Composite membranes of special highly reinforced fluorine-containing proton or ion exchange membranes, composite membrane electrodes, special highly reinforced fluorine-chlorine-containing alkaline battery membranes, special release membranes, and methods for producing the same

Abstract

The present invention discloses 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 a method for producing the same. The special high strength fluorine-containing proton or ion exchange membrane composite membrane comprises at least two layers of micropore reinforced membrane, each layer of micropore reinforced membrane is filled with fluorine-containing proton or ion exchange resin on both sides, the composite membrane has a tensile strength of >40MPa in both directions, a room temperature ionic conductivity of >0.007S / cm, and an extremely low air permeability, with the time required for 100ml of air to permeate the composite membrane being >5 minutes as measured by a Gurley air permeability meter.

Description

Technical Field

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

Background Art

[0002] As a highly efficient power generation device that directly converts fuel and chemical energy into electrical energy, the proton exchange membrane fuel cell (PEMFC) has attracted attention in various industries because it has higher energy conversion efficiency, is environmentally friendly, has advantages such as low-temperature startup and low noise compared to conventional batteries. Its core component is the proton exchange membrane arranged in the center of the fuel cell, which provides a channel for transporting protons generated at the cathode to the anode. The most commercially available proton exchange membranes are still the perfluorosulfonic acid Nafion series membranes (thickness > 25 μm) of DuPont in the United States, which were commercialized the earliest, and are mainly obtained by melt extrusion rolling and stretching. In recent years, the Gore-Select membrane series of W. L. Gore & Associates in the United States are ultra-thin (thickness < 25 μm) single-layer microporous PTFE reinforced membranes, mainly obtained by casting and coating a single-layer microporous PTFE reinforced membrane (see U.S. Patent Nos. US5547551A and US5599614A), and a small number of companies in China are imitating them.

[0003] The fluorine-containing sulfonic acid resin has a molecular structure consisting of a fluorocarbon main chain with a low polarizability of the main chain and hydrophilic sulfonic acid groups or carboxylic acid groups in the side chain that can adsorb water molecules, and a side chain having a sulfonic acid group at the end. Due to the strong difference in polarity between the hydrophobic main chain and the hydrophilic side chain, a microphase separation structure is formed inside the membrane, which plays an important role in its mechanical performance and transport performance. Therefore, the perfluorosulfonic acid resin membrane has basic properties such as excellent proton conductivity, low gas permeability, good mechanical performance and dimensional stability, and low contact resistance with the catalyst layer, meeting the usage conditions as a proton exchange membrane. There are many methods for manufacturing a proton exchange membrane from a sulfonic acid resin solution. For example, there are the casting method, the dipping method, the spraying method, etc. Currently, the manufacturing process of proton exchange membranes and various reinforced composite proton exchange membranes is complex and continuous production is difficult.

[0004] Patent CN101771159B (Patent No. ZL201010104002.7) discloses a method for manufacturing a proton exchange membrane in which sulfonated polyether ether ketone and sulfonated polyether sulfone are blended to form a membrane solution, this membrane solution is put into a mold, the solvent is evaporated to form a membrane, and then a proton exchange membrane is obtained through vacuum drying and acid treatment. The production of its product membrane is carried out in unit units, with low production efficiency and high costs.

[0005] Patent CN100513460 (Patent No. ZL200710011141.3) discloses a novel method for forming a proton exchange membrane using a single-layer stretched polytetrafluoroethylene microporous membrane as a base membrane. First, it is 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 complex manufacturing process, low efficiency, high production and use costs of fuel cells, and limits the commercialization of fuel cells.

[0006] Patent CN106968110B (ZL201710251603.2) discloses a fluorine-chlorine-containing conductive polymer double-sided filled composite membrane. However, in the film manufacturing method, a release paper is used, and it is easy to cause fluff contamination due to the release paper quality when producing high-quality films.

[0007] A release film is a film with a separable surface. After the release film and a specific material come into contact under limited conditions, it has no tackiness or has slight tackiness. Usually, in order to increase the release force of a plastic film, a surface modification treatment is carried out by corona or plasma treating the plastic film and then applying a release agent, or most commonly, by applying a silicone-containing release agent, a fluorine-containing release agent, etc. to the surface layer of the film material, so as to exhibit a very light and stable release force against various organic adhesives. Currently, the commonly seen one in the market is silicone release paper (film), all of which use silicone as the release agent, and the biggest drawback is that silicone may remain on the product surface during peeling.

[0008] The polycarbonate insulating release film is also a common type of release film. Its component is 2,2'-bis(4-hydroxyphenyl) propane polycarbonate, commonly known as polycarbonate, which is a polymer containing carbonate groups obtained by polycondensation of bisphenol A in the molecular chain. It is an amorphous, odorless, non-toxic, highly transparent colorless or slightly yellow thermoplastic engineering plastic, with excellent physical and mechanical properties, especially excellent impact resistance, high tensile strength, flexural strength, and compressive strength, small creep, and stable dimensions. Therefore, it is widely used in various fields. However, the polycarbonate insulating release film functions by adding other auxiliaries or applying a release agent.

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

[0010] Patent CN1840324A discloses a method for manufacturing a release film with complex processes, which requires the application of a release agent and is likely to cause contamination of the film surface during the casting process.

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

[0012] With the development of a low-carbon and clean economy, the requirements and applications for fluorine-containing proton exchange membranes or ion exchange membranes and their corresponding release films are increasing. Practically, the release film needs to have functions such as isolation, filling, protection, preventing the release agent from contaminating the casting paint, heat dissipation, etc. The requirements for the cleanliness, mechanical strength, and service life of the fluorine-containing proton exchange membrane or ion exchange membrane are becoming increasingly important.

Summary of the Invention

Problems to be Solved by the Invention

[0013] In view of the problems of the above prior art, the present invention is made. Its purpose is to solve the problems of the prior art that the manufacturing process of the exchange membrane is complex, contamination by the release agent is likely to occur, and continuous manufacturing is difficult, and to provide a composite membrane of a special high-reinforcement type fluorine-containing proton or ion exchange membrane, a composite membrane electrode, or a membrane for a special high-reinforcement type fluorine-chlorine-containing alkaline battery.

Means for Solving the Problems

[0014] To achieve the above technical problems, the present invention adopts the following technical forms.

[0015] <The First Form of the Present Invention> In the first embodiment of the present invention, there is provided a special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane including at least two layers of microporous reinforcing membranes, both sides of each layer of microporous reinforcing membrane being filled with a fluorine-containing proton or ion exchange resin, and the weight ratio of the microporous reinforcing 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, an extremely low air permeability, and the time required for 100 ml of air to permeate through the composite membrane measured by a Gurley air permeability meter is >5 minutes.

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

[0017] The microporous reinforcing membrane preferably has 2 to 50 layers.

[0018] The microporous reinforcing membrane preferably has 2 to 30 layers.

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

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

[0021] Preferably, the method for producing the microporous reinforcing membrane includes steps such as spinning by 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, uniformly converging nano- or micro-sized fibers to form a random network-like microporous structure, forming a microporous film after heat setting, and the resin used is a thermoplastic fluorine-containing or chlorine-containing resin, a carbon fiber precursor or a resin that can be induced into carbon fiber, and the method is to extrude the microporous film into a paste form and perform biaxial stretching.

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

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

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

[0025] <Second Form of the Present Invention> In the second form of the present invention, a special high-reinforcement type fluorine-containing proton or ion exchange membrane composite membrane for use in a battery separator is provided, which includes at least two layers of microporous reinforcing membranes, both sides of each layer of microporous reinforcing membranes are filled with fluorine-containing protons or ion exchange resins, and the weight ratio of the microporous reinforcing membrane to the fluorine-containing proton or ion exchange resin is 5:95 to 40:60. The weight ratio of the microporous reinforcing membrane to the fluorine-containing proton or ion exchange resin is 10:90 to 30:70, and the composite membrane electrode of the special high-reinforcement type fluorine-containing proton or ion exchange membrane has a total weight of 2 to 500 g / m 2 and a thickness of 1 μm to 300 μm. The composite membrane electrode of the special high-reinforcement type fluorine-containing proton or ion exchange membrane has a tensile strength of >40 MPa in both directions, a room temperature ionic conductivity of >0.007 S / cm, an extremely low air permeability, and the time required for 100 ml of air to permeate through the composite membrane electrode measured by a Gurley air permeability meter is >5 minutes.

[0026] Preferably, it includes a special release film attached to the lowermost layer of the composite membrane, and the component of the special release film is selected from engineering plastics containing bisphenol A as the main component or engineering plastics containing hexafluorodimethyl bisphenol A as the main component. However, the engineering plastic containing bisphenol A as the main component is a polymer obtained by polymerizing or copolymerizing bisphenol A, and its weight ratio exceeds 50%. The engineering plastic containing hexafluorodimethyl phenol A as the main component is a polymer obtained by polymerizing or copolymerizing hexafluorodimethyl phenol A, and its weight ratio exceeds 50%.

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

[0028] Preferably, the microporous reinforcing membrane is 2 to 50 layers.

[0029] Preferably, the microporous reinforcing film has 2 to 30 layers.

