Isolation film and its use

Abstract

The present application provides an isolation film, which is formed by hydrolyzing a resin film, the resin film comprising: a non-hydrolyzable organic polymer; and a hydrolyzable organic polymer, which is hydrolyzable after being treated by at least one of an acid aqueous solution, an alkali aqueous solution and pure water, and the content of the hydrolyzable organic polymer is 10-70 parts by weight per 100 parts by weight of the resin film. The isolation film of the present application has good ion conduction and is extremely suitable for use in various batteries.

Description

Technical Field

[0001] This invention relates to a separating membrane and its application, and more particularly to an ion-conducting separating membrane and its application. Background Technology

[0002] Internationally common energy storage devices include hydrogen fuel cells, vanadium redox flow batteries, and lithium-ion batteries. Energy storage systems are one of the key factors for the success of renewable energy development because they have regulation functions, backup capacity, and instantaneous power supply capabilities. They can mitigate the impact of instantaneous changes in the power supply system on the power grid and have become an indispensable and important part.

[0003] Each energy storage method has its own advantages and disadvantages, and the separator plays an important role in the battery. As the market demands higher battery safety and performance, the separator is required to have high ion conductivity, prevent electrons from passing through the positive and negative electrodes, and prevent leakage caused by solid, liquid or gas passage, which would reduce the capacity. It is also required to prevent safety issues such as cracking, leakage, gas leakage or combustion. Summary of the Invention

[0004] In view of the above problems, the object of the present invention is to provide a separator with high ion conductivity.

[0005] To achieve the above objectives, the present invention provides a separating membrane formed by hydrolyzing a resin membrane, the resin membrane comprising:

[0006] Non-hydrolyzable organic polymers; and

[0007] Hydrolyzable organic polymers are those that can be hydrolyzed after treatment with at least one of acidic aqueous solutions, alkaline aqueous solutions, and pure water;

[0008] The content of the hydrolyzable organic polymer is 10 to 70 parts by weight relative to 100 parts by weight of the resin film.

[0009] More preferably, the non-hydrolyzable organic polymer comprises polybenzimidazole, polybenzoxazole, polybenzothiazole, polyetherketone, polyphenylene ether, polyethersulfone, polysulfone, polyphenylene sulfide, polypropylene, polyethylene, polystyrene, or any combination thereof. More preferably, the non-hydrolyzable organic polymer has hydrophilic functional groups on its side chains. Particularly preferably, the hydrophilic functional groups comprise sulfonic acid groups, phosphate groups, carboxylic acid groups, amide groups, or hydroxyl groups.

[0010] More preferably, the hydrolyzable organic polymer has repeating units as shown in formula (1):

[0011]

[0012] Wherein, X1 is a tetravalent group containing at least one aromatic or alicyclic group; Y1 is a divalent group containing at least one aromatic or alicyclic group, and at least one of X1 and Y1 contains at least one functional group selected from ester bond, amide bond, sulfonic acid group, phosphate group, carboxylic acid group, amide group, hydroxyl group and nitro group.

[0013] More preferably, X1 is a tetravalent group selected from formulas (2), (3), (4), (5), or (6):

[0014]

[0015] In this context, R1 independently represents -H, -F, -CF3, -SO3H, -PO3H2, -COOH, -OH, and straight-chain or branched alkyl or phenyl groups with 1 to 6 carbon atoms; R2 independently represents straight-chain or branched hydrocarbon groups with 2 to 36 carbon atoms or cyclic hydrocarbon groups with 3 to 20 carbon atoms; R3 independently represents straight-chain or branched hydrocarbon groups with 1 to 6 carbon atoms; and L1 independently represents -O-, -S-, -SO2-, single bond, -NH-, -C(=O)-, -CH=CH-, -C≡C-, -CH2-, -(CH2)2-, -C(CH3)2-, -C(CF3)2-, -C(=O)O-, -OC(=O)-, -C(=O)NH-, or -NH. C(=O)-; n is any integer from 0 to 5, each representing an independent integer; m is any integer from 1 to 5.

[0016] More preferably, Y1 is a divalent group represented by formula (7), formula (8), or formula (9):

[0017]

[0018] Where L2 can be independently represented as -O-, -S-, -SO2-, single bond, -NH-, -C(=O)-, -CH=CH-, -C≡C-, -CH2-, -(CH2)2-, -C(CH3)2-, -C(CF3)2-, -C(=O)O-, -OC(=O)-, -C(=O)NH-, or -NH C(=O)-; R4 is a straight-chain or branched hydrocarbon group or phenyl group with 1 to 6 carbon atoms, which can be independently represented by -H, -F, -CF3, -SO3H, -PO3H2, -COOH, -OH; R5 is a straight-chain or branched hydrocarbon group or phenyl group with 1 to 6 carbon atoms, which can be independently represented by -H, -F, -CF3, -SO3H, -PO3H2, -COOH, -OH; R6 and R7 are straight-chain or branched hydrocarbon groups with 1 to 9 carbon atoms; n represents any integer from 0 to 5.

[0019] Preferably, the ionic conductivity of this separator is increased by more than 10% compared to a separator that has not undergone hydrolysis.

[0020] Preferably, the elongation at break of the separator is greater than 10%.

[0021] More preferably, the separator has a thickness of 0.1 micrometers to 100 micrometers.

[0022] More preferably, the resin film further comprises a filler material, the content of which is greater than 0 parts by weight and not more than 60 parts by weight relative to 100 parts by weight of the resin film. More preferably, the filler material is selected from flame retardants, hydrophilic materials composed of acidic and alkaline substances, ceramic oxides, lithium salts, organic acids, ionic liquids, or any combination thereof.

[0023] More preferably, the resin film is formed from a composition comprising: the non-hydrolyzable organic polymer; the hydrolyzable organic polymer; and, if necessary, an organic solvent.

[0024] The present invention also provides a composite membrane comprising: the above-mentioned separator membrane.

[0025] The present invention further provides a battery comprising:

[0026] Anode layer;

[0027] Cathode layer; and

[0028] The aforementioned isolation membrane is disposed between the anode layer and the cathode layer.

[0029] Preferably, the battery comprises a fuel cell, a flow battery, or a lithium battery.

