratory of Carbon Fiber and Functional Polymer Education, School of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China. Abstract: Reactive terminal epoxy hyperbranched polyphenylene ether (EHPPO) was prepared and modified with bisphenol A epoxy resin. The resin was then cured with an acid anhydride curing agent. The thermal, mechanical, and dielectric properties of the cured samples were characterized. A comparative modification study was also conducted using hyperbranched polyphenylene ether (CHPPO), which has the same molecular backbone structure but non-reactive benzyl end groups. The results showed that the two different modifiers each have advantages in modifying bisphenol A epoxy resin. The EHPPO-modified epoxy resin exhibited superior thermal performance and tensile strength, while the CHPPO-modified epoxy resin had a lower dielectric constant. The films obtained as in the above (1A) to (1C) have a high releasing effect and do not leave any residue, even without corona treatment or application of a releasing agent. Example 2

[0108] (Proton exchange resin solution or ion exchange resin solution or mixture) S1 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent number (meq / g) approximately 830%], 40% ethanol, 40% water).

[0109] S2 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent number (meq / g) approximately 790], 40% ethanol, 40% water).

[0110] L1 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent number (meq / g) approximately 1000], 40% n-propanol, 40% water).

[0111] L2 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent number (meq / g) approximately 950], 40% ethanol, 40% water).

[0112] L3 (weight ratio: 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent number (meq / g) approximately 1100], 40% n-propanol, 40% water).

[0113] L4 (weight ratio: approximately 10% platinum black powder, 10% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent number (meq / g) approximately 1100], 40% n-propanol, 40% water.)

[0114] L5 (weight ratio: approximately 5% ZrO2 zirconia nanopowder, approximately 15% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent number (meq / g) approximately 1100], 40% n-propanol, 40% water).

[0115] LC6 (weight ratio: approximately 5% ZrO2 zirconia nanopowder, approximately 15% [tetrafluoroethylene and CF2=CF-O-CF2CF2CF2-COOH fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) approximately 1000], 40% n-propanol, 40% water).

[0116] LC7 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-COOH fluorine-containing proton exchange resin copolymer, its acid equivalent number (meq / g) approximately 950], 40% n-propanol, 40% water).

[0117] L8 (weight ratio: approximately 10% platinum / carbon black powder, 10% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent number (meq / g) approximately 1100], 40% n-propanol, 40% water). Example 3

[0118] (For comparison) (Release film 1A, one layer of 10 μm thick microporous reinforced film)

[0119] A proton exchange resin solution S1 (weight ratio: about 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) about 830], 40% ethanol, 40% water) is applied to a release film 1A having a thickness of about 25 μm, and then a microporous polytetrafluoroethylene reinforced membrane having a thickness of about 10 μm is coated thereon, dried with a blower, and then the same proton exchange resin solution is further applied to the microporous polytetrafluoroethylene reinforced membrane. The composite membrane was then dried with a fan, and finally heated to 120°C in an oven and baked for 5 minutes, after which it was removed and cooled. The fluorine-containing proton exchange membrane could be smoothly peeled off from the release film 1A, with no visible residue on the release film. The peeled fluorine-containing proton exchange membrane was flat and had a thickness of about 16-18 μm, a density of about 2.20, an acid equivalent number (meq / g) of about 1000, a tensile strength (TD) and a MD of 40-50 MPa, and a room temperature proton / ionic conductivity of >0.012 (S / cm). The time required for 100 ml of air to pass through the composite membrane was >15 minutes, as measured using a Gurley air permeability meter. Example 4

[0120] (Release film 1A, two layers of 5μm thick microporous reinforced film) A proton exchange resin solution S1 (weight ratio: about 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) about 830%, 40% ethanol, 40% water) was applied to a release film 1A having a thickness of about 25 μm, and then a thin microporous polytetrafluoroethylene reinforced membrane (continuous phase) having a thickness of about 5 μm was coated thereon and dried with a blower. Thereafter, the same proton exchange resin solution was further coated on the microporous polytetrafluoroethylene reinforced membrane, and then another thin microporous polytetrafluoroethylene reinforced membrane (continuous phase) having a thickness of about 5 μm was coated thereon and dried with a blower. The same proton exchange resin solution was applied to a fluoroethylene-reinforced membrane, which was then dried with a fan and finally heated to 120°C in an oven and baked for 5 minutes. After removal and cooling, the fluorine-containing proton exchange membrane was peeled off smoothly from the release film 1A, with no visible residue remaining on the release film. The peeled fluorine-containing proton exchange membrane was flat and had a thickness of about 16-18 μm, a density of about 2.19, an acid equivalent (meq / g) of about 1020, and tensile strengths (TD and MD) of 60-70 MPa. Unexpectedly, the tensile strength was superior to that of the 10 μm-thick single-layer microporous-reinforced membrane of Example 3. The room-temperature proton / ionic conductivity was greater than 0.012 (S / cm). The time required for 100 ml of air to pass through this composite membrane, as measured using a Gurley air permeability tester, was greater than 15 minutes. Example 5