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

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

[0032] Preferably, the method for manufacturing the microporous reinforcing film includes steps such as spinning by 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, uniformly converging nano- or micro-sized fibers into a random network-like microporous structure, forming a microporous film after heat setting, and the resin used is a thermoplastic fluorine-containing or chlorine-containing resin, a carbon fiber precursor or a resin that can be induced into carbon fiber, and the method is to extrude the microporous film into a paste shape and perform biaxial stretching.

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

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

[0035] Preferably, the microporous reinforcing film has 2 to 20 layers.

[0036] <The third embodiment of the present invention> In the third embodiment of the present invention, there is provided a special highly reinforced fluorine-chlorine-containing alkaline battery membrane including at least two layers of microporous reinforcing films, both sides of each layer of microporous reinforcing film being filled with a fluorine-containing proton exchange resin or an ion exchange resin, and the weight ratio of the microporous reinforcing film to the fluorine-containing proton exchange resin or the ion exchange resin being 5:95 to 40:60. The total weight of the highly reinforced fluorine-chlorine-containing alkaline battery membrane is 20 to 500 g / m 2 and its thickness is 10 μm to 260 μm. The tensile strength of the highly reinforced fluorine-chlorine-containing alkaline battery membrane in both directions is > 40 MPa, the room temperature ionic conductivity of the highly reinforced fluorine-chlorine-containing alkaline battery membrane is > 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 measured with a Gurley air permeability meter is > 5 minutes.

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

[0038] Preferably, the microporous reinforcing film has 2 to 50 layers.

[0039] Preferably, the microporous reinforcing film has 2 to 30 layers.

[0040] Preferably, it further includes a special release film without a release agent, and the component of the special release film is selected from engineering plastics containing bisphenol A as the main component or engineering plastics containing hexafluorodimethyl bisphenol A as the main component. However, the engineering plastic containing bisphenol A as the main component is a polymer obtained by polymerizing or copolymerizing bisphenol A, and its weight ratio exceeds 50%. The engineering plastic containing hexafluorodimethylphenol A as the main component is a polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A, and its weight ratio exceeds 50%.

[0041] Preferably, the polymer obtained by polymerizing or copolymerizing bisphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, epoxy resin, or their mixed copolymer. The polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, epoxy resin, or their mixed copolymer.

[0042] Preferably, the microporous reinforcing film has a dry weight of 0.5~30g / m 2 and an open porosity of 40%~95%, a thickness of 0.5~30μm, and a tensile strength of >40MPa in both directions.

[0043] Preferably, the manufacturing method and material of the microporous reinforcing film are selected from the following.

[0044] (1) Perform processes such as spinning by 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 to uniformly converge nano or μm-sized fibers into a random network-like microporous structure, and form a microporous film after heat setting. The resin used is a thermoplastic fluorine-containing or chlorine-containing resin, a carbon fiber precursor or a resin that can be induced into carbon fiber.

[0045] (2) The stretched microporous polytetrafluoroethylene film, microporous polyolefin film, or modified polyolefin film obtained by extruding the microporous film into a paste form and biaxially stretching it.

[0046] Preferably, one or more of metal nanopowders, metal oxide nanopowders, carbon powders, graphite powders, graphene, and rare metal powders are mixed into the solution of the fluorine-containing proton exchange resin or ion exchange resin, and the total weight of them 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 - 1500. The selectable fluorine-containing proton exchange resin or ion exchange resin includes fluorine-containing sulfonic acid resin and fluorine-containing carboxylic acid resin, and the perfluorocarboxylic acid resin:perfluorosulfonic acid resin is filled in the special high-reinforcement type fluorine-chlorine-containing alkaline battery membrane at a dry weight ratio of 1:9 - 5:5.

[0048] <The fourth form of the present invention> In the fourth form of the present invention, a manufacturing method used for the composite membrane of the special high-reinforcement type fluorine-containing proton or ion exchange membrane described in the first form of the present invention, the composite membrane electrode described in the second form, or the fluorine-chlorine-containing alkaline battery membrane described in the third form is provided, including the following steps.

[0049] Step 1 Cast and coat the fluorine-containing proton exchange resin solution or fluorine-containing ion exchange resin solution on one side of the special release film to make it conform.

[0050] Step 2 Cover the coated resin solution with a microporous reinforcing membrane, and fully make the resin solution coated on the release film and the covered microporous reinforcing membrane conform to obtain a composite membrane.

[0051] Step 3 Dry the composite membrane obtained in Step 2.

[0052] Step 4: Further perform a cast coating of the resin solution on the upper surface of the microporous reinforcing membrane of the composite membrane, and thoroughly mix the cast-coated resin solution and the coated microporous reinforcing membrane to obtain a composite membrane.

[0053] Step 5: Dry the composite membrane obtained in Step 4.

[0054] Preferably, further perform a coating of the resin solution on the microporous reinforcing membrane of the composite membrane obtained in Step 2, thoroughly mix and fill the upper and lower surfaces of the microporous reinforcing membrane and the resin solution to form a composite membrane, and then dry all the materials together.

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

[0056] Preferably, the void volume of the microporous reinforcing 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 microporous reinforcing membrane to the fluorine-containing proton exchange resin or ion exchange resin is 5:95 - 40:60.

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

[0059] Preferably, the component of the special release film is selected from engineering plastics containing bisphenol A as a main component or engineering plastics containing hexafluorodimethyl bisphenol A as a main component, provided that the engineering plastics containing bisphenol A as a main component is a polymer obtained by polymerizing or copolymerizing bisphenol A, and its weight ratio exceeds 50%, and the engineering plastics containing hexafluorodimethyl phenol A as a main component is a polymer obtained by polymerizing or copolymerizing hexafluorodimethyl phenol A, and its weight ratio 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 their mixed copolymer, and the polymer obtained by polymerizing or copolymerizing hexafluorodimethyl phenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or their mixed copolymer.

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

[0062] <The fifth form of the present invention> In a fifth aspect of the present invention, there is provided a special release film without a release agent for manufacturing a battery separator by a cast coating method. The components of the special release film without a release agent are selected from engineering plastics containing bisphenol A as a main component or engineering plastics containing hexafluorodimethyl bisphenol A as a main component. However, the engineering plastic containing bisphenol A as a main component is a polymer obtained by polymerizing or copolymerizing bisphenol A, and its weight ratio exceeds 50%. The engineering plastic containing hexafluorodimethyl phenol A as a main component is a polymer obtained by polymerizing or copolymerizing hexafluorodimethyl phenol A, and its weight ratio exceeds 50%.

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

[0064] Preferably, the special release film without a release agent has a thickness of 10 to 500 μm, a width of at least 100 mm, and does not deform at 100 °C of heat resistance.

[0065] Preferably, the thickness of the special release film without the release agent in the previous stage is 25 to 300 μm.

[0066] In addition, the special release film without a release agent is used for manufacturing a battery separator by a cast coating method.

[0067] By adopting the above technical form, the composite membrane, composite membrane electrode and fluorine-chlorine-containing alkaline battery membrane of the special high-reinforcement type fluorine-containing proton or ion exchange membrane of the present invention are not likely to be contaminated by the release agent, can be heat-treated several times, and have a heat resistance of at least 100 °C. The multi-layer microporous reinforcing membrane can conceal the bubble defects that may occur from a single coating membrane, can greatly improve productivity, can greatly increase the tensile strength of the composite membrane, composite membrane electrode and fluorine-chlorine-containing alkaline battery membrane, improve the dimensional stability of the composite membrane, composite membrane electrode and fluorine-chlorine-containing alkaline battery membrane, is extremely important for the service life, enables high-speed continuous production, meets the requirements of commercial mass production, and the obtained product membrane has high cleanliness and stability.

[0068] The manufacturing method of the composite membrane, composite membrane electrode and fluorine-chlorine-containing alkaline battery membrane of the present invention has simple steps, can reduce production costs, and more importantly, avoids the problem that the release film contains a small amount of released release agent, and greatly improves the yield of the final product. The special release film without the release agent of the present invention can have a release function without corona treatment or coating of the release agent, can be used for continuous production, simplifies the production process, and can reduce the manufacturing cost.

[0069] <Embodiments for Carrying Out the Invention> The present invention will be further described below. It should be noted that this embodiment is based on the technical form of the present invention, shows detailed embodiments and specific operation procedures, but the protection scope of the present invention is not limited to this embodiment.

[0070] (1) The composite membrane, composite membrane electrode or fluorine-chlorine-containing alkaline battery membrane of the special high-reinforcement type fluorine-containing proton or ion exchange membrane includes at least two layers of microporous reinforcing membranes, and both sides of each layer of microporous reinforcing membrane (continuous phase) are filled with a fluorine-containing proton exchange resin or an ion exchange resin. (2) A special release film is attached to the lower surface of the composite membrane, composite membrane electrode or fluorine-chlorine-containing alkaline battery membrane of the special high-reinforcement type fluorine-containing proton or ion exchange membrane.

[0071] The fluorine-containing proton exchange resin or ion exchange resin may be, for example, a commercially available product of Nafion, 3M, or Solvay, or it can also be manufactured with reference to the manufacturing method of the fluorine-containing chlorine-containing conductive polymer resin disclosed in Patent CN106947027B (Patent No. ZL201710251598.5).