[0030] The present invention, through the design of the hydrolyzable polymer and its dosage, enables the separator of the present invention to have high ionic conductivity and low swelling, and can effectively prevent vanadium ions in the electrolyte of flow batteries and hydrogen gas in fuel cells from passing through. Therefore, it has low vanadium ion permeability and low hydrogen permeability, which helps to improve the safety of batteries when applied to batteries. Attached Figure Description

[0031] Figure 1 This is the FTIR image of the separator membrane before hydrolysis in Example 1 of the present invention.

[0032] Figure 2 This is the FTIR image of the isolation membrane (i.e., after hydrolysis) in Embodiment 1 of the present invention.

[0033] Figure 3 This is the FTIR image of the separator membrane before hydrolysis in Example 9 of the present invention.

[0034] Figure 4This is the FTIR image of the isolation membrane (i.e., after hydrolysis) in Example 9 of the present invention. Detailed Implementation

[0035] The separator provided by this invention is different from the known separators, and it has high ion conductivity, low swelling and volume stability, high mechanical properties, low vanadium ion permeability, and low hydrogen permeability.

[0036] In this invention, the separator is formed by hydrolyzing a resin membrane, which comprises: a non-hydrolyzable organic polymer; and a hydrolyzable organic polymer that can be hydrolyzed after treatment with at least one (e.g., two or three) of an acidic aqueous solution, an alkaline aqueous solution, and pure water; wherein, relative to 100 parts by weight of the resin membrane, the content of the hydrolyzable organic polymer is 10 to 70 parts by weight (more preferably 20 to 70 parts by weight, more preferably 30 to 70 parts by weight, and particularly preferably 40 to 70 parts by weight).

[0037] This non-hydrolyzable organic polymer possesses non-hydrolyzable covalent bonds, such as imidazole bonds, oxazole bonds, carbon-carbon bonds, sulfone bonds, biphenyl groups, fluorine groups, ketone groups, and ether groups. Therefore, even when subjected to hydrolysis, its structure remains unaffected. This non-hydrolyzable organic polymer includes, but is not limited to, polybenzimidazole (PBI), polybenzoxazole (PBO), polybenzothiazole (PBT), polyetherketone (PEEK), polyphenylene ether (PPO), polyethersulfone (PES), polysulfone, polyphenylene sulfide (PPS), polypropylene (PP), polyethylene (PE), and polystyrene (PS). This non-hydrolyzable organic polymer can be used alone or in combination with two or more (e.g., three or four types).

[0038] In this invention, the non-hydrolyzable organic polymer preferably has hydrophilic functional groups on its side chains, which facilitates the hydrolysis reaction of the hydrolyzable polymer of this invention. The hydrophilic functional groups are preferably sulfonic acid groups, phosphate groups, carboxylic acid groups, amide groups, or hydroxyl groups.

[0039] In this invention, the content of the non-hydrolyzable organic polymer relative to 100 parts by weight of the resin film can be from 30 parts by weight to 90 parts by weight (more preferably from 30 parts by weight to 80 parts by weight, more preferably from 30 parts by weight to 70 parts by weight, and particularly preferably from 30 parts by weight to 60 parts by weight).

[0040] In this invention, the hydrolyzable organic polymer is preferably a repeating unit as shown in formula (1):

[0041]

[0042] In formula (1), X1 is a tetravalent group containing at least one aromatic or alicyclic group; Y1 is a divalent group containing at least one aromatic or alicyclic group, and at least one of X1 and Y1 contains at least one functional group selected from ester bond, amide bond, sulfonic acid group, phosphate group, carboxylic acid group, amide group, hydroxyl group, and nitro group. For example, X1 contains at least one functional group selected from ester bond, amide bond, sulfonic acid group, phosphate group, carboxylic acid group, amide group, hydroxyl group, and nitro group, while Y1 does not contain any one of the functional groups selected from ester bond, amide bond, sulfonic acid group, phosphate group, carboxylic acid group, amide group, hydroxyl group, and nitro group. Alternatively, Y1 contains at least one functional group selected from ester bond, amide bond, sulfonic acid group, phosphate group, carboxylic acid group, amide group, hydroxyl group, and nitro group, while X1 does not contain any one of the functional groups selected from ester bond, amide bond, sulfonic acid group, phosphate group, carboxylic acid group, amide group, hydroxyl group, and nitro group. Alternatively, both X1 and Y1 contain at least one functional group selected from ester, amide, sulfonic acid, phosphate, carboxylic acid, amide, hydroxyl, and nitro groups. Furthermore, more specifically, the hydrolyzable organic polymer may have at least one (e.g., at least two, at least three, at least four, at least five) repeating units as shown in Formula (1).

[0043] In this invention, at least one of X1 and Y1 contains at least one (e.g., two or three) functional groups selected from ester bond, amide bond, sulfonic acid group, phosphate group, carboxylic acid group, amide group, hydroxyl group, and nitro group. For example, at least one of X1 and Y1 simultaneously contains an ester bond and a hydroxyl group; at least one of X1 and Y1 simultaneously contains an ester bond and a sulfonic acid group; at least one of X1 and Y1 simultaneously contains an ester bond and a phosphate group; or at least one of X1 and Y1 simultaneously contains an ester bond and a carboxylic acid group.

[0044] X1 can be a tetravalent group derived from a dianhydride monomer. X1 can be the same or different each time it appears. X1 can be selected from the tetravalent groups shown in formula (2), formula (3), formula (4), formula (5), or formula (6):

[0045]

[0046]

[0047] In formulas (2) to (4), R1 may be the same or different each time it appears, and may each independently represent -H, -F, -CF3, -SO3H, -PO3H2, -COOH, -OH, straight-chain or branched alkyl or phenyl groups with 1 to 6 carbon atoms. R2 may be the same or different each time it appears, and may each independently represent a straight-chain or branched hydrocarbon group with 2 to 36 carbon atoms or a cyclic hydrocarbon group with 3 to 20 carbon atoms. R3 may be the same or different each time it appears, and may each independently represent a straight-chain or branched hydrocarbon group with 1 to 6 carbon atoms. Each occurrence of L1 can be the same or different, and can independently represent -O-, -S-, -SO2-, single bond, -NH-, -C(=O)-, -CH=CH-, -C≡C-, -CH2-, -(CH2)2-, -C(CH3)2-, -C(CF3)2-, -C(=O)O-, -OC(=O)-, -C(=O)NH-, or -NH C(=O)-. Each occurrence of n can be the same or different, and can independently represent any integer from 0 to 5, for example: 1, 2, 3, or 4. m represents any integer from 1 to 5, for example: 1, 2, 3, or 4.