[0121] (Release film 1A, 3-layer 3μm thick microporous reinforced film) A proton exchange resin solution S1 (weight ratio: about 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) about 830], 40% ethanol, 40% water) was applied to a release film 1A having a thickness of about 25 μm, and a thinner microporous polytetrafluoroethylene reinforced membrane (continuous phase) having a thickness of about 3 μm was coated thereon and dried with a blower. Thereafter, the same proton exchange resin solution was further applied to the microporous polytetrafluoroethylene reinforced membrane ... The polytetrafluoroethylene reinforced membrane (continuous phase) was coated with the same proton exchange resin solution and dried with a fan. The microporous polytetrafluoroethylene reinforced membrane was then coated with the same proton exchange resin solution and dried with a fan. Finally, the membrane was heated to 120°C in an oven and baked for 5 minutes, then removed and cooled. The fluorine-containing proton exchange membrane could be smoothly peeled off from the release film 1A. No visible residue remained on the release film. The peeled fluorine-containing proton exchange membrane was flat and had a thickness of about 16-18 μm, a density of about 2.18, and an acid equivalent number (meq / g) of about 1040. The tensile strengths (TD and MD) were both 80-90 MPa. Unexpectedly, the strength was superior to that of the single-layer 10 μm-thick microporous reinforced membrane of Example 3. The room temperature proton / ion conductivity (Ionic It was found that the conductivity was >0.012 (S / cm) and the time required for 100 ml of air to pass through the composite membrane was >15 minutes as measured by a Gurley permeability meter. Example 6

[0122] (Release film 1B, two-layer microporous reinforced film) A proton exchange resin solution S2 (weight ratio: about 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) about 790], 40% ethanol, 40% water) was applied to a release film 1B having a thickness of about 25 μm, and then a thinner microporous polytetrafluoroethylene reinforced membrane (continuous phase) having a thickness of about 2 μm was coated on the release film 1B. The membrane was then dried with a blower, and the same proton exchange resin solution was then coated on the microporous polytetrafluoroethylene reinforced membrane, and another thinner microporous polytetrafluoroethylene reinforced membrane (continuous phase) having a thickness of about 2 μm was then coated on the membrane. The microporous polytetrafluoroethylene reinforced membrane was then coated with the same proton exchange resin solution, dried with a fan, and finally heated to 120°C in an oven and baked for 5 minutes, then removed and cooled. The fluorine-containing proton exchange membrane was peeled smoothly from the release film 1B, with no visible residue on the release film. The peeled fluorine-containing proton exchange membrane was flat and had a thickness of about 8-9 μm, a density of about 2.20, an acid equivalent number (meq / g) of about 1010, a tensile strength (TD) and a MD of >100 MPa, a room temperature proton / ionic conductivity (Ionic Conductivity) of >0.013 (S / cm), and the time required for 100 ml of air to pass through this composite membrane was >15 minutes, as measured by a Gurley air permeability meter. Example 7

[0123] (Release film 1C, two-layer microporous reinforced film) A proton exchange resin solution S1 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) approximately 830], 40% ethanol, 40% water) was applied to a release film 1C having a thickness of approximately 25 μm, and a thinner microporous polytetrafluoroethylene reinforced membrane (continuous phase) having a thickness of approximately 1 μm was coated thereon, and dried with a blower. Thereafter, the same proton exchange resin solution was again applied to the microporous polytetrafluoroethylene reinforced membrane, and a thinner microporous polytetrafluoroethylene reinforced membrane (continuous phase) having a thickness of approximately 1 μm was coated thereon. After drying with a fan, the same proton exchange resin solution was applied to the microporous polytetrafluoroethylene reinforced membrane, which was then dried with a fan again. Finally, it was heated to 120°C in an oven and baked for 5 minutes, then removed and cooled. The fluorine-containing proton exchange membrane could be smoothly peeled off from the release film 1C, with no visible residue on the release film. The peeled fluorine-containing proton exchange membrane was flat and had a thickness of approximately 5-6 μm, a density of approximately 2.20, an acid equivalent number (meq / g) of the composite membrane of approximately 990, a tensile strength (TD) and a MD of >120 MPa, a room temperature proton / ionic conductivity of >0.015 (S / cm), and the time required for 100 ml of air to pass through this composite membrane was >15 minutes, as measured using a Gurley air permeability meter. Example 8