[0072] The reinforcing composite membrane, composite membrane electrode, or fluorine-chlorine-containing alkaline battery membrane includes at least two layers of microporous reinforcing membranes, and both sides of each layer of the microporous reinforcing membrane are filled with a fluorine-containing proton exchange resin or ion exchange resin. The overall manufacturing method includes the following steps.

[0073] <Method for manufacturing microporous reinforcing membrane> The process and materials for manufacturing the microporous reinforcing membrane can be selected from the following two groups.

[0074] (1) A method in which processes such as spinning are performed by melt spinning, wet spinning, wet phase change method, temperature difference phase change method, dry solvent method, electrospinning, and ultra-high-speed centrifugal spinning, and nano- or μm-sized fibers are uniformly converged to form a random network-like microporous structure, and a microporous film is formed after heat setting. The resins used are preferably thermally fusible fluorine-containing resins or chlorine-containing resins, carbon fiber precursors, or resins that can be induced into carbon fibers such as polyacrylonitrile (PAN) or its copolymers, polyimide, polyamide (nylon), polyester (PET), aramid, polyether ketone (PEEK), etc. (2) A microporous reinforcing membrane (for example, a stretched microporous polytetrafluoroethylene membrane, or a microporous polyolefin membrane (polyethylene, polypropylene, etc.), a modified polyolefin membrane) can be obtained by paste extrusion + biaxial stretching.

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

[0076] <Method for manufacturing a highly reinforced composite membrane, a composite membrane electrode, or a special highly reinforced fluorine-chlorine-containing alkaline battery membrane> Without including the release agent, a fluorine-containing proton exchange resin or an ion exchange resin solution may be cast-coated on a release film that can withstand drying at at least 100°C, and at least two layers of microporous reinforcing films may be coated. By means of multiple casting coatings or dipping methods, the fluorine-containing proton exchange resin solution or the ion exchange resin solution is filled into the pores on both sides of the microporous reinforcing film as completely as possible. Here, the fluorine-containing proton exchange resin or the ion exchange resin has an acid equivalent number (meq / g) of sulfonic acid or carboxylic acid of 400 - 1500, preferably 500 - 1100, more preferably 600 - 950. The composite material is dried to remove the solvent to manufacture a composite membrane, a composite membrane electrode, or a special highly reinforced fluorine-chlorine-containing alkaline battery membrane of a special highly reinforced fluorine-containing proton or ion exchange membrane.

[0077] The method for manufacturing the special reinforced fluorine-containing composite membrane or membrane electrode of the present invention includes the following steps.

[0078] Step 1 Cast-coat and let it conform a fluorine-containing proton exchange resin solution or a fluorine-containing ion exchange resin solution on one side of a release film that does not contain a special release agent.

[0079] Step 2 Coat the microporous reinforcing membrane with the coated resin solution, and thoroughly blend the resin solution coated on the release film and the coated microporous reinforcing membrane to obtain a composite membrane.

[0080] Step 3 Dry the composite membrane obtained in Step 2.

[0081] Step 4 Further cast and coat a resin solution on the upper surface of the microporous reinforcing membrane of the composite membrane, and dry it twice to obtain a finished product.

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

[0083] The manufacturing method of the special reinforcing fluorine-containing composite membrane or film electrode of the present invention has a simple process, can reduce production costs, and more importantly, avoids the problem that the release film contains a small amount of free release agent, and greatly improves the yield of the final product. More than 60%, preferably more than 80%, and most preferably more than 90% of the void volume on both sides of the microporous reinforcing membrane after drying is filled with a fluorine-containing proton exchange resin. The dry weight ratio of the microporous reinforcing 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 reinforcing fluorine-containing composite membrane is 3 to 60 g / m 2 and the thickness is 2 μm to 30 μm. The tensile strength (TD, MD) of the highly reinforcing composite membrane is >40 MPa in both directions, preferably >50 MPa, and most preferably >80 MPa. The room temperature ionic conductivity (Ionic Conductivity) of the reinforcing composite membrane is >0.007 (S / cm), preferably >0.013 (S / cm), more preferably >0.018 (S / cm). The air permeability of the reinforcing composite membrane is extremely low. The time required for 100 ml of air to pass through this composite membrane measured by a Gurley air permeability meter is >5 minutes, preferably >15 minutes.

[0084] Further, the microporous reinforcing membrane of the composite membrane obtained in Step 2 is further coated with the resin solution, and the upper and lower surfaces of the microporous reinforcing membrane and the resin solution are sufficiently mixed and filled to form a composite membrane, and then all the materials are dried together.

[0085] Alternatively, after Step 3, Step 2 is repeated to coat N layers of microporous reinforcing membranes. However, the number of microporous reinforcing membranes may be 2 to 50 layers, preferably a highly reinforced fluorine-containing composite membrane with 2 to 30 layers of microporous reinforcing membranes. However, the total dry weight ratio of the fluorine-containing proton exchange resin or ion exchange resin in the microporous reinforcing membrane is (5:95) to (40:60). The highly reinforced fluorine-containing composite membrane includes 2 to 50 layers of microporous reinforcing membranes, preferably 2 to 30 layers of microporous reinforcing membranes. Both surfaces of each layer of microporous reinforcing membrane are filled with a fluorine-containing proton exchange resin or ion exchange resin. 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 most preferably 10 to 250 g / m 2 and its thickness is 2 μm to 250 μm, preferably 3 μm to 150 μm, most preferably 5 μm to 130 μm. The tensile strength (TD, MD) of the highly reinforced fluorine-containing composite membrane is >40 MPa in both directions, preferably >50 MPa, most preferably >80 MPa. The room temperature ionic conductivity of the highly reinforced fluorine-containing composite membrane (Ionic Conductivity) >0.007 (S / cm), preferably >0.013 (S / cm), 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 pass through this composite membrane measured by a Gurley air permeability meter is >5 minutes, preferably >15 minutes.

[0086] The dry weight ratio of the microporous reinforcing 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. The fluorine-containing proton exchange resin or ion exchange resin includes, but is not limited to, selectable fluorine-containing sulfonic acid resins and fluorine-containing carboxylic acid resins. One or more of metal nano powders, metal oxide nano powders, carbon powders, graphite powders, graphene, and rare metal powders are mixed into the fluorine-containing proton exchange resin solution or fluorine-containing ion exchange resin solution, and the total weight thereof does not exceed 80% of the dry weight of the fluorine-containing proton exchange resin or ion exchange resin. The metal nano powder includes, but is not limited to, silver, platinum alloy or palladium, or a platinum / carbon composite. The metal oxide powder includes, but is not limited to, zirconia and ceria.

[0088] The advantage of the material of the present invention is that since such a release film does not contain any coating release agent, the risk of the release agent contaminating the product membrane electrode can be eliminated. By casting and coating the multi-layer microporous reinforcing film multiple times, the bubble defects that can be formed by a single-layer coating film can be hidden and significantly reduced, the yield can be significantly improved. Unexpectedly, the multi-layer microporous membrane composite film also contributes to the improvement of the tensile strength of the composite film, improves the dimensional stability of the composite film, which is extremely important for the service life, enables high-speed continuous production, meets the requirements of commercial mass production, and it has been discovered that the obtained product film has high cleanliness and stability.

[0089] <Composite film of special high-reinforcement type fluorine-containing proton or ion exchange membrane, composite membrane electrode, special high-reinforcement type fluorine-chlorine-containing alkaline battery membrane> The high-reinforcement composite film and composite membrane electrode of the present invention include at least two layers of microporous reinforcing films. Both sides of each layer of the microporous reinforcing film are filled with a fluorine-containing proton exchange resin or ion exchange resin. The weight ratio of the microporous reinforcing film 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 this reinforcing composite film 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 and its thickness is 1 μm to 300 μm, preferably 2 μm to 200 μm, most preferably 3 μm to 100 μm. The tensile strength (refer to ASTM D882 test method) (TD, MD) of the reinforced composite membrane and the composite membrane electrode is >40 MPa in both directions, preferably >50 MPa, 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 Test Method) of the reinforced composite membrane is >0.007 (S / cm), preferably >0.013 (S / cm), more preferably >0.018 (S / cm), and the air permeability of the reinforced composite membrane and the composite membrane electrode is extremely low. The time required for 100 ml of air measured by a Gurley air permeability meter to pass through this composite membrane and the composite membrane electrode is >5 minutes, preferably >15 minutes.

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

[0091] One or more of metal nano - powders, metal oxide nano - powders, carbon powders, graphite powders, graphene, rare metal powders, etc. may be mixed into the fluorine - containing proton exchange resin or ion exchange resin solution, and the mixture may be filled into the pores on both sides of the microporous membrane at once.

[0092] The total weight of the metal nano powder, metal oxide nano powder, 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 nano powder includes, but is not limited to, silver, platinum or palladium, or a platinum / carbon composite. The metal oxide powder includes, but is not limited to, zirconia and ceria.