[0048] The following are examples of several types of X1.

[0049] For example, when n is 0, X1 can be a tetravalent group as shown below:

[0050]

[0051]

[0052] X1 can also be a tetravalent group, as shown in the following examples:

[0053]

[0054]

[0055] The hydrolyzable organic polymer may have one or more (e.g., three, four, or five) of the aforementioned tetravalent groups.

[0056] In formula (1), Y1 is a divalent group as shown in formula (7), formula (8), or formula (9):

[0057]

[0058]

[0059] L2 can appear repeatedly or be different, and can independently represent -O-, -S-, -SO2-, single bond, -NH-, -C(=O)-, -CH=CH-, -C≡C-, -CH2-, -(CH2)2-, -C(CH3)2-, -C(CF3)2-, -C(=O)O-, -OC(=O)-, -C(=O)NH-, or -NH C(=O)-; R4 can appear the same or different each time, and can each independently represent -H, -F, -CF3, -SO3H, -PO3H2, -COOH, -OH, straight-chain or branched hydrocarbon groups with 1 to 6 carbon atoms or phenyl groups; R5 can appear the same or different each time, and can each independently represent -H, -F, -CF3, -SO3H, -PO3H2, -COOH, -OH, straight-chain or branched hydrocarbon groups with 1 to 6 carbon atoms or phenyl groups; R6 can appear the same or different each time, and can each independently represent straight-chain or branched hydrocarbon groups with 1 to 9 carbon atoms; R7 can appear the same or different each time, and can each independently represent straight-chain or branched hydrocarbon groups with 1 to 9 carbon atoms; n represents any integer from 0 to 5, for example: 1, 2, 3 or 4.

[0060] The following are examples of several types of Y1.

[0061] For example, when n is 0, Y1 can be a divalent group as shown in the following examples:

[0062]

[0063] For example, when n is 1, Y1 can be a divalent group as shown in the following examples:

[0064]

[0065] Y1 can also be a divalent group in the following examples:

[0066]

[0067] The hydrolyzable organic polymer may have one or more (e.g., three, four, or five) of the aforementioned divalent groups.

[0068] In this invention, the hydrolyzable organic polymer is preferably hydrolyzed after hydrolysis in acidic aqueous solution, alkaline aqueous solution, and pure water.

[0069] Considering ionic conductivity, the hydrolyzable polymer is preferably one with imide bonds in its structure. This is because the hydrolysis of an amide bond produces one carboxylic acid group and one hydroxyl group, while the hydrolysis of an ester bond produces one carboxylic acid group and one hydroxyl group. In contrast, the hydrolysis of an imide bond produces two carboxylic acid groups and one amino group. The imide bond produces more hydrophilic functional groups after hydrolysis than amide and ester bonds, thus exhibiting superior ionic conductivity.

[0070] In some embodiments of the present invention, the equilibrium swelling ratio of the isolation membrane after immersion in water, acid, or alkali is less than 1.1.

[0071] In this invention, the resin film can be formed from a composition comprising the non-hydrolyzable organic polymer; the hydrolyzable organic polymer; and, if necessary, an organic solvent. Preferably, the resin film preparation process includes an organic solvent. The resin film (separator precursor) can be formed by coating the composition and then heat-treating it to remove the organic solvent. In some embodiments, the hydrolyzable organic polymer content in the composition is 10 to 70 parts by weight relative to 400 parts by weight of the organic solvent. In some embodiments, the non-hydrolyzable organic polymer content in the composition is 30 to 90 parts by weight relative to 400 parts by weight of the organic solvent. In some embodiments, the hydrolyzable organic polymer content is 10 to 70 parts by weight relative to 500 parts by weight of the composition. In some embodiments, the non-hydrolyzable organic polymer content is 30 to 90 parts by weight relative to 500 parts by weight of the composition.

[0072] The method for preparing the separator precursor of the present invention may include the following steps: mixing a non-hydrolyzable organic polymer, a hydrolyzable organic polymer and an organic solvent to obtain a mixture (composition); forming a coating film on a substrate with the mixture; and subjecting the coating film to heat treatment.

[0073] The method for preparing the separator membrane of the present invention may include the following steps: mixing a non-hydrolyzable organic polymer, a hydrolyzable organic polymer, and an organic solvent to obtain a mixture (composition); forming a coating film on a substrate using the mixture; subjecting the coating film to heat treatment; and hydrolyzing the heat-treated coating film. In the present invention, the hydrolysis can be carried out in an acidic aqueous solution, an alkaline aqueous solution, or pure water. In some embodiments, the hydrolysis is performed by first treating with an alkaline aqueous solution and then with an acidic aqueous solution. In some embodiments, the hydrolysis is performed by first treating with an acidic aqueous solution and then with an alkaline aqueous solution.

[0074] The conditions of the mixing treatment (e.g., temperature and time) are adjusted according to the types of the non-hydrolyzable organic polymer, the hydrolyzable organic polymer, and the organic solvent. In some embodiments of the invention, the temperature range of the mixing treatment is 60°C to 100°C, and the time range is 2 hours to 4 hours. One type of organic solvent may be used alone, or multiple types may be used in combination (e.g., two, three, or four types). The organic solvent includes, but is not limited to, N-methylpyrrolidone, 2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, dichlorobenzene, dioxane, toluene, xylene, chloroform, acetone, butanone, ethanol, and methanol. Based on 100 parts by weight of the total amount of the organic solvent, the total amount of the non-hydrolyzable organic polymer and the hydrolyzable organic polymer is preferably 2 to 55 parts by weight.

[0075] The coating film can be formed by methods such as blade coating, spin coating, or spray coating. In some embodiments of the present invention, the mixture is coated onto a substrate to form the coating film. The purpose of the heat treatment is to remove organic solvents and to make the separator film precursor dense. The temperature of the heat treatment is adjusted according to the composition of the mixture. In some embodiments of the present invention, the temperature of the heat treatment is between 60°C and 250°C, for example: 80°C, 100°C, 120°C, 150°C, 180°C, 210°C, 230°C.