[0124] (Release film 1A, 5-layer microporous reinforced film, 2 layers of polytetrafluoroethylene on the front and back, 3 layers of polypropylene in the middle) A proton exchange resin solution S1 (weight ratio: about 20% tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) about 830, 40% ethanol, 40% water) was cast-coated onto a release film 1A having a thickness of about 150 μm, and then a thin microporous polytetrafluoroethylene reinforced membrane having a thickness of about 3 μm was coated thereon and dried with a blower. Thereafter, the same proton exchange resin solution was again applied to the microporous polytetrafluoroethylene reinforced membrane, and then a thin microporous polypropylene reinforced membrane having a thickness of about 4 μm was coated thereon and dried with a blower. Thereafter, the same proton exchange resin solution was again applied to the microporous polypropylene ... the same proton exchange resin solution was again applied to the microporous polypropylene reinforced membrane, and then the same proton exchange resin solution was again applied to the microporous polypropylene reinforced membrane, and then the same proton exchange resin solution was again applied to the microporous polypropylene reinforced membrane. The resulting mixture was then coated with a thin, microporous polypropylene-reinforced membrane about 4 μm thick and dried with a fan. The same proton exchange resin solution was then applied to the microporous polypropylene-reinforced membrane, and a thin, microporous polytetrafluoroethylene-reinforced membrane about 3 μm thick was then coated with the same proton exchange resin solution and dried with a fan. The resulting mixture was then heated to 120°C in an oven and baked for 5 minutes before being removed and cooled. The fluorine-containing proton exchange membrane was peeled off smoothly from the release film 1A, with no visible residue on the release film. The peeled fluorine-containing proton exchange membrane was flat and about 28-30 μm thick, had a density of about 2.1, and the acid equivalent number (meq / g) of the composite membrane was about 1050. The tensile strengths (TD and MD) were both >70 MPa, and the room temperature proton / ionic conductivity (Ionic The composite membrane has a conductivity of >0.011 (S / cm) and the time required for 100 ml of air to pass through it, as measured by a Gurley permeability meter, is >15 minutes. Example 9

[0125] (Release film 1A, 10-layer microporous reinforced membrane, 2-layer polytetrafluoroethylene on the front and back, 8-layer polyacrylonitrile PAN in the middle) A proton exchange resin solution L1 (weight ratio: about 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) about 1000], 40% n-propanol, and 40% water) was cast-coated onto a release film 1A having a thickness of about 150 μm, and then a microporous polytetrafluoroethylene reinforced membrane having a thickness of about 3 μm was coated thereon, followed by drying with a blower. Thereafter, a proton exchange resin solution L2 (weight ratio: about 20% [tetrafluoroethylene] A fluorine-containing proton exchange resin copolymer (ethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H, containing 40% ethanol and 40% water) was coated onto a thin polyacrylonitrile PAN-reinforced membrane about 3-4 μm thick and dried with a blower. The same proton exchange resin solution L2 was then coated onto the thin polyacrylonitrile PAN-reinforced membrane about 3-4 μm thick and dried with a blower. The same proton exchange resin solution L2 was then coated onto the thin polyacrylonitrile PAN-reinforced membrane about 3-4 μm thick and dried with a blower. The same proton exchange resin solution L2 was then coated onto the thin polyacrylonitrile PAN-reinforced membrane about 3-4 μm thick and dried with a blower. The same proton exchange resin solution L2 was applied to a thin polyacrylonitrile PAN reinforced membrane having a thickness of about 3-4 μm, and dried with a blower. Thereafter, the same proton exchange resin solution L2 was applied to the microporous polyacrylonitrile PAN reinforced membrane, and then ... The same proton exchange resin solution L2 is applied to a microporous polyacrylonitrile PAN reinforced membrane, and a thin polyacrylonitrile PAN reinforced membrane with a thickness of about 3 to 4 μm is coated, and dried with a blower; thereafter, the same proton exchange resin solution L2 is applied to a microporous polyacrylonitrile PAN reinforced membrane, and a thin polyacrylonitrile PAN reinforced membrane with a thickness of about 3 to 4 μm is coated, and dried with a blower; thereafter, the same proton exchange resin solution L2 is applied to a microporous polyacrylonitrile PAN reinforced membrane, and a thin polyacrylonitrile PAN reinforced membrane with a thickness of about 3 to 4 μm is coated, and dried with a blower; thereafter,The same proton exchange resin solution L2 was applied to a microporous polyacrylonitrile PAN-reinforced membrane, which was then coated with a thin polytetrafluoroethylene-reinforced membrane approximately 3 μm thick. The membrane was then dried with a fan and finally heated to 130°C in an oven. After baking for 10 minutes, the membrane was removed and cooled. The fluorine-containing proton exchange membrane could be smoothly peeled off from the release film 1A, with no visible residue remaining on the release film. The peeled fluorine-containing proton exchange membrane was flat and approximately 58-60 μm thick, had a density of approximately 2.1, a composite membrane acid equivalent (meq / g) of approximately 1050, a tensile strength (TD) and a MD of >50 MPa, and a room-temperature proton / ionic conductivity of >0.01 (S / cm). The time required for 100 ml of air to pass through the composite membrane measured using a Gurley air permeability meter was >15 minutes. Example 10