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

[0094] In some embodiments of the present invention, the composite membrane electrode of the obtained special high-reinforcement fluorine-containing proton or ion exchange membrane includes at least two layers of microporous reinforcement membranes, and both sides of each layer of microporous reinforcement membrane are filled with fluorine-containing proton exchange resin or ion exchange resin. Preferably, there are 2 to 30 layers of microporous reinforcement membranes, and most preferably 2 to 15 layers of microporous reinforcement membranes. The total weight of the reinforcement 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 Its thickness (refer to 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 high-reinforcement composite membrane electrode is >40 MPa in both directions, preferably >50 MPa, and most preferably >80 MPa. The room-temperature ionic conductivity (Ionic Conductivity) of the high-reinforcement 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 high-reinforcement composite membrane is very low, and the time required for 100 ml of air to pass through the composite membrane measured by a Gurley air permeability meter is >5 minutes, preferably >15 minutes.

[0095] In other embodiments of the present invention, the special high-reinforcement fluorine-containing proton or ion exchange membrane composite membrane electrode includes at least two layers of microporous reinforcement membranes, preferably 2 to 45 layers of microporous reinforcement membranes, and most preferably 2 to 20 layers of microporous reinforcement membranes. Both sides of the microporous reinforcement membrane are filled with fluorine-containing proton exchange resin or ion exchange resin, and the weight ratio of the microporous reinforcement 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 this high-reinforcement composite membrane electrode is 70 to 500 g / m 2 and preferably 80 to 300 g / m 2 and most preferably 100 to 200 g / m 2and its thickness is 30 μm to 300 μm, preferably 50 μm to 200 μm, 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, most preferably > 80 MPa. The room temperature ionic conductivity of the highly reinforced composite membrane electrode (Ionic Conductivity) > 0.007 (S / cm), preferably > 0.013 (S / cm), 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 measured by a Gurley air permeability meter to permeate through this composite membrane > 5 minutes, preferably > 15 minutes.

[0096] In another embodiment of the present invention, the special reinforced fluorine-chlorine-containing alkaline battery membrane includes three layers of microporous reinforced membranes, and both sides of each layer of microporous reinforced membrane are filled with a fluorine-containing proton exchange resin or an 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). 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 , most preferably 5 to 200 g / m 2 and the thickness of the microporous reinforced membrane is 1 μm to 300 μm, preferably 2 μm to 200 μm, most preferably 3 μm to 100 μm. The tensile strength (refer to ASTM D882 test method) (TD, MD) of the highly reinforced fluorine-chlorine-containing membrane is > 40 MPa in both directions, preferably > 50 MPa, most preferably > 80 MPa. The room temperature proton / ion conductivity of the reinforced composite membrane (Ionic Conductivity, GB / T20042.3 - 2009 Proton Exchange Membrane Fuel Cells - Part 3: Measurement Methods for Proton Exchange Membranes) > 0.007 (S / cm), preferably > 0.013 (S / cm), more preferably > 0.018 (S / cm). And the air permeability of the reinforced composite membrane is extremely low, and the time required for 100 ml of air measured by a Gurley air permeability meter to permeate through the composite membrane > 5 minutes, preferably > 15 minutes.

[0097] In yet another embodiment of the present invention, the special high-reinforcement fluorine-chlorine-containing alkaline battery membrane comprises 3 to 30 layers of microporous reinforcement membranes, and both sides of each layer of microporous reinforcement membrane are filled with a fluorine-containing proton exchange resin or an ion exchange resin. The high-reinforcement fluorine-chlorine-containing alkaline battery composite membrane has one entire surface coated with a perfluorocarboxylic acid resin and the other entire surface coated with a perfluorosulfonic acid resin. The total weight ratio of the microporous reinforcement 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 high-reinforcement chlorine alkaline battery composite membrane is 20 to 450 g / m 2 , preferably 50 to 300 g / m 2 , most preferably 100 to 250 g / m 2 . Its thickness is 10 μm to 230 μm, preferably 25 μm to 150 μm, most preferably 50 μm to 130 μm. The tensile strength (TD, MD) of the high-reinforcement fluorine-chlorine-containing alkaline battery composite membrane is >40 MPa in both directions, preferably >50 MPa, most preferably >80 MPa. The room-temperature ionic conductivity (Ionic Conductivity) of the high-reinforcement fluorine-chlorine-containing alkaline battery composite membrane is >0.007 (S / cm), preferably >0.013 (S / cm), more preferably >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 through the composite membrane measured by a Gurley air permeability meter is >5 minutes, preferably >15 minutes.

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

[0099] The special high-reinforcement fluorine-chlorine-containing alkaline battery membrane of the present invention is not likely to be contaminated by a release agent, can be heat-treated multiple times, and has a heat resistance of at least 100 °C. The multi-layer microporous reinforcement membrane can conceal the bubble defects that may occur from a single coating membrane, can significantly improve productivity, and also contributes to the improvement of the tensile strength of the special high-strength fluorine-chlorine-containing alkaline battery membrane, improves the dimensional stability of the special high-strength fluorine-chlorine-containing alkaline battery membrane, is extremely important for the service life, enables high-speed continuous production, meets the requirements of commercial mass production, and the obtained product membrane has high cleanliness and stability.

[0100] <Release film without release agent> One of the objectives of the present invention is to eliminate the deficiencies of the conventional production process. Since the conventional release film contains a trace amount of free release agent, especially a silicon-containing release agent, it is easily adsorbed by the cast coating material and contaminates the final product, making it difficult to clean, which is extremely disadvantageous in producing a high-quality and highly clean proton exchange membrane. The present invention provides a release film without a release agent (that is, the film itself has a release function physically and does not require corona or application of a release agent), can be used for continuous production, and a fluorine-containing proton exchange resin solution or an ion exchange resin solution can be applied to such a release film without a release agent by the casting method, and it will not deform even when dried at least at 100 °C, and a high-quality fluorine-containing proton exchange membrane or a fluorine-containing ion exchange membrane can be manufactured. Moreover, by one or more cast coatings, such a modified film without a release agent can be applied to the surface, and a microporous reinforcement membrane can be further coated on the coating solution. By drying and repeatedly processing the applied fluorine-containing sulfonic acid or carboxylic acid resin solution, the mass production of the fluorine-containing proton exchange membrane can be made more convenient and the production cost can be further reduced.

[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, has a width of at least 100 mm, can withstand heat of at least 100 °C without deformation, preferably can withstand heat of 120 °C without deformation, can be used for manufacturing a fluorine-containing proton exchange membrane, a fluorine-containing ion exchange membrane, etc., and can be applied to a battery separator. The manufacturing process of the battery separator uses a fluorine-containing proton exchange resin solution or a fluorine-containing ion exchange resin solution with excellent film-forming properties, cast-coats such a release film, dries it to form a film and shape it, and winds it onto a roll.

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

[0103] The membrane surface does not contain any additional coating release agent, does not require corona treatment, can cast the coating film one or more times, and can improve the strength of the composite membrane by coating the microporous reinforcing membrane during the casting process. It has been discovered that a proton exchange membrane or an ion exchange membrane that is unexpectedly easy to peel off after drying and casting and has no residual solvent or release agent contamination can be formed. The advantage of the material of the present invention is that since such a release film does not contain a coated release agent, there is no risk of the release agent contaminating the product film. By casting and coating a multi-layer microporous reinforcing membrane multiple times, the bubble defects that may occur from a single coating film can be hidden and significantly reduced, the productivity can be greatly improved, continuous production can be realized, the requirements of commercial mass production can be met, the cleanliness and stability of the obtained product film are high, and the waste recovery is convenient.

[0104] When manufacturing a battery separator by the casting coating method using a special release film without a release agent, the manufacturing process is as follows: 1. Apply a fluorine-containing proton exchange resin solution or a fluorine-containing ion exchange resin solution to one side of the special release film to make it adhere, then cover the applied resin solution with a microporous reinforcing membrane, and fully make the resin solution applied to the special release film and the covered microporous reinforcing membrane adhere, and then dry it. 2. Perform a second casting coating of the resin solution on the composite membrane (placed on the special engineering plastic film) obtained in step 1 on the covered first layer of the microporous reinforcing membrane, then cover the second cast-coated resin solution with a second layer of the microporous reinforcing membrane, and fully make the resin solution applied to the special release film and the covered microporous reinforcing membrane adhere, and then dry. After drying, the void volume on both sides of each layer of the microporous reinforcing membrane is filled with a fluorine-containing proton exchange resin by more than 60%, preferably more than 80%, and most preferably more than 90%. 3. Repeat step 2 at least 0 to 48 times, preferably 0 to 28 times, and finally apply a resin solution to the layer of the covered ultra-microporous reinforcing membrane and further dry it, so as to obtain a high-reinforcement type proton exchange membrane, ion exchange membrane or membrane electrode having at least 2 layers (2 to 50 layers, preferably 2 to 30 layers) of microporous reinforcing membranes.

Example 1

[0105] (Release film without release agent) (1A) The carbonate resin obtained by polycondensing bisphenol A (without adding any auxiliaries or release agents) is melt-extruded and biaxially stretched to obtain transparent films with thicknesses of about 300 μm, 150 μm, and 25 μm (used as it is without corona treatment).