[0076] The method for preparing the separator membrane of the present invention involves a hydrolysis step, which can improve the performance of the obtained separator membrane, for example, more preferably, ionic conductivity. In some embodiments, the hydrolysis step is carried out in an acidic or alkaline aqueous solution. More specifically, the hydrolysis step is carried out as follows: the separator membrane precursor (resin membrane) with density is immersed in a 4M sodium hydroxide aqueous solution (alkali) at 25°C to 70°C for 24 hours, or a 4M lithium hydroxide aqueous solution can be immersed for 24 hours, or a 4M sulfuric acid aqueous solution (acid) can be immersed for 24 hours; then washed three times with deionized water; and then dried at 120°C for 1 hour to obtain the separator membrane. In a preferred embodiment, the separator membrane precursor is hydrolyzed in pure water.

[0077] In a preferred embodiment, the ionic conductivity of the separator is increased by more than 10% compared to the separator (resin membrane) that has not undergone hydrolysis. In another preferred embodiment, the elongation at break of the separator is greater than 10%.

[0078] In this invention, the thickness of the separator is not particularly limited and can be adjusted according to its actual application, but its thickness is preferably 0.1 micrometers to 100 micrometers.

[0079] In this invention, the resin film may further include a filler material, the content of which is greater than 0 parts by weight and not more than 60 parts by weight relative to 100 parts by weight of the resin film, more preferably 10 parts by weight to 60 parts by weight, and more preferably 20 parts by weight to 60 parts by weight.

[0080] In this invention, the composition may further comprise a filler material in an amount greater than 0 parts by weight and not more than 60 parts by weight relative to 500 parts by weight of the composition, more preferably 10 parts by weight to 60 parts by weight, and more preferably 20 parts by weight to 60 parts by weight.

[0081] In this invention, the filler material may be a flame retardant, a hydrophilic material composed of an acidic substance and a basic substance, a ceramic oxide, a lithium salt, an organic acid, an ionic liquid, or any combination thereof. The hydrophilic material may be composed of an acidic substance (e.g., a Lewis acid) and a basic substance (a Lewis base). The hydrophilic material includes, but is not limited to, melamine sulfate, melamine hydrochloride, melamine polyphosphate, melamine pyrophosphate, melamine cyanurate, melamine oxalate, metal orthophosphate, or any combination thereof.

[0082] The present invention also provides a composite membrane comprising the above-described separator membrane.

[0083] The present invention further provides a battery comprising: an anode layer; a cathode layer; and the aforementioned separator disposed between the anode layer and the cathode layer. This battery includes, but is not limited to, fuel cells, flow batteries, and lithium batteries.

[0084] The present invention will be further described with reference to the following embodiments, but it should be understood that these embodiments are for illustrative purposes only and should not be construed as limiting the implementation of the present invention.

[0085] Material sources and preparation in the examples:

[0086] Preparation Example 1: Preparation of Polybenzimidazole

[0087] A 500 mL four-necked reaction flask was set up, and dry nitrogen gas was introduced into it. Then, 2 g of 2,2-bis(4-carboxyphenyl)-hexafluoropropane (purchased from TCI), 6 g of monosodium 2-sulfodium terephthalate (purchased from TCI), 6 g of 3,3'-diaminobenzidine (purchased from TCI), 30 g of P₂O₅ (purchased from Sigma Aldrich), and 460 g of polyphosphoric acid (purchased from ARCOS) were added sequentially. The mixture was stirred uniformly with a mechanical motor, and the temperature was raised to 200 °C for 24 hours. A large amount of deionized water was poured into the resulting reaction solution to precipitate a solid. The solid was washed with a 10wt% NaOH aqueous solution, then repeatedly washed with a large amount of deionized water until neutral, and then dried in an oven at 140℃ for 24 hours to obtain polybenzimidazole powder.

[0088] Preparation Example 2: Preparation of Polybenzoxazole

[0089] A 500mL four-necked reaction flask was set up, and dry nitrogen gas was introduced into it. Then, 9.1g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (purchased from TCI), 9.8g of 2,2-bis(4-carboxyphenyl)hexafluoropropane (purchased from TCI), 30g of P2O5 (purchased from Sigma-Aldrich), and 460g of polyphosphoric acid (purchased from ARCOS) were added sequentially. The mixture was stirred uniformly with a mechanical motor, and the temperature was raised to 200℃ for 24 hours. A large amount of deionized water was poured into the resulting reaction solution to precipitate a solid. The solid was washed with a 10wt% NaOH aqueous solution, and then repeatedly washed with a large amount of deionized water until neutral. It was then dried in an oven at 140℃ for 24 hours to obtain polybenzothiazole powder.

[0090] Preparation Example 3: Preparation of Polyamide-Imide

[0091] A 500mL four-necked reaction flask was set up, and dry nitrogen gas was introduced into it. Then, 24g of 4,4-(hexafluoroisopropylidene) phthalic anhydride (6FDA) (purchased from TCI), 12g of 4,4'-diaminobenzoyl aniline (DABA) (purchased from TCI), and 140g of N-methylpyrrolidone (purchased from Sheng Yi Chemical) were added sequentially. The mixture was stirred uniformly with a mechanical motor for 24 hours, and then heated to 180°C and maintained at that temperature for 4 hours to carry out a thermal ring-closure reaction. A large amount of methanol was poured into the resulting reaction solution to precipitate a solid. The solid was washed with methanol and then dried in an oven at 140°C for 24 hours to obtain polyamide-polyimide powder.

[0092] Preparation Example 4: Preparation of Polyester Imide

[0093] A 500mL four-necked reaction flask was set up, and dry nitrogen gas was introduced into it. Then, 22g of ethylene glycol bis(triphenyltriglyceridyl anhydride) (TMEG) (purchased from TCI), 11g of diaminodiphenyl ether (4,4'-Oxydianiline, ODA) (purchased from TCI), and 140g of N-methylpyrrolidone (purchased from Sheng Yi Chemical) were added sequentially. The mixture was stirred uniformly with a mechanical motor for 24 hours, and then heated to 180°C and maintained at that temperature for 4 hours to carry out a thermal ring-closure reaction. A large amount of methanol was poured into the resulting reaction solution to precipitate a solid. The solid was washed with methanol and then dried in an oven at 140°C for 24 hours to obtain polyester-polyamide-imide powder.