[0126] (Release film 1B and 15-layer microporous reinforced film, both made of expanded polytetrafluoroethylene) Proton exchange membrane electrode containing platinum black on both sides: Ultrafine powder of metallic platinum is called "platinum black" because it is black in color. It has an apparent density of 15.8 to 17.6 and a specific surface area of ​​40 to 60 m 2 / g, particle size: <10 nm. Platinum black powder and proton exchange resin solution L4 (weight ratio: about 10% platinum black powder, 10% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent number (meq / g) about 1100], 40% n-propanol, 40% water) were cast-coated onto a release film 1B with a thickness of about 150 μm, and then a thin microporous polytetrafluoroethylene reinforced membrane with a thickness of about 3 μm was coated and dried with a blower. After that, proton exchange resin solution L1 (weight ratio: about 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer] was coated onto the microporous polytetrafluoroethylene reinforced membrane. A proton exchange resin copolymer containing fluorine-containing proton exchange resin, its acid equivalent (meq / g) approximately 1000, 40% n-propanol, and 40% water was further applied to the microporous polytetrafluoroethylene-reinforced membrane, which was then coated with a thin, approximately 3 μm-thick membrane and dried with a blower. The microporous polytetrafluoroethylene-reinforced membrane was then coated with a proton exchange resin solution L2 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) approximately 950], 40% ethanol, and 40% water). The microporous polytetrafluoroethylene-reinforced membrane was then coated with a thin, approximately 3 μm-thick membrane and dried with a blower. The following steps were then repeated 10 times.The proton exchange resin solution L2 is further applied to the microporous polytetrafluoroethylene reinforced membrane, and a thin microporous polytetrafluoroethylene reinforced membrane with a thickness of about 3 μm is coated and dried with a blower. Then, the proton exchange resin solution L1 is further applied to the microporous polytetrafluoroethylene reinforced membrane, and a thin microporous polytetrafluoroethylene reinforced membrane with a thickness of about 3 μm is coated and dried with a blower. Finally, the proton exchange resin solution L4 containing platinum black is applied to the microporous polytetrafluoroethylene reinforced membrane. The mixture was further coated and dried with a fan, and finally heated to 130°C in an oven and baked for 10 minutes, then removed and cooled. The fluorine-containing proton exchange membrane containing platinum black on both sides could be smoothly peeled off from the release film 1B, with no visible residue on the release film. The peeled fluorine-containing proton exchange membrane containing platinum black on both sides was flat and had a thickness of approximately 87-90 μm, a density of approximately 2.2, a tensile strength in the TD and MD both greater than 50 MPa, a room temperature proton / ionic conductivity of greater than 0.08 (S / cm), and the time required for 100 ml of air to pass through this composite membrane was greater than 15 minutes, as measured using a Gurley air permeability meter. Example 11

[0127] (Release film 1A, 20-layer microporous reinforced film, both expanded polytetrafluoroethylene) Reinforced Chlor-Alkaline Battery Separator: Nanometal zirconium oxide powder was mixed with a perfluorocarboxylic acid resin solution to obtain LC6 (weight ratio: approximately 5% ZrO2 zirconia nanopowder, 15% [tetrafluoroethylene and CF2=CF-O-CF2CF2CF2-COOH fluorine-containing proton exchange resin copolymer, its acid equivalent number (meq / g) approximately 1000], 40% n-propanol, 40% water), cast-coated onto a release film 1A with a thickness of approximately 150 μm, and then coated with a thin microporous polytetrafluoroethylene reinforcement film with a thickness of approximately 3 μm. The film was then dried with a blower and then coated with a microporous polytetrafluoroethylene. A perfluorocarboxylic acid resin solution LC7 (weight ratio: about 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-COOH fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) about 950], 40% n-propanol, 40% water) was applied to a tetrafluoroethylene reinforced membrane, and a thin microporous polytetrafluoroethylene reinforced membrane with a thickness of about 3 μm was coated and dried with a blower. After that, the perfluorocarboxylic acid resin solution LC7 (weight ratio: about 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-COOH fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) about 950], 40% n-propanol, 40% water) was applied to the microporous polytetrafluoroethylene reinforced membrane. [Fluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-COOH fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) about 950], 40% ethanol, 40% water) was applied to a thin microporous polytetrafluoroethylene reinforced membrane about 3 μm thick, and dried with a fan. [Then, the same perfluorocarboxylic acid resin solution LC7 was further applied to the microporous polytetrafluoroethylene reinforced membrane, and another microporous polytetrafluoroethylene reinforced membrane about 3 μm thick was coated and dried with a fan. Repeated 13 times], [then coating the microporous polytetrafluoroethylene reinforced membrane with perfluorosulfonic acid resin solution L2, and then coating a thin microporous polytetrafluoroethylene reinforced membrane with a thickness of about 3 μm, and drying with a fan; this process is repeated 13 times], finally coating the microporous polytetrafluoroethylene reinforced membrane with nano-zirconia powder-containing perfluorosulfonic acid resin solution L5, drying with a fan, and finally heating it in an oven to 130 degrees, baking it for 10 minutes, then removing and cooling it, so that both sides contain zirconia and one side contains perfluorocarboxylic acid resin;A reinforced composite membrane is obtained, the other side of which contains a fluorine-containing sulfonic acid resin. This reinforced composite membrane can be smoothly peeled off from the release film 1A, with no visible residue on the release film. The peeled membrane, which contains zirconia on both sides, is flat and has a thickness of about 115 to 120 μm, a density of about 2.2, a tensile strength TD and MD both greater than 50 MPa, a room temperature proton / ion conductivity greater than 0.01 (S / cm), and the time required for 100 ml of air to pass through this composite membrane, as measured using a Gurley air permeability meter, is greater than 15 minutes. Example 12