[0106] (1B) The polycarbonate resin obtained by polycondensing hexafluorodimethylphenol A (without adding any auxiliaries or release agents) is melt-extruded and biaxially stretched to obtain transparent films with thicknesses of about 300 μm, 150 μm, and 25 μm (used as it is without corona treatment).

[0107] (1C) A release film with the above thickness is manufactured, but polyphenylene ether-p-bisphenol A type epoxy resin (EHPPO type, without adding any auxiliaries or release agents and used as it is without corona treatment) is used. The resin manufacturing process is hyperbranched polyphenylene e JPEG0007697636000001.jpg5170 Teng, Li Xiaoyu, Wang Haiqiao, Key Laboratory of Carbon Fiber and Functional Polymers of the Ministry of Education, College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, Abstract: Reactive terminal epoxy hyperbranched polyphenylene ether (EHPPO) was manufactured, added to bisphenol A type epoxy resin for modification, and cured with an acid anhydride curing agent. The thermal, mechanical, and dielectric properties of the cured samples were characterized. Also, a comparative modification study was carried out using hyperbranched polyphenylene ether (CHPPO) with the same molecular main chain structure and non-reactive benzyl group as the terminal group. From these results, two different modifiers have respective advantages in the modification effect of bisphenol A type epoxy resin. The epoxy resin modified with EHPPO is superior in thermal performance and tensile strength, and the epoxy resin modified with CHPPO has a lower dielectric constant. The films obtained as described in the above (1A) to (1C) have a high release effect and no residue even without corona treatment or application of a release agent.

Example 2

[0108] (Formulation of Proton Exchange Resin Solution, Ion Exchange Resin Solution, or Mixture) S1 (by weight: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 830%], 40% ethanol, 40% water).

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

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

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

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

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

[0114] L5 (by weight: about 5% ZrO2 zirconia nano powder, about 15% [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).

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

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

[0117] L8 (by weight: about 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) about 1100], 40% n-propanol, 40% water).

Example 3

[0118] (For comparison) (Release film 1A, a microporous reinforcing film with a thickness of 10 μm for one layer)

[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 number (meq / g) about 830], 40% ethanol, 40% water) was applied to a release film 1A with a thickness of about 25 μm, and then coated with a microporous polytetrafluoroethylene reinforcing film with a thickness of about 10 μm, dried with a blower, and then the same proton exchange resin solution was further applied to the microporous polytetrafluoroethylene reinforcing film and dried with a blower. Finally, it was heated to 120 degrees in an oven, baked for 5 minutes, taken out and cooled. The fluorine-containing proton exchange membrane could be smoothly peeled off from the release film 1A, there was no residue visible on the release film, the thickness of the peeled fluorine-containing proton exchange membrane was flat and about 16 - 18 μm, the density was about 2.20, the acid equivalent number (meq / g) of the composite membrane was about 1000, the tensile strength TD and MD were both 40 - 50 MPa, the proton / ionic conductivity at room temperature (Ionic Conductivity) > 0.012 (S / cm), and the time required for 100 ml of air to permeate through this composite membrane measured by a Gurley permeameter was > 15 minutes.

Example 4

[0120] (Release film 1A, two layers of microporous reinforcing film with a thickness of 5 μm) 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 number (meq / g) about 830%, 40% ethanol, 40% water]) was applied to a release film 1A with a thickness of about 25 μm, and then covered with a thin microporous polytetrafluoroethylene reinforcing film (continuous phase) with a thickness of about 5 μm, dried with a blower, and then the same proton exchange resin solution was further applied to the microporous polytetrafluoroethylene reinforcing film, and then covered with the same thin microporous polytetrafluoroethylene reinforcing film (continuous phase) with a thickness of about 5 μm, dried with a blower, and then the same proton exchange resin solution was also applied to the microporous polytetrafluoroethylene reinforcing film, and also dried with a blower. Finally, it was heated to 120 degrees in an oven, baked for 5 minutes, taken out and cooled. The fluorine-containing proton exchange membrane could be smoothly peeled off from the release film 1A, there was no residue visible on the release film, the thickness of the peeled fluorine-containing proton exchange membrane was flat and about 16 - 18 μm, the density was about 2.19, the acid equivalent number (meq / g) of the composite membrane was about 1020, the tensile strength TD and MD were both 60 - 70 MPa. Unexpectedly, it had better tensile strength than when using the single-layer microporous reinforcing film with a thickness of 10 μm in Example 3, the proton / ionic conductivity at room temperature (Ionic Conductivity) > 0.012 (S / cm), and it was found that the time required for 100 ml of air to pass through this composite membrane measured by a Gurley air permeability meter > 15 minutes.

Example 5

[0121] (Release film 1A, three layers of microporous reinforcing film with a thickness of 3 μm) 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 number (meq / g) about 830], 40% ethanol, 40% water) is applied to a release film 1A with a thickness of about 25 μm, and then covered with a thinner microporous polytetrafluoroethylene reinforcing film (continuous phase) with a thickness of about 3 μm, dried with a blower, and then the same proton exchange resin solution is further applied to the microporous polytetrafluoroethylene reinforcing film, and covered with a thinner microporous polytetrafluoroethylene reinforcing film (continuous phase) with a thickness of about ~3 μm, dried with a blower, and then the same proton exchange resin solution is further applied to the microporous polytetrafluoroethylene reinforcing film, and covered with a thinner microporous polytetrafluoroethylene reinforcing film (continuous phase) with a thickness of about ~3 μm, dried with a blower, and then the same proton exchange resin solution is further applied to the microporous polytetrafluoroethylene reinforcing film and dried with a blower. Finally, it is heated to 120 degrees in an oven, baked for 5 minutes, taken out and cooled. The fluorine-containing proton exchange membrane can be smoothly peeled off from the release film 1A, there is no visual residue on the release film, the thickness of the peeled fluorine-containing proton exchange membrane is flat and about 16 - 18 μm, the density is about 2.18, the acid equivalent number (meq / g) of the composite membrane is about 1040, the tensile strength TD and MD are both 80 - 90 MPa. Unexpectedly, its strength is superior to that when using the single-layer microporous reinforcing film with a thickness of 10 μm in Example 3, the room-temperature proton / ionic conductivity (Ionic Conductivity) > 0.012 (S / cm), and it is found that the time required for 100 ml of air to pass through this composite membrane measured by a Gurley permeameter > 15 minutes.

Example 6

[0122] (Release film 1B, two layers of microporous reinforcing films) 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 number (meq / g) is about 790], 40% ethanol, 40% water) is applied to a release film 1B with a thickness of about 25 μm, and then covered with a thinner microporous polytetrafluoroethylene reinforcing film (continuous phase) with a thickness of about ~2 μm, dried with a blower, and then the same proton exchange resin solution is also applied to the microporous polytetrafluoroethylene reinforcing film, and then covered with a thinner microporous polytetrafluoroethylene reinforcing film (continuous phase) with a thickness of about ~2 μm, dried with a blower, and then the same proton exchange resin solution is further applied to the microporous polytetrafluoroethylene reinforcing film, dried with a blower, and finally heated in an oven to 120 degrees, baked for 5 minutes, taken out and cooled. The fluorine-containing proton exchange membrane can be smoothly peeled off from the release film 1B, there is no visual residue on the release film, the thickness of the peeled fluorine-containing proton exchange membrane is flat and about 8 - 9 μm, the density is about 2.20, the acid equivalent number (meq / g) of the composite membrane is about 1010, the tensile strength TD and MD are both >100 MPa, the proton / ionic conductivity at room temperature (Ionic Conductivity) >0.013 (S / cm), and the time required for 100 ml of air to pass through this composite membrane measured by a Gurley permeameter >15 minutes.

Example 7

[0123] (Release film 1C, two layers of microporous reinforcing films) 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 number (meq / g) about 830], 40% ethanol, 40% water) was applied to a release film 1C with a thickness of about 25 μm, and then covered with a thinner microporous polytetrafluoroethylene reinforcing film (continuous phase) with a thickness of about ~1 μm, dried with a blower, and then the same proton exchange resin solution was applied to the microporous polytetrafluoroethylene reinforcing film, and then covered with a thin microporous polytetrafluoroethylene reinforcing film (continuous phase) with a thickness of about ~1 μm, dried with a blower, and then the same proton exchange resin solution was further applied to the microporous polytetrafluoroethylene reinforcing film and dried with a blower. Finally, it was heated to 120 degrees in an oven, baked for 5 minutes, taken out and cooled. The fluorine-containing proton exchange membrane could be smoothly peeled off from the release film 1C, there was no residue visible on the release film, the thickness of the peeled fluorine-containing proton exchange membrane was flat and about 5 - 6 μm, the density was about 2.20, the acid equivalent number (meq / g) of the composite membrane was about 990, the tensile strength TD and MD were both >120 MPa, the room temperature proton / ionic conductivity (Ionic Conductivity) >0.015 (S / cm), and the time required for 100 ml of air to pass through this composite membrane measured by a Gurley air permeability meter >15 minutes.