[0094] Preparation Example 5: Preparation of Polybenzenesulfonic Acid-Imide

[0095] A 500mL four-necked reaction flask was set up, and dry nitrogen gas was introduced into it. Then, 24g of 4,4-(hexafluoroisopropylidene) phthalic anhydride (6FDA) (purchased from TCI), 19g of 4,4'-diaminobenzidine-2,2'-disulfonic acid (BDSA) (purchased from TCI), and 140g of N-methylpyrrolidone (purchased from Sheng Yi Chemical) were added sequentially. The mixture was stirred uniformly with a mechanical motor for 24 hours, and then heated to 180℃ and maintained at that temperature for 4 hours to carry out a thermal ring-closure reaction. A large amount of methanol was poured into the resulting reaction solution to precipitate a solid. The solid was washed with methanol and dried in an oven at 140℃ for 24 hours to obtain hexafluoropolyimide powder.

[0096] Preparation Example 6: Preparation of Polybenzoic Acid-Imide

[0097] A 500mL four-necked reaction flask was set up, and dry nitrogen gas was introduced into it. Then, 24g of 4,4-(hexafluoroisopropylidene) phthalic anhydride (6FDA) (purchased from TCI), 15g of 6,6'-diamino-3,3'-methylenedibenzoic acid (MBAA) (purchased from TCI), and 140g of N-methylpyrrolidone (purchased from Sheng Yi Chemical) were added sequentially. The mixture was stirred uniformly with a mechanical motor for 24 hours, and then heated to 180℃ and maintained at that temperature for 4 hours to carry out a thermal ring-closure reaction. A large amount of methanol was poured into the resulting reaction solution to precipitate a solid. The solid was washed with methanol and dried in an oven at 140℃ for 24 hours to obtain a transparent polyimide powder.

[0098] Filling material preparation

[0099] Flame retardant: melamine cyanurate (purchased from: Neptunus Chemical Co., Ltd.)

[0100] Lithium salt: HQ-115 (purchased from 3M)

[0101] Ionic liquid: Imidazolium 1-hexyl-3-methyltetrafluoromethanesulfonate (purchased from Sigma Aldrich)

[0102] Ceramic oxides: Lithium lanthanum zirconium oxide Li7La3Zr2O 12 Preparation of (LLZO)

[0103] In the experiment, Li7La3Zr2O was prepared using the traditional solid-state method. 12 (LLZO) The specific steps are as follows: Accurately weigh LiOH·H2O (95%, Alfa), ZrO2 (99%, Alfa), and La2O3 (99.95%, Alfa) using an electronic balance according to the stoichiometric ratio. An excess of 10% LiOH·H2O is weighed to compensate for the loss of Li element during high-temperature sintering. After preparing the materials, ball milling and discharging are performed. The prepared raw materials are loaded into a ball mill jar at once, and a certain amount of anhydrous ethanol is added. The jar is sealed and then placed in a planetary ball mill for 12 hours. After ball milling, the uniformly mixed slurry is poured into a clean mortar, which is then dried under a heat lamp. The dried powder is placed in a crucible and placed in a high-temperature furnace, where it is calcined at 1100℃ for 12 hours to obtain a precursor with a certain crystal structure. After calcination, the resulting powder is ball-milled a second time for 12 hours, and then sieved to obtain lithium lanthanum zirconium oxide (Li7La3Zr2O). 12 (LLZO) powder.

[0104] Example 1

[0105] Using a mixer, 7 g (70 parts by weight) of polybenzimidazole, 3 g (30 parts by weight) of polyamide-polyimide, and 40 g (400 parts by weight) of N-methylpyrrolidone were mixed at 120°C and 1 atm for 2 hours to form a colloidal mixture. This colloidal mixture was coated onto a glass substrate to form a 200 μm thick film. The coating was then heat-treated by drying at 90–150°C for 5 minutes, followed by curing at 250°C for 1 hour to obtain a 20 μm thick precursor for the release liner (i.e., a resin film).

[0106] Examples 2 to 7 and Comparative Examples 1 to 4

[0107] The membrane precursors (i.e., membranes that have not yet been hydrolyzed) of Examples 2 to 7 and Comparative Examples 1 to 4 were prepared using the same steps as in Example 1, with the main difference being the change in the types and amounts of each component, as shown in Table 1.

[0108] Example 8

[0109] Using a mixer, 4 g (40 parts by weight) of polybenzazole, 4 g (40 parts by weight) of polyamide-polyimide, 2 g (20 parts by weight) of melamine cyanurate, and 40 g (400 parts by weight) of N-methylpyrrolidone (purchased from Sheng Yi Chemical) were mixed at 120°C and 1 atm for 2 hours to form a colloidal mixture, which was then dispersed three times by a three-roll mill. This colloidal mixture was coated onto a glass substrate to form a 200 μm thick coating. The coating was then heat-treated to form a heat-treated coating, wherein the heat treatment consisted of drying at 150–250°C for 30 minutes to obtain a 20 μm thick separator film precursor (resin film).

[0110] Examples 9 to 11 and Comparative Examples 5 to 7

[0111] The membrane precursors (i.e., membranes that have not yet been hydrolyzed) of Examples 9 to 11 and Comparative Examples 5 to 7 were prepared using the same steps as in Example 8, with the main difference being the change in the types and amounts of each component, as shown in Table 2.

[0112] Example 12

[0113] Using a mixer, 4 g (40 parts by weight) of polybenzazole, 4 g (40 parts by weight) of polyamide-polyimide, 2 g (20 parts by weight) of lithium salt, and 40 g (400 parts by weight) of N-methylpyrrolidone (purchased from Sheng Yi Chemical) were mixed at 120°C and 1 atm under nitrogen for 2 hours to form a colloidal mixture. This colloidal mixture was coated onto a glass substrate to form a 200 μm thick coating. The coating was then heat-treated to form a heat-treated coating, wherein the heat treatment was performed at 150–250°C under nitrogen for 30 minutes to obtain a 20 μm thick separator film precursor (resin film).