[0128] (Release film 1B, 30-layer microporous reinforced film, both of which are stretched polytetrafluoroethylene films pre-filled with ceria CeO2) Reinforced proton exchange membrane: L3 (weight ratio: 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) about 1100], 40% n-propanol, 40% water) was cast-coated onto a release film 1B with a thickness of about 300 μm, and then a thin microporous polytetrafluoroethylene reinforced membrane with a thickness of about 3 μm [pre-filled weight ratio (ceria CeO2:polytetrafluoroethylene) about 10%] was coated, dried with a blower, and then A perfluorosulfonic acid resin solution L2 (weight ratio: approximately 20% [tetrafluoroethylene and CF2 = CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) approximately 950], 40% ethanol, 40% water) was applied to a microporous polytetrafluoroethylene reinforced membrane, and then a thin microporous polytetrafluoroethylene reinforced membrane (containing 10% ceria CeO2) with a thickness of approximately 3 μm was coated, dried with a blower, and then the microporous polytetrafluoroethylene The perfluorocarboxylic acid resin solution L2 was applied to the reinforced membrane, and then a thin microporous polytetrafluoroethylene reinforced membrane (containing 10% ceria CeO2) with a thickness of about 3 μm was coated, dried with a blower, [the same perfluorosulfonic acid resin solution L2 was then applied to the microporous polytetrafluoroethylene reinforced membrane, and then a microporous polytetrafluoroethylene reinforced membrane (containing 10% ceria CeO2) with a thickness of about 3 μm was coated, dried with a blower, and this process was repeated 27 times], and finally the microporous polytetrafluoroethylene reinforced membrane was coated with the perfluorocarboxylic acid resin solution L2. The fluorine-containing sulfonic acid resin solution L3 was applied, dried with a fan, and finally heated to 130 degrees in an oven and baked for 10 minutes, then removed and cooled. The ceria-containing fluorine-containing sulfonic acid resin reinforced membrane was peeled off smoothly from the release film 1B, with no visible residue on the release film. The peeled ceria-containing reinforced fluorine-containing proton exchange membrane was flat and had a thickness of approximately 175 to 180 μm, a density of approximately 2.2, a tensile strength TD and MD both >50 MPa, a room temperature proton / ionic conductivity >0.01 (S / cm), and the time required for 100 ml of air to pass through this composite membrane was >15 minutes, as measured by a Gurley air permeability meter. Example 13

[0129] (Release film 1A, 45-layer microporous reinforced film, both of which are expanded polytetrafluoroethylene films pre-filled with ceria CeO2) Reinforced proton exchange membrane: L5 (weight ratio: 5% zirconia ZrO2, 15% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent number (meq / g) approximately 1100], 40% n-propanol, 40% water) was cast coated onto a release film 1A of approximately 300 μm in thickness, and then coated onto a thin microporous polytetrafluoroethylene reinforced membrane of approximately 3 μm in thickness [pre-filled weight ratio (ceria CeO2:polytetrafluoroethylene) ~10%], dried with a blower, and then A perfluorosulfonic acid resin solution L2 (weight ratio: approximately 20% [tetrafluoroethylene and CF2 = CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) approximately 950], 40% ethanol, 40% water) was applied to a microporous polytetrafluoroethylene reinforced membrane, and a thin microporous polytetrafluoroethylene reinforced membrane (containing 10% ceria CeO2) with a thickness of approximately 3 μm was dried with a blower. After that, the perfluorosulfonic acid resin solution L2 was applied to the microporous polytetrafluoroethylene reinforced membrane. The perfluorosulfonic acid resin solution L2 was applied to a thin microporous polytetrafluoroethylene reinforced membrane (containing 10% ceria CeO2) having a thickness of about 3 μm, and dried with a blower. [Then, the same perfluorosulfonic acid resin solution L2 was applied to the microporous polytetrafluoroethylene reinforced membrane, and another microporous polytetrafluoroethylene reinforced membrane (containing 10% ceria CeO2) having a thickness of about 3 μm was applied to the microporous polytetrafluoroethylene reinforced membrane, and dried with a blower. This process was repeated 37 times.] Finally, the fluorine-containing sulfonic acid resin solution L5 was applied to the microporous polytetrafluoroethylene reinforced membrane. The mixture was coated, dried with a fan, and finally heated to 130°C in an oven and baked for 10 minutes. After that, it was removed and cooled, yielding a fluorine-containing sulfonic acid resin-reinforced membrane containing zirconia on both sides and ceria in the interior. This reinforced composite membrane could be peeled smoothly from the release film 1A, leaving no visible residue on the release film. The peeled ceria-reinforced fluorine-containing proton exchange membrane was flat and approximately 260-270 μm thick, had a density of approximately 2.2, a tensile strength in both TD and MD of >50 MPa, and a room-temperature proton / ionic conductivity of >0.The membrane has a permeability of 0.01 (S / cm), and the time required for 100 ml of air to pass through the composite membrane, as measured by a Gurley permeability meter, is >15 minutes. Example 14