Example 8

[0124] (Release film 1A, 5 layers of microporous reinforcing film, 2 layers of polytetrafluoroethylene on the front and back, 3 layers of polypropylene in the middle) Proton exchange resin solution S1 (weight ratio: about 20% tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, acid equivalent (meq / g) about 830, containing 40% ethanol and 40% water) was cast-coated on a release film 1A with a thickness of about 150 μm, and then coated with a thin microporous polytetrafluoroethylene reinforcing film with a thickness of about ~3 μm, dried with a blower, and then the same proton exchange resin solution was applied to the microporous polytetrafluoroethylene reinforcing film again, and then coated with a thin microporous polypropylene reinforcing film with a thickness of about ~4 μm, dried with a blower, and then the same proton exchange resin solution was further applied to the microporous polypropylene reinforcing film, and then coated with a thin microporous polypropylene reinforcing film with a thickness of about ~4 μm, dried with a blower, and then the same proton exchange resin solution was applied to the microporous polypropylene reinforcing film again, and then coated with a thin microporous polypropylene reinforcing film with a thickness of about ~4 μm, dried with a blower, and then the same proton exchange resin solution was applied to the microporous polypropylene reinforcing film again, and then coated with a thin microporous polytetrafluoroethylene reinforcing film with a thickness of about ~3 μm, dried with a blower, and then the same proton exchange resin solution was applied to the microporous polytetrafluoroethylene reinforcing film again, dried with a blower again, and finally heated in an oven to 120 degrees, baked for 5 minutes, taken out and cooled. The fluorine-containing proton exchange membrane can be smoothly peeled off from the release film 1A, there is no residue visible on the release film, the thickness of the peeled fluorine-containing proton exchange membrane is flat and about 28 - 30 μm, the density is about 2.1, the acid equivalent number (meq / g) of the composite membrane is about 1050, the tensile strength TD and MD are both >70 MPa, the proton / ionic conductivity at room temperature (Ionic Conductivity) >0.011 (S / cm), and the time required for 100 ml of air to pass through this composite membrane measured by a Gurley air permeability meter >15 minutes.

Example 9

[0125] (Release film 1A, 10 layers of microporous reinforcing film, 2 layers of polytetrafluoroethylene on the front and back, 8 layers of polyacrylonitrile PAN in the middle) The 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 number (meq / g) about 1000], containing 40% n-propanol and 40% water) was cast-coated on a release film 1A with a thickness of about 150 μm, and then coated with a microporous polytetrafluoroethylene reinforcing film with a thickness of about 3 μm, and dried with a blower. Then, the proton exchange resin solution L2 (weight ratio: about 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent number (meq / g) about 950], containing 40% ethanol and 40% water) was applied to the microporous polytetrafluoroethylene reinforcing film, and then coated with a thin polyacrylonitrile PAN reinforcing film with a thickness of about 3 - 4 μm, and dried with a blower. Then, the same proton exchange resin solution L2 was applied to the microporous polyacrylonitrile PAN reinforcing film, and then coated with a thin polyacrylonitrile PAN reinforcing film with a thickness of about 3 - 4 μm, and dried with a blower. Then, the same proton exchange resin solution L2 was applied to the microporous polyacrylonitrile PAN reinforcing film, and then coated with a thin polyacrylonitrile PAN reinforcing film with a thickness of about 3 - 4 μm, and dried with a blower. Then, the same proton exchange resin solution L2 was applied to the microporous polyacrylonitrile PAN reinforcing film, and then coated with a thin polyacrylonitrile PAN reinforcing film with a thickness of about 3 - 4 μm, and dried with a blower. Then, the same proton exchange resin solution L2 was applied to the microporous polyacrylonitrile PAN reinforcing film, and then coated with a thin polyacrylonitrile PAN reinforcing film with a thickness of about 3 - 4 μm, and dried with a blower. Then, the same proton exchange resin solution L2 was applied to the microporous polyacrylonitrile PAN reinforcing film, and then coated with a thin polyacrylonitrile PAN reinforcing film with a thickness of about 3 - 4 μm, and dried with a blower. Then, the same proton exchange resin solution L2 was applied to the microporous polyacrylonitrile PAN reinforcing film, and then coated with a thin polyacrylonitrile PAN reinforcing film with a thickness of about 3 - 4 μm, and dried with a blower. Then, the same proton exchange resin solution L2 was applied to the microporous polyacrylonitrile PAN reinforcing film, and then coated with a thin polyacrylonitrile PAN reinforcing film with a thickness of about 3 - 4 μm, and dried with a blower. Then, the same proton exchange resin solution L2 was applied to the microporous polyacrylonitrile PAN reinforcing film, and then coated with a thin polyacrylonitrile PAN reinforcing film with a thickness of about 3 - 4 μm, and dried with a blower. Then, the same proton exchange resin solution L2 was applied to the microporous polyacrylonitrile PAN reinforcing film, and then coated with a thin polyacrylonitrile PAN reinforcing film with a thickness of about 3 - 4 μm, and dried with a blower. Then, the same proton exchange resin solution L2 was applied to the microporous polyacrylonitrile PAN reinforcing film, and then coated with a thin polyacrylonitrile PAN reinforcing film with a thickness of about 3 - 4 μm, and dried with a blower. Then,The same proton exchange resin solution L2 was applied to the microporous polyacrylonitrile PAN reinforcing membrane, and then coated with a thin polytetrafluoroethylene reinforcing membrane with a thickness of about 3 μm, dried with a blower, and finally heated to 130 °C in an oven, baked for 10 minutes, taken out and cooled. The fluorine-containing proton exchange membrane can be smoothly peeled off from the release film 1A, there is no visual residue on the release film, the thickness of the peeled fluorine-containing proton exchange membrane is flat and about 58 - 60 μm, the density is about 2.1, the acid equivalent number (meq / g) of the composite membrane is about 1050, the tensile strength TD and MD are both > 50 MPa, the proton / ionic conductivity at room temperature (Ionic Conductivity) > 0.01 (S / cm), and the time required for 100 ml of air to pass through this composite membrane measured with a Gurley permeameter > 15 minutes.

Example 10

[0126] (Release film 1B, 15 layers of microporous reinforcing membranes, both are stretched polytetrafluoroethylene) Proton exchange membrane electrode containing platinum black on both sides: The extremely fine powder of metallic platinum is black, so it is called "platinum black", the apparent density is 15.8 - 17.6, and the specific surface area is 40 - 60 m 2 / g, particle size: <10 nm. Platinum black powder and proton exchange resin solution 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) are cast-coated on a release film 1B with a thickness of approximately 150 μm, and then covered with a thin microporous polytetrafluoroethylene reinforcing film with a thickness of approximately ~3 μm, dried with a blower, and then proton exchange resin solution 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) is further applied to the microporous polytetrafluoroethylene reinforcing film, and then covered with a thin microporous polytetrafluoroethylene reinforcing film with a thickness of approximately ~3 μm, dried with a blower, and then 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 number (meq / g) approximately 950], 40% ethanol, 40% water) is further applied to the microporous polytetrafluoroethylene reinforcing film, and then covered with a thin microporous polytetrafluoroethylene reinforcing film with a thickness of approximately ~3 μm, dried with a blower, [then the following steps are 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 further applied to the microporous polytetrafluoroethylene reinforced membrane and dried with a blower. Finally, it is heated to 130 degrees in an oven, baked for 10 minutes, taken out and cooled. The fluorine-containing proton exchange membrane containing platinum black on both sides can be smoothly peeled off from the release film 1B, there is no residue visible on the release film, and the thickness of the peeled fluorine-containing proton exchange membrane containing platinum black on both sides is flat and about 87 - 90 μm, the density is about 2.2, the tensile strength TD and MD are both >50 MPa, the room temperature proton / ionic conductivity (Ionic Conductivity) >0.08 (S / cm), and the time required for 100 ml of air to pass through this composite membrane measured with a Gurley air permeability meter >15 minutes.