[0114] Example 13 and Comparative Examples 8 to 9

[0115] The membrane precursors (i.e., membranes that have not yet been hydrolyzed) of Examples 13 and 8 to 9 were prepared using the same steps as in Example 12, with the main difference being the change in the types and amounts of each component, as shown in Table 2.

[0116] The hydrolysis method of the separator membrane precursor in the above embodiments and comparative examples is to soak it in a 4M sulfuric acid aqueous solution at 25°C for 24 hours, wash it three times with deionized water, and dry it at 120°C for 1 hour to complete the separator membrane hydrolysis.

[0117] Evaluation Project

[0118] Porosity (%) measurement: using a mercury porosimeter (brand: Micromeritics; model: [model number missing]). IV 9520) The isolation membranes of Examples 1 to 13 and Comparative Examples 1 to 9 were measured.

[0119] Tensile strength (MPa) and elongation at break (%) were measured using a tensile testing machine (brand: LLOYD; model: LRX) for the release films of Examples 1 to 13 and Comparative Examples 1 to 9, with a pulling speed of 100 mm / min.

[0120] Measurement of acid content (%): The separating membranes of Examples 1 to 13 and Comparative Examples 1 to 9 were weighed (W1, in grams), then immersed in an aqueous sulfuric acid solution (comprising sulfuric acid and water, with a sulfuric acid concentration of 3M) at a temperature of 25 ± 3°C for 7 days. Afterward, they were removed, the sulfuric acid solution adhering to the surface was wiped dry, and then weighed (W2, in grams). The acid content (%) was calculated as [(W2 - W1) / W1] × 100%.

[0121] Measurement of moisture content (%): The release films of Examples 1 to 13 and Comparative Examples 1 to 9 were weighed (W1, in grams), then immersed in an aqueous solution at 80°C for 1 day. Afterwards, they were removed and the aqueous solution adhering to the surface was wiped dry to form an absorbent release film, which was then weighed (W2, in grams). The moisture content (%) was calculated as [(W2-W1) / W1]×100%.

[0122] Ionic conductivity (mS / cm) measurement: The impedance values ​​of the isolation membranes of Examples 1 to 13 and Comparative Examples 1 to 9 were measured using a quadrupole conductivity meter from BekkTECH LLC, USA, and by the Autolab AC impedance analysis method at 25°C. The ionic conductivity (S / cm) is calculated as 1 / [(impedance value × membrane width × membrane thickness) / reference electrode spacing], where the membrane width, membrane thickness, and reference electrode spacing are in cm.

[0123] Vanadium ion diffusion rate (%): A 2.5M sulfuric acid aqueous solution was mixed with VOSO4 to form a first mixture, wherein the concentration of VOSO4 in the first mixture was 1M and the concentration of sulfuric acid was 2.5M. A 2.5M sulfuric acid aqueous solution was mixed with MgSO4 to form a second mixture, wherein the concentration of MgSO4 in the second mixture was 1M and the concentration of sulfuric acid was 2.5M. The experimental ambient temperature was 25±3℃. The separating membranes of Examples 1 to 13 and Comparative Examples 1 to 9 were placed in a container having a accommodating space, and the accommodating space was divided into a first accommodating space (left side) and a second accommodating space (right side). The first mixture and the second mixture were respectively introduced into the first accommodating space and the second accommodating space. The first mixture and the second mixture were irradiated with light of wavelength 766 nm, and the absorbance (Av) of the first mixture and the absorbance (A) of the second mixture were calculated using ultraviolet-visible spectroscopy, Fick's Law, and Beer's Law. Mg Next, the vanadium ions begin to pass through the isolation membrane, and the above steps are repeated at different measurement times (t) to obtain the absorbance (A) of the first mixture at different measurement times. V ) and the absorbance of the second mixture (A) Mg ). For ln(A V -2A Mg A graph was plotted against the measurement time to obtain the first formula, and the mass transfer coefficient (ks) was calculated using this first formula. Then, this mass transfer coefficient was substituted into the second formula to calculate the vanadium ion diffusion rate (D). The first formula is ln(A... V -2A Mg )=lnA V-(2×ks×A×t) / V A The second formula is D = ks × d, where A is the contact area of ​​the separator (in cm²). 2 ), t is the measurement time, V A The volume of the second accommodating space (in cm³) 3 ), where d is the thickness of the separator (in cm).

[0124] Gas permeation rate (%): In this test, the oxygen gas permeation rate is tested using the pressure difference method. A pre-treated sample is placed between the upper and lower test chambers and clamped. First, the low-pressure chamber (lower chamber) is evacuated, then the entire system is evacuated. Once the specified vacuum level is reached, the lower chamber is closed, and a certain pressure of test gas is introduced into the high-pressure chamber (upper chamber), ensuring a constant pressure difference across the sample. Under the influence of this pressure gradient, the gas permeates from the high-pressure side to the low-pressure side. By monitoring the pressure on the low-pressure side, the barrier properties of the tested sample are determined. A micro oxygen permeation analyzer, model 8001 (Oxygen Permeation Analyzer), is used to measure the oxygen transmission rate (OTR) of relevant samples. At room temperature, with the membrane evacuated on one side and oxygen introduced on the other, the micro oxygen permeation analyzer obtains the amount of oxygen permeating through a unit area of ​​the sample per unit time. Q = K·A·Δp, where Q is the permeation rate of gas through the isolation membrane, K is the permeation coefficient of a certain gas through the isolation membrane, A is the area of ​​the isolation membrane, and Δp is the gas pressure difference across the isolation membrane.

[0125] Table 1

[0126]

[0127] Table 2

[0128]

[0129] Please see Figure 1 This is an FTIR image of the separator membrane in Example 1 before hydrolysis. From this FTIR image, it can be observed that at a wavelength of 1777 cm⁻¹... -1 With 1722cm -1 There are two characteristic peaks, representing the absorption peaks of the C=O bonds in symmetrical imides and asymmetrical amides, respectively. Please refer to [link / reference needed]. Figure 2 The image shown is the FTIR spectrum of the separator membrane after hydrolysis in Example 1. After acid treatment and hydrolysis, the wavelength at 1771 cm⁻¹ in the FTIR spectrum is... -1 With 1714cm -1The two characteristic peaks became significantly smaller, indicating that the content of imide and amide bonds decreased and the separator membrane had been hydrolyzed.