[0130] (Release film 1B, 3-layer microporous reinforced film) Proton exchange resin solution L8 (weight ratio: approximately 10% platinum / carbon black, 10% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) approximately 1100], 40% n-propanol, 40% water) was cast-coated onto release film 1B with a thickness of approximately 150 μm, and then a thin microporous polytetrafluoroethylene reinforced membrane with a thickness of approximately 3 μm (containing 10% ceria CeO2) was coated and dried with a blower. Thereafter, proton exchange resin solution L2 was applied to the microporous polytetrafluoroethylene reinforced membrane, and then a thin microporous polytetrafluoroethylene reinforced membrane with a thickness of approximately 3 μm (containing 10% ceria CeO2) was coated and dried with a blower. Next, the microporous polytetrafluoroethylene reinforced membrane was coated with proton exchange resin solution L2, and then covered with a thin microporous polytetrafluoroethylene reinforced membrane (containing 10% ceria CeO2) with a thickness of approximately 3 μm. This was then dried with a fan. Next, the microporous polytetrafluoroethylene reinforced membrane was coated with proton exchange resin solution L8, and then dried with a fan. Finally, the membrane was heated to 120°C in an oven and baked for 5 minutes. After that, it was removed and cooled. The fluorine-containing proton exchange membrane was peeled smoothly from the release film 1B, and no visible residue remained on the release film. The peeled fluorine-containing proton exchange membrane electrode was approximately 28 μm thick. The membrane's tensile strengths (TD and MD) were both 80-90 MPa. The room-temperature proton / ionic conductivity (Ionic Conductivity) was greater than 0.012 (S / cm). The time required for 100 ml of air to pass through this composite membrane was greater than 15 minutes, as measured using a Gurley air permeability meter. It is suitable for use as a membrane electrode in a fuel cell. <Comparative Example 1>

[0131] (PET base film, no release agent, single layer micropore reinforced film) PET (CAS: 25038-59-9) base membranes were coated with proton exchange resin solution S1 (approximately 20% by weight [tetrafluoroethylene and CF₂=CF-O-CF₂CF₂-SO₃H fluorine-containing proton exchange resin copolymer, acid equivalent (meq / g) approximately 830], 40% ethanol, and 40% water) on a 25 μm-thick PET base membrane without any release agent. The resulting cast slurry was evenly distributed, and then coated onto an approximately 8-9 μm-thick microporous polytetrafluoroethylene-reinforced membrane. The same proton exchange resin solution was then applied to the microporous polytetrafluoroethylene-reinforced membrane, dried with a fan, and finally heated to 120°C in an oven for 5 minutes. After baking, the membrane was removed and cooled. The fluorine-containing proton exchange membrane could not be peeled from the PET base membrane, and even when immersed in water, it could not be peeled off smoothly. PET is the most common commercially available release film material, and the base film is also made from aromatic engineering plastics and does not contain any release agents. However, the PET base film is not suitable for producing fluorine-containing proton exchange membranes, whereas the release films proposed in the above examples of the present invention, such as 1A, 1B, and 1C, have excellent performance suitable for the application, which was an unexpected result. <Comparative Example 2>

[0132] (PET base film, no release agents, corona treated, single layer microporous reinforced film) PET base membrane (CAS: 25038-59-9) was corona-treated without any release agent. Proton exchange resin solution S1 (weight ratio: approximately 20% tetrafluoroethylene and CF₂=CF-O-CF₂CF₂-SO₃H fluorine-containing proton exchange resin copolymer, acid equivalent (meq / g) approximately 830, 40% ethanol, 40% water) was applied to the corona-treated PET base membrane, approximately 25 μm thick. The resulting cast slurry was evenly distributed, and then coated onto an approximately 8-9 μm thick microporous polytetrafluoroethylene-reinforced membrane. The microporous polytetrafluoroethylene-reinforced membrane was then dried with a fan. The same proton exchange resin solution was then applied to the same membrane, dried with a fan, and finally heated to 120°C in an oven for 5 minutes. After baking, the membrane was removed and cooled. The fluorine-containing proton exchange membrane could not be peeled from the corona-treated PET base membrane, and even when immersed in water, it could not be peeled off smoothly. PET is the most common commercially available release film material, and the base film is also made from aromatic engineering plastics and does not contain any release agents. However, the PET base film is not suitable for producing fluorine-containing proton exchange membranes, whereas the release films proposed in the above examples of the present invention, such as 1A, 1B, and 1C, have excellent performance suitable for the application, which was an unexpected result. <Comparative Example 3>