Example 11

[0127] (Release film 1A, 20 layers of microporous reinforcing membranes, both are stretched polytetrafluoroethylene) Reinforced chlor-alkali battery separator: Mix nano metal zirconium oxide powder into a perfluorocarboxylic acid resin solution to obtain LC6 (by weight: about 5% ZrO2 zirconia nano powder, 15% [tetrafluoroethylene and CF2=CF-O-CF2CF2CF2-COOH fluorine-containing proton exchange resin copolymer, its acid equivalent number (meq / g) is about 1000], 40% n-propanol, 40% water). Cast and coat it on a release film 1A with a thickness of about 150 μm, and then coat it with a thin microporous polytetrafluoroethylene reinforcing film with a thickness of about ~3 μm, and dry it with a blower. Then, apply a perfluorocarboxylic acid resin solution LC7 (by weight: about 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-COOH fluorine-containing proton exchange resin copolymer, its acid equivalent number (meq / g) is about 950], 40% n-propanol, 40% water) on the microporous polytetrafluoroethylene reinforcing film, and coat it with a thin microporous polytetrafluoroethylene reinforcing film with a thickness of about ~3 μm, and dry it with a blower. Then, apply a perfluorocarboxylic acid resin solution LC7 (by weight: about 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-COOH fluorine-containing proton exchange resin copolymer, its acid equivalent number (meq / g) is about 950], 40% ethanol, 40% water) on the microporous polytetrafluoroethylene reinforcing film, and coat it with a thin microporous polytetrafluoroethylene reinforcing film with a thickness of about ~3 μm, and dry it with a blower. [Then, repeat the process of applying the same perfluorocarboxylic acid resin solution LC7 on the microporous polytetrafluoroethylene reinforcing film and coating it with a microporous polytetrafluoroethylene reinforcing film with a thickness of about ~3 μm and drying it with a blower 3 times], [Then, repeat the process of applying a perfluorosulfonic acid resin solution L2 on the microporous polytetrafluoroethylene reinforcing film and coating it with a thin microporous polytetrafluoroethylene reinforcing film with a thickness of about ~3 μm and drying it with a blower 13 times]. Finally, apply a perfluorosulfonic acid resin solution L5 containing nano zirconia powder on the microporous polytetrafluoroethylene reinforcing film, dry it with a blower, and finally heat it to 130 degrees in an oven, bake it for 10 minutes, then take it out and cool it. Both sides contain zirconia, one side contains perfluorocarboxylic acid resin,On the other hand, a reinforced composite membrane containing a fluorine-containing sulfonic acid resin is obtained, and this reinforced composite membrane can be smoothly peeled off from the release film 1A, with no residues visible on the release film. The thickness of the fluorine-chlorine-containing alkaline battery membrane containing zirconia on both peeled surfaces is flat and about 115 - 120 μm, the density is about 2.2, the tensile strength TD and MD are both > 50 MPa, the proton / ion conductivity (Ionic Conductivity) at room temperature > 0.01 (S / cm), and the time required for 100 ml of air to pass through this composite membrane measured with a Gurley permeameter > 15 minutes.

Example 12

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

Example 13

[0129] (Release film 1A, 45-layer microporous reinforcing film, both pre-filled with ceria CeO2 in stretched polytetrafluoroethylene film) Reinforced proton exchange membrane: L5 (containing 5% zirconia ZrO2, 15% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 1100], 40% n-propanol, and 40% water) was cast-coated on a release film 1A with a thickness of approximately 300 μm, and then a thin microporous polytetrafluoroethylene reinforcing film with a thickness of approximately ~3 μm [pre-filled with a weight ratio (ceria CeO2: polytetrafluoroethylene) of ~10%] was dried with a blower. After that, a perfluorosulfonic acid resin solution L2 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 950], 40% ethanol, and 40% water) was applied to the microporous polytetrafluoroethylene reinforcing film, and then a thin microporous polytetrafluoroethylene reinforcing film with a thickness of approximately ~3 μm (containing 10% ceria CeO2) was dried with a blower. After that, a perfluorocarboxylic acid resin solution L2 was applied to the microporous polytetrafluoroethylene reinforcing film, and a thin microporous polytetrafluoroethylene reinforcing film with a thickness of approximately ~3 μm (containing 10% ceria CeO2) was coated and dried with a blower. [After that, the process of applying the same perfluorosulfonic acid resin solution L2 to the microporous polytetrafluoroethylene reinforcing film and coating a microporous polytetrafluoroethylene reinforcing film with a thickness of approximately ~3 μm (containing 10% ceria CeO2) and drying it with a blower was repeated 37 times], finally, a fluorine-containing sulfonic acid resin solution L5 was applied to the microporous polytetrafluoroethylene reinforcing film and dried with a blower. Finally, it was heated to 130 degrees in an oven, baked for 10 minutes, taken out and cooled to obtain a fluorine-containing sulfonic acid resin reinforcing film containing zirconia on both sides and ceria inside. This reinforcing composite film could be smoothly peeled off from the release film 1A, and there was no visible residue on the release film. The thickness of the peeled reinforcing fluorine-containing proton exchange membrane containing ceria was flat and approximately 260 - 270 μm, the density was approximately 2.2, and the tensile strength TD and MD were both >50 MPa, and the room temperature proton / ionic conductivity (Ionic Conductivity) >0.It is 01 (S / cm), and the time required for 100 ml of air measured with a Gurley air permeability meter to pass through this composite membrane is > 15 minutes.

Example 14

[0130] (Release film 1B, three-layer microporous reinforcing film) Proton exchange resin solution L8 (weight ratio: about 10% platinum / carbon black, 10% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) is about 1100], 40% n-propanol, 40% water) was cast-coated on a release film 1B with a thickness of about 150 μm, and then a thin microporous polytetrafluoroethylene reinforcing film (containing 10% ceria CeO2) with a thickness of about ~3 μm was coated, dried with a blower, and then proton exchange resin solution L2 was applied to the microporous polytetrafluoroethylene reinforcing film, and then a thin microporous polytetrafluoroethylene reinforcing film (containing 10% ceria CeO2) with a thickness of about ~3 μm was coated, dried with a blower, and then proton exchange resin solution L2 was applied to the microporous polytetrafluoroethylene reinforcing film, and then a thin microporous polytetrafluoroethylene reinforcing film (containing 10% ceria CeO2) with a thickness of about ~3 μm was coated, dried with a blower, and then proton exchange resin solution L8 was applied to the microporous polytetrafluoroethylene reinforcing film, and dried with a blower, and finally heated to 120 degrees in an oven, baked for 5 minutes, taken out and cooled, and the fluorine-containing proton exchange membrane can be smoothly peeled off from the release film 1B, there is no residue visible on the release film, the thickness of the peeled fluorine-containing proton exchange membrane electrode is about ~28 μm, the tensile strength TD and MD of the membrane are both 80 - 90 MPa, the room temperature proton / ionic conductivity (Ionic Conductivity) > 0.012 (S / cm), and the time required for 100 ml of air measured with a Gurley air permeability meter to pass through this composite membrane is > 15 minutes. It is suitable for the membrane electrode application of fuel cells. <Comparative Example 1>

[0131] (PET original film, containing no release agent at all, one-layer microporous reinforcing film) The PET (CAS: 25038-59-9) original film does not contain any release agent on its surface. The proton exchange resin solution S1 (weight ratio: about 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of about 830], 40% ethanol, 40% water) is applied to a PET original film without a release agent and having a thickness of about 25 μm. A microporous polytetrafluoroethylene reinforcing film with good flatness of the cast slurry and a thickness of about 8 - 9 μm is coated, dried with a blower, and then the same proton exchange resin solution is applied to the microporous polytetrafluoroethylene reinforcing film and dried with a blower. Finally, it is heated to 120 degrees in an oven, baked for 5 minutes, taken out and cooled. The fluorine-containing proton exchange membrane cannot be peeled off from the PET original film and cannot be smoothly peeled off even when immersed in water. PET is the most common commercially available release film material and is also an original film made from aromatic engineering plastics without any release agent, but the PET original film is not suitable for making a fluorine-containing proton exchange membrane. In contrast, the release films proposed in the above examples of the present invention, such as 1A, 1B, 1C, have excellent performance suitable for application, which is an unexpected result. <Comparative Example 2>

[0132] (PET original film, without any release agent, corona-treated, one layer of microporous reinforcing film) The PET base film (CAS: 25038-59-9) contains no release agent on its surface but has been corona-treated. A proton exchange resin solution S1 (weight ratio: about 20% tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of about 830, containing 40% ethanol and 40% water) was applied to the corona-treated PET base film with a thickness of about 25 μm. The cast slurry had good flatness and was coated with a microporous polytetrafluoroethylene reinforcing film with a thickness of about 8 - 9 μm, then dried with a blower. After that, the same proton exchange resin solution was applied to the microporous polytetrafluoroethylene reinforcing film and dried with a blower. Finally, it was heated to 120 degrees in an oven, baked for 5 minutes, taken out and cooled. The fluorine-containing proton exchange membrane could not be peeled off from the corona-treated PET base film and could not be smoothly peeled off even when immersed in water. PET is the most common commercially available release film material and is also a base film made from aromatic engineering plastics, containing no release agent at all. However, the PET base film is not suitable for making fluorine-containing proton exchange membranes. In contrast, the release films proposed in the above examples of the present invention, such as 1A, 1B, and 1C, have excellent performance suitable for application, which is an unexpected result. <Comparative Example 3>

[0133] (The PET release film contains a silicone release agent and has one layer of microporous reinforcing film) As conventional release films, those obtained by subjecting PET (CAS: 25038-59-9) to corona treatment and adding a release agent, for example, silicon-containing or fluorine-containing release agents have been widely used. 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 number (meq / g) about 830], 40% ethanol, 40% water) was applied to a silicone release agent-containing PET release film with a thickness of about 25 μm. The flatness of the cast slurry was poor, there was an internal aggregation phenomenon, and a microporous polytetrafluoroethylene reinforcing film with a thickness of about 8 - 9 μm was coated, dried with a blower, then the same proton exchange resin solution was applied to the microporous polytetrafluoroethylene reinforcing film and dried with a blower. Finally, it was heated to 120 degrees in an oven, baked for 5 minutes, taken out and cooled. The fluorine-containing proton exchange membrane could be smoothly peeled off from this (PET / silicone) release film, and there was no visual residue on the release film. The thickness of the peeled fluorine-containing proton exchange membrane electrode was about 10 - 18 μm, and the flatness was poor. According to infrared IR analysis, silicon-containing contaminants remained on the film surface. Such a release film is not suitable for application in the production of high-quality proton exchange membranes. <Comparative Example 4>