[0130] Figure 3 This is the FTIR image of the separator membrane before hydrolysis in Example 9. The wavelength at 1780 cm⁻¹ can be observed from this image. -1 With 1739cm -1 There are two characteristic peaks, which are the absorption peaks of the C=O bond of symmetrical imide and asymmetrical amide, respectively. Figure 4 The image shown is the FTIR spectrum of the separator membrane after hydrolysis in Example 9. The FTIR spectrum after acid treatment and hydrolysis has a wavelength of 1774 cm⁻¹. -1 With 1715cm -1 The two characteristic peaks became significantly smaller, indicating that the content of imide and amide bonds decreased and the separator membrane had been hydrolyzed.

[0131] Referring to Tables 1 and 2, the separators of Examples 1 and 7, after being hydrolyzed by immersion in a 4M sulfuric acid solution, exhibit high ionic conductivity, high elongation at break, low vanadium ion diffusion rate, and low gas permeation rate. These effectively prevent vanadium ions in the electrolyte of vanadium redox flow batteries or fuel gas from passing through in fuel cells, thus significantly improving battery safety and lifespan. Therefore, they indeed achieve the objectives of this invention. The separators of Examples 8 and 13, which contain additional filler material, also exhibit high ionic conductivity after hydrolysis by immersion in a 4M sulfuric acid solution, but their vanadium ion diffusion rate and gas permeation rate are slightly higher than those of the separators of Examples 1 and 7.

[0132] Referring to Tables 1 and 2, the separators of Comparative Examples 1 and 2 used only components of non-hydrolyzable organic polymers, and their ionic conductivity could not be measured after hydrolysis treatment with 4M sulfuric acid solution at room temperature. The separator of Comparative Example 3 contained 80% by weight of hydrolyzable organic polymers; after hydrolysis treatment with 4M sulfuric acid solution at room temperature, the membrane ruptured and became unusable, making membrane formation impossible for testing. The separator of Comparative Example 5 contained 70% by weight of filler material; after hydrolysis treatment with 4M sulfuric acid solution at room temperature, the membrane ruptured and became unusable. The separators of Comparative Examples 4 and 6-9, which were not subjected to hydrolysis treatment with 4M sulfuric acid solution at room temperature, all had their ionic conductivity unmeasurable.

[0133] Although the separators in Comparative Examples 4 and 6 to 9 used components of the non-hydrolyzable and hydrolyzable organic polymers of the present invention, they were not hydrolyzed by soaking in a 4M sulfuric acid solution. As a result, the ionic conductivity of these separators could not be measured, and they could not be used in batteries. In contrast, the separators in Examples 1 to 7 of the present invention, which included components of the non-hydrolyzable and hydrolyzable organic polymers of the present invention, were hydrolyzed by soaking in a 4M sulfuric acid solution at room temperature. This improved their hydrophilicity and resulted in excellent ionic conductivity, making them suitable for use in flow batteries, fuel cells, or lithium batteries.

[0134] Application Examples 1 and 2

[0135] Flow battery fabrication and testing:

[0136] Measurement of coulombic efficiencies (%), voltage efficiencies (%), and energy efficiencies (%) of the flow battery: A single cell with an effective area of ​​5 cm x 5 cm was constructed using a polyvinyl chloride (PVC) frame, the separators from Examples 2 and 3, graphite felt electrodes, bipolar plates, and 100 mL of electrolyte. The electrolyte was prepared by mixing 456 g of VOSO4 powder with 1000 mL of sulfuric acid aqueous solution, wherein the sulfuric acid concentration in the aqueous solution was 3 M. The single cell was charged and discharged using a battery charge / discharge tester [Brand: Chroma; Model: Model 17011], and the charge was measured. Then, the coulombic efficiency, energy efficiency, and voltage efficiency were calculated based on the charge, with a current density of 100 mA / cm². 2 The cutoff voltage range is 0.7V to 1.6V, and the flow rate is 50mL / min. The electrical detection results are shown in Table 3, Application Examples 1 and 2.

[0137] Table 3

[0138]

[0139] Referring to Tables 1, 2 and 3, the separators of Examples 2 and 3 have high coulombic efficiency and low vanadium ion diffusion rate, which can prevent vanadium ions in the flow battery from diffusing into each other within the separator. The test results of Application Examples 1 and 2 in Table 3 are shown respectively. The separator containing hydrolyzable organic polymer has excellent electrical properties in flow battery applications after hydrolysis.

[0140] Application Examples 3 and 4

[0141] Fabrication of membrane electrode assembly for fuel cells:

[0142] The precursors (resin membranes) of the separator membranes from Examples 2 and 13 were hydrolyzed by immersion in a 4M sulfuric acid solution and then immersed in 10M phosphoric acid at 60°C for 1 hour to obtain a phosphorylated separator membrane with an area of ​​6x6cm. 2 The gas diffusion electrode in the membrane electrode element is a 5x5cm electrode. 2Carbon paper, with a thickness of 280 micrometers, is used as both the cathode and anode gas diffusion layers. Next, a commercially available Pt / C catalyst slurry is coated onto both the cathode and anode gas diffusion layers and dried at 160°C, thus forming electrode catalyst layers on both layers. The cathode gas diffusion layer with the electrode catalyst layer constitutes the cathode gas diffusion electrode, and the anode gas diffusion layer with the electrode catalyst layer constitutes the anode gas diffusion electrode. The total Pt content is approximately 1 mg / cm³. 2 Next, the electrode catalyst layer of the cathode gas diffusion electrode and the electrode catalyst layer of the anode gas diffusion electrode are respectively placed on both sides of the aforementioned phosphorylated separator membrane (phosphorylated PBI electrolyte membrane), and then a hot pressing process is performed to form a membrane electrode element. The temperature of the hot pressing process is, for example, between 130°C and 160°C, and the pressure is, for example, between 20 MPa and 30 MPa. The electrical performance test results of the fuel cell are shown in Application Examples 3 and 4 in Table 4, respectively.