[0133] (PET release film contains silicone release agent, one layer of microporous reinforced film) Conventional release films have been prepared by corona treating PET (CAS: 25038-59-9) and adding a release agent, such as a silicon- or fluorine-containing release agent. A proton exchange resin solution S1 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) approximately 830], 40% ethanol, and 40% water) was applied to a PET release film containing a silicone release agent with a thickness of approximately 25 μm. The resulting cast slurry had poor flatness and internal agglomeration. The film was then coated with a microporous polytetrafluoroethylene reinforced membrane with a thickness of approximately 8 to 9 μm, dried with a blower, and then coated with a microporous polytetrafluoroethylene reinforced membrane. The same proton exchange resin solution was applied, dried with a fan, and finally heated to 120°C in an oven and baked for 5 minutes, then removed and cooled. The fluorine-containing proton exchange membrane could be smoothly peeled off from this (PET / silicone) release film, with no visible residue on the release film. The peeled fluorine-containing proton exchange membrane electrode had a thickness of approximately 10-18 μm and poor flatness. Infrared analysis revealed that silicon-containing contaminants remained on the membrane surface. This release film is also unsuitable for use in producing high-quality proton exchange membranes. <Comparative Example 4>

[0134] (PET release film contains a fluorine-containing release agent and is a single-layer microporous reinforced film) We used a PET release film with a fluorine-containing release agent on its surface. Proton exchange resin solution S1 (approximately 20% by weight [tetrafluoroethylene and CF₂=CF-O-CF₂CF₂-SO₃H fluorine-containing proton exchange resin copolymer, acid equivalent (meq / g) approximately 830], 40% ethanol, and 40% water) was applied to a 25 μm-thick PET release film. The resulting cast slurry was evenly distributed, and then coated onto a microporous polytetrafluoroethylene-reinforced membrane approximately 8–9 μm thick. The membrane was then dried with a fan. The same proton exchange resin solution was then applied to the microporous polytetrafluoroethylene-reinforced membrane, dried with a fan, and finally heated to 120°C in an oven for 5 minutes. After cooling, the fluorine-containing proton exchange membrane could not be peeled from the (PET / fluorine) release film; however, it could only be peeled by immersing in water. The fluorine-containing proton exchange membrane was approximately 13–16 μm thick and partially damaged on the surface. Such release films are also not suitable for application in the production of high-quality proton exchange membranes.

[0135] As is clear from the above examples and comparative examples, the release film not containing the special release agent used in the present invention is used for a special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane, a composite membrane electrode, or a fluorine-chlorine-containing alkaline battery membrane, and has superior performance to a composite membrane obtained from a release film containing a conventional release agent.

[0136] Those skilled in the art will recognize that various modifications and variations are possible based on the above-described technical forms and concepts, and it is intended that all of these modifications and variations be included within the scope of the claims of the present invention.

Claims

1. A special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane, comprising at least two micropore-reinforced membrane layers, each of which is filled with a fluorine-containing proton or ion exchange resin on both sides, the weight ratio of the micropore-reinforced membrane to the fluorine-containing proton or ion exchange resin being 5:95 to 40:60, the thickness of the composite membrane being 1 μm to 300 μm, the composite membrane having a tensile strength of >40 MPa in both directions, a room temperature ionic conductivity of >0.007 S / cm, and an extremely low air permeability, such that the time required for 100 ml of air to permeate the composite membrane is >5 minutes as measured using a Gurley air permeability meter.

2. The weight ratio of the microporous reinforced membrane to the fluorine-containing proton or ion exchange resin is 10:90 to 30:70, or the total weight of the composite membrane is 2 to 500 g / m ２ 2. The special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane according to claim 1,

3. A composite membrane electrode of a special highly reinforced fluorine-containing proton or ion exchange membrane used for a battery separator, comprising at least two layers of micropore-reinforced membrane, each of which is filled with a fluorine-containing proton or ion exchange resin on both sides, the weight ratio of the micropore-reinforced membrane to the fluorine-containing proton or ion exchange resin being 5:95 to 40:60, the weight ratio of the micropore-reinforced membrane to the fluorine-containing proton or ion exchange resin being 10:90 to 30:70, and the total weight of the composite membrane electrode of the special highly reinforced fluorine-containing proton or ion exchange membrane being 2 to 500 g / m ２ and a thickness of 1 μm to 300 μm, wherein the composite membrane electrode of the special highly reinforced fluorine-containing proton or ion exchange membrane has a tensile strength of >40 MPa in both directions, an ionic conductivity at room temperature of >0.007 S / cm, and an extremely low air permeability, such that the time required for 100 ml of air to permeate the composite membrane electrode as measured with a Gurley air permeability meter is >5 minutes.

4. The battery includes at least two microporous reinforced membranes, each of which is filled with a fluorine-containing proton exchange resin or ion exchange resin on both sides, and the weight ratio of the microporous reinforced membrane to the fluorine-containing proton exchange resin or ion exchange resin is 5:95 to 40:60, and the total weight of the highly reinforced fluorine-chlorine-containing alkaline battery membrane is 20 to 500 g / m ２ and a thickness of 10 μm to 260 μm, wherein the highly reinforced fluorine-chlorine-containing alkaline battery membrane has a tensile strength of >40 MPa in both directions, a room temperature ionic conductivity of >0.007 S / cm, and an air permeability of the highly reinforced fluorine-chlorine-containing alkaline battery membrane such that the time required for 100 ml of air to permeate the composite membrane as measured with a Gurley air permeability meter is >5 minutes.