[0134] (The PET release film contains a fluorine-containing release agent and one layer of microporous reinforcing film) A PET release film having a fluorine-containing release agent on its surface was adopted. A proton exchange resin solution S1 (weight ratio: about 20 [tetrafluoroethylene and a fluorine-containing proton exchange resin copolymer of CF2=CF-O-CF2CF2-SO3H, with an acid equivalent (meq / g) of about 830], 40% ethanol, 40% water) was applied to a fluorine release agent-containing PET release film with a thickness of about 25 μm. The cast slurry had good flatness, and was then coated with a microporous polytetrafluoroethylene reinforcing film with a thickness of about 8 - 9 μm, and dried with a blower. After that, the same proton exchange resin solution was applied to the microporous polytetrafluoroethylene reinforcing film and dried with a blower. Finally, it was heated to 120 degrees in an oven, baked for 5 minutes, taken out and cooled. The fluorine-containing proton exchange membrane could not be peeled off from the (PET / fluorine) release film, and could only be peeled off after being immersed in water. The thickness of the fluorine-containing proton exchange membrane was about 13 - 16 μm, and the surface was partially damaged. Such a release film is not suitable for application in the production of high-quality proton exchange membranes either.

[0135] As is clear from the above examples and comparative examples, the release film without the special release agent used in the present invention is used for a composite membrane of a special high-reinforcement type fluorine-containing proton or ion exchange membrane, a composite membrane electrode or a fluorine-chlorine-containing alkaline battery membrane, and has better performance than the composite membrane obtained from the conventional release film containing a release agent.

[0136] Those skilled in the art can make various changes and modifications based on the above technical forms and ideas, and all of these changes and modifications are intended to be included in the scope of the claims of the present invention.

Claims

1. A composite membrane of a special highly reinforced fluorine-containing proton or ion exchange membrane that is substantially free of contamination by a release agent (hereinafter referred to as "the composite membrane"), The composite membrane comprises at least two microporous reinforced membrane layers, Both sides of the microporous reinforcement membrane of each layer are filled with a fluorine-containing proton or ion exchange resin, and the weight ratio of the microporous reinforcement membrane to the fluorine-containing proton or ion exchange resin is 5:95 to 40:60; The thickness of the composite membrane is 1 μm to 300 μm; The composite membrane has a tensile strength in both the MD and TD directions exceeding 40 MPa, and a room temperature ionic conductivity exceeding 0.007 S / cm; The air permeability is so low that the time required for 100 ml of air to permeate through the composite membrane exceeds 5 minutes as measured by a Gurley air permeability meter; The composite film further includes a special release film attached to the bottom layer thereof, the special release film being made of an engineering plastic that does not contain a release agent; And the engineering plastic is Engineering plastics containing bisphenol A as a main component, or and an engineering plastic containing hexafluorodimethylbisphenol A as a main component. The engineering plastic containing bisphenol A as a main component is a polymer obtained by polymerizing or copolymerizing bisphenol A, and the weight ratio of the polymer exceeds 50%, and the engineering plastic containing hexafluorodimethyl bisphenol A as a main component is a polymer obtained by polymerizing or copolymerizing hexafluorodimethyl bisphenol A, and the weight ratio of the polymer exceeds 50%. The composite membrane is characterized by:

2. In the composite membrane according to Claim 1, the weight ratio of the microporous reinforcing membrane to the fluorine-containing proton or ion exchange resin is 10:90 to 30:70, or the total amount of the composite membrane is 2 to 500 g / m ２ The composite membrane characterized by this.

3. A composite membrane electrode using the composite membrane according to claim 1 or 2 as a battery separator, The total weight of the composite membrane electrode is 2 to 500 g / m ２ , its thickness is 1 μm to 300 μm, the tensile strength in both the MD direction and the TD direction exceeds 40 MPa in both directions, the room temperature ionic conductivity exceeds 0.007 S / cm, the air permeability is extremely low, and the time required for 100 ml of air measured by a Gurley air permeability meter to permeate through this composite membrane electrode exceeds 5 minutes A composite membrane electrode comprising:

4. 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, 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 there is substantially no contamination by release agents; The total weight is 20 to 500 g / m ２ and its thickness is 10 μm to 260 μm, The tensile strength in the MD direction and the TD direction exceeds 40 MPa, and the room temperature ionic conductivity of the special highly reinforced fluorine-chlorine-containing alkaline battery membrane exceeds 0.007 S / cm; The time required for 100 ml of air to pass through, as measured by a Gurley air permeability meter, exceeds 5 minutes. The present invention further includes a special release film attached to the bottom layer of the micropore-reinforced film, the special release film being made of an engineering plastic that does not contain a release agent; And the engineering plastic is Engineering plastics containing bisphenol A as a main component, or and an engineering plastic containing hexafluorodimethylbisphenol A as a main component. The engineering plastic containing bisphenol A as a main component is a polymer obtained by polymerizing or copolymerizing bisphenol A, and the weight ratio of the polymer exceeds 50%, and the engineering plastic containing hexafluorodimethyl bisphenol A as a main component is a polymer obtained by polymerizing or copolymerizing hexafluorodimethyl bisphenol A, and the weight ratio of the polymer exceeds 50%. A membrane for a special highly reinforced fluorine-chlorine containing alkaline battery.

5. The alkaline battery membrane according to claim 4, wherein the weight ratio of the micropore-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 any one of claims 1-2, wherein the micropore-reinforced membrane comprises 2-50 layers, or the electrode according to claim 3, or the membrane for an alkaline battery according to claims 4-5.

7. 6. The membrane or electrode according to any one of claims 1-2, wherein the micropore-reinforced membrane comprises 2-30 layers, or the electrode according to claim 3, or the membrane for an alkaline battery according to claims 4-5.

8. The composite membrane according to claim 1, 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 hexafluorodimethylbisphenol A is any one of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof. The membrane or electrode according to claim 4.

9. The dry weight of the microporous reinforcing film is 0.5 to 30 g / m ２ wherein the open pore ratio of the microporous reinforcing film is 40 to 95%, the thickness is 0.5 to 30 μm, and the tensile strength is greater than 40 MPa, and the composite film according to claims 1 to 2, or the electrode according to claim 3, or the film for an alkaline battery according to claims 4 to 5. The film or electrode according to any one of the above. **Claim 10**: A method for manufacturing a microporous reinforcing film according to any one of the composite films of claims 1 to 2, the electrodes of claim 3, or the films for alkaline batteries of claims 4 to 5, comprising: spinning by melt spinning, wet spinning, wet phase inversion method, temperature difference phase inversion method, dry solvent method, electrospinning method or ultra-high speed centrifugal spinning method to uniformly converge nano or micro-sized fibers to form a random network-like microporous structure, and obtaining a microporous film after heat setting; and extruding the microporous film into a paste form and biaxially stretching it. A method for manufacturing a microporous reinforcing film, characterized by comprising the above steps. **Claim 11**: In the method for manufacturing a microporous reinforcing film according to claim 10, a step of mixing one or more of metal nano powder, metal oxide powder, carbon powder, graphite powder, graphene, and rare metal powder in a solution of a fluorine-containing proton exchange resin or an ion exchange resin, and performing the mixing under the condition that the total weight thereof does not exceed 80% of the dry weight of the fluorine-containing proton exchange resin or the ion exchange resin. **Claim 12**: In the method according to claim 11, the metal nano powder includes one of silver, platinum or palladium, or a platinum / carbon composite material, and the metal oxide powder includes one of zirconia or ceria. **Claim 13** Step 1: Casting and coating a fluorine-containing proton exchange resin solution or a fluorine-containing ion exchange resin solution on one side of a special release film to make it conform; Step 2: Coating the coated resin solution with a microporous reinforcing film, and sufficiently conforming the resin solution coated on the special release film and the coated microporous reinforcing film to obtain a composite film; Step 3: Drying the composite film obtained in Step 2; Step 4: Further performing casting and coating of a resin solution on the upper surface of the microporous reinforcing film of the composite film, and sufficiently conforming the cast and coated resin solution and the coated microporous reinforcing film to obtain a composite film; Step 5: Drying the composite film obtained in Step 4. A manufacturing method according to any one of the composite films of claims 1 to 2, the electrodes of claim 3, or the films for alkaline batteries of claims 4 to 5, characterized by comprising the above steps. **Claim 14** The method according to claim 13, further comprising coating the resin solution on the microporous reinforcing film of the composite film obtained in the step 2, allowing the upper and lower surfaces of the microporous reinforcing film to be fully compatible with the resin solution and filling them to form a composite film, and further drying all the materials together at once.

15. The method according to claim 13 or 14, characterized in that the step 2, step 3, and step 4 are repeated at least once on the composite film obtained in step 4.

16. The method according to any one of claims 13 to 15, characterized in that the void volume filled with the fluorine-containing proton exchange resin solution or the fluorine-containing ion exchange resin solution in the microporous reinforcing film is at least 60% to 90%.

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