5. 5. The special highly reinforced fluorine-chlorine-containing alkaline battery membrane according to claim 4, wherein the weight ratio of the microporous reinforced membrane to the fluorine-containing proton or ion exchange resin is 10:90 to 30:

70.

6. 6. The membrane or electrode according to claim 1, further comprising the special release film attached to the bottom layer of the composite film, wherein the component of the special release film is selected from engineering plastics containing bisphenol A as a main component and engineering plastics containing hexafluorodimethylbisphenol A as a main component, wherein the engineering plastic containing bisphenol A as a main component is a polymer obtained by polymerizing or copolymerizing bisphenol A and the weight ratio thereof is greater than 50%, and the engineering plastic containing hexafluorodimethylphenol A as a main component is a polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A and the weight ratio thereof is greater than 50%.

7. The membrane or electrode according to any one of claims 1 to 5, characterized in that the microporous reinforced membrane has 2 to 50 layers.

8. The membrane or electrode according to any one of claims 1 to 5, characterized in that the microporous reinforced membrane has 2 to 30 layers.

9. 7. The membrane or electrode according to claim 6, wherein the polymer obtained by polymerizing or copolymerizing bisphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, and a mixed copolymer thereof, and the polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, and a mixed copolymer thereof.

10. The dry weight of the microporous reinforced membrane is 0.5 to 30 g / m ２ and having both 40-95% thereof, a thickness of 0.5-30 μm, and a tensile strength greater than 40 MPa.

11. The membrane or electrode according to any one of claims 1 to 5, characterized in that the method for producing the micropore-reinforced membrane comprises a method of carrying out a spinning process such as melt spinning, wet spinning, wet phase change method, temperature difference phase change method, dry solvent method, electrostatic spinning, or ultra-high speed centrifugal spinning to uniformly converge nano- or micro-sized fibers into a random network micropore structure, which is then heat-set to form a microporous film, using a thermoplastic fluorine-containing or chlorine-containing resin, a carbon fiber precursor, or a resin that can be derived from carbon fiber, and extruding the microporous film into a paste form and biaxially stretching the extruded film.

12. 12. The membrane or electrode according to claim 11, wherein the solution of fluorine-containing proton exchange resin or ion exchange resin is mixed with one or more of metal nanopowder, metal oxide nanopowder, carbon powder, graphite powder, graphene, and rare metal powder, and the total weight thereof does not exceed 80% of the dry weight of the fluorine-containing proton exchange resin or ion exchange resin.

13. 13. The membrane or electrode of claim 12, wherein the metal nanopowder comprises one of silver, platinum or palladium, or a platinum / carbon composite, and the metal oxide powder comprises one of zirconia or ceria.

14. Step 1: Cast-coating a fluorine-containing proton exchange resin solution or a fluorine-containing ion exchange resin solution onto one side of a special release film and allowing it to blend in; Step 2: Coating a micropore reinforced membrane with the coated resin solution, and allowing the resin solution coated on the special release film and the coated micropore reinforced membrane to blend well together to obtain a composite membrane; Step 3: drying the composite membrane obtained in step 2; Step 4: further cast-coating a resin solution on the upper surface of the microporous reinforced membrane of the composite membrane, and allowing the cast-coated resin solution and the coated microporous reinforced membrane to fully blend together to obtain a composite membrane; Step 5: drying the composite membrane obtained in step 4; A method for producing the membrane or electrode according to any one of claims 1 to 5, comprising:

15. The method according to claim 14, characterized in that the resin solution is further coated on the microporous reinforced membrane of the composite membrane obtained in step 2, the resin solution is fully mixed with both the upper and lower surfaces of the microporous reinforced membrane and filled to form a composite membrane, and then all materials are dried together.

16. 16. The method according to claim 14 or 15, wherein the composite membrane obtained in step 4 is subjected to step 2+step 3+step 4 at least once.

17. The method according to any one of claims 14 to 16, wherein the void volume of the microporous reinforced membrane filled with the fluorine-containing proton exchange resin solution or the fluorine-containing ion exchange resin solution is at least 60% to 90%, preferably at least 80%.

18. The components of the special release film are selected from engineering plastics containing bisphenol A as a main component, or engineering plastics containing hexafluorodimethylbisphenol A as a main component, wherein the engineering plastics containing bisphenol A as a main component are polymers obtained by polymerizing or copolymerizing bisphenol A and the weight ratio thereof exceeds 50%, and the engineering plastics containing hexafluorodimethylphenol A as a main component are polymers obtained by polymerizing or copolymerizing hexafluorodimethylphenol A and the weight ratio thereof exceeds 50%.

19. The special release film not containing a release agent according to claim 18, characterized in that the polymer obtained by polymerizing or copolymerizing bisphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof, and the polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof.

20. The special release film containing no release agent according to claim 18, characterized in that the thickness of the special release film containing no release agent is 10 to 500 μm, preferably 25 to 300 μm, the width is at least 100 mm, and the film is heat resistant to 100°C without deformation.

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