[0143] Power density test of fuel cell: First, the battery was activated. The activation steps are as follows: (1) Under the open circuit potential (OCV) state, hydrogen gas was introduced into the anode at 200 c.c. / min and air was introduced into the cathode at 500 c.c. / min. The battery was then heated to 120°C. (2) When the battery temperature reached 120°C, a certain current of 200 mA / cm was applied. 2 (3) When the battery temperature reaches 180°C, the reaction gas flow rate is changed to an equivalent ratio of 1.2 (hydrogen) and 2 (air). (4) The battery is continuously operated for 24 to 72 hours until the battery voltage reaches a stable state. After the battery is activated, hydrogen and air (dosage ratio of about 1:2) are introduced under operating conditions with a temperature between 100°C and 180°C. Under these conditions, the current density and power value of the battery at 0.6V are measured.

[0144] Table 4

[0145]

[0146] Referring to Tables 1, 2 and 4, the separator membranes in Examples 2 and 13 are hydrolyzed, thus having high ionic conductivity and low gas permeation rate, which can effectively prevent fuel gas in the fuel cell from diffusing into each other within the separator membrane. The electrical test results of their application in fuel cells are shown in Application Examples 3 and 4, respectively. Among them, the hydrolyzed separator membrane in Application Example 3 has a higher current density when applied to the fuel cell.

[0147] Application Examples 5 and 6

[0148] Lithium-ion battery manufacturing:

[0149] Solid polymer electrolytes (SPEs) were prepared by mixing PEO (MW = 300,000, Sigma Aldrich) with LiTFSI (HQ-115, 3M) (PEO:LiTFSI = 10:1) and acetonitrile (anhydrous, Sigma Aldrich) using a high-speed mixer. LiFePO4 (LFP) powder (purchased from MTI), PEO / LiTFSI, and carbon black (w:w:w = 60:25:15) were mixed with acetonitrile using a high-speed mixer. The LFP active material loading was 1.5 mg / cm³. 2 The slurry was then cast onto aluminum foil using a scraper. The electrodes were then dried in a vacuum oven at 60°C for at least 48 hours. The separator precursors of Examples 3 and 11 were hydrolyzed by soaking in 4M sulfuric acid solution, then soaked in 4M LiOH aqueous solution (Sigma Aldrich) for 24 hours, washed three times with deionized water, and vacuum baked at 200°C for 1 hour. The lithium foil / SPE / separator / SPE / LFP were then pressed into button batteries (lithium foil, Sigma Aldrich). The electrical performance test results of the lithium batteries are shown in Application Examples 5 and 6 in Table 5, respectively. A battery charge / discharge tester [Brand: Chroma; Model: Model 17011] was used to test the single battery at 60°C, charging and discharging at different rates C / 10, C / 5, C / 2, and 1C, and the average charge was measured over 10 cycles.

[0150] Table 5

[0151]

[0152] Referring to Tables 1, 2 and 5, the separator precursors of Examples 3 and 11 were hydrolyzed by soaking in a 4M lithium hydroxide aqueous solution (alkali) and then made into batteries. They were applied to lithium batteries, and the electrical test results of Application Examples 5 and 6 show that they can be charged and discharged.

[0153] In summary, through the design of the non-hydrolyzable polymer, the hydrolyzable polymer, and their dosage, the separator of this invention possesses high ionic conductivity, high elongation at break, low vanadium ion diffusion rate, and low gas permeability. This not only effectively prevents vanadium ions from passing through the electrolyte and reduces vanadium ion permeability, but also results in high coulombic efficiency in flow battery applications and superior electrical properties in fuel cell and lithium battery applications, effectively improving battery safety and lifespan. Therefore, the separator of this invention can be used in vanadium redox flow batteries, fuel cells, or lithium batteries.

[0154] The above description is merely a preferred embodiment of the present invention and should not be construed as limiting the scope of the present invention. Any simple equivalent changes and modifications made in accordance with the scope of the patent application and the description of the invention shall still fall within the scope of the patent of the present invention.

Claims

1. A separating membrane formed by hydrolyzing a resin membrane, the resin membrane comprising: Non-hydrolyzable organic polymers; and Hydrolyzable organic polymers are those that can be hydrolyzed after treatment with at least one of acidic aqueous solutions, alkaline aqueous solutions, and pure water; in, The content of the hydrolyzable organic polymer is 10 to 70 parts by weight relative to 100 parts by weight of the resin film. The non-hydrolyzable organic polymer includes polybenzimidazole, polybenzoxazole, polybenzothiazole, polyetherketone, polyphenylene ether, polyethersulfone, polysulfone, polyphenylene sulfide, polypropylene, polyethylene, polystyrene, or any combination thereof; The hydrolyzable organic polymer is a repeating unit as shown in formula (1): (1)， Wherein, X1 is a tetravalent group containing at least one aromatic or alicyclic group; Y1 is a divalent group containing at least one aromatic or alicyclic group, and at least one of X1 and Y1 contains at least one functional group selected from ester bond, amide bond, sulfonic acid group, phosphate group, carboxylic acid group, amide group, hydroxyl group and nitro group.

2. The separator membrane of claim 1, wherein the non-hydrolyzable organic polymer has hydrophilic functional groups on its side chains.

3. The separator membrane of claim 2, wherein the hydrophilic functional group comprises a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, an amide group, or a hydroxyl group.

4. The separator as claimed in claim 1, wherein X1 is a tetravalent group selected from formula (2), formula (3), formula (4), formula (5) or formula (6): (2)， (3)， (4)， (5)， (6)， in, R1 can independently represent -H, -F, -CF3, -SO3H, -PO3H2, -COOH, -OH, or a straight-chain or branched alkyl or phenyl group with 1 to 6 carbon atoms; R2 can independently represent a straight-chain or branched hydrocarbon group with 2 to 36 carbon atoms, or a cyclic hydrocarbon group with 3 to 20 carbon atoms; R3 can independently represent a straight-chain or branched hydrocarbon group with 1 to 6 carbon atoms, or a straight-chain or branched hydrocarbon group with -H, -F, -CF3, -SO3H, -PO3H2, -COOH, -OH; L1 can independently represent -O-, -S-, -SO2-, a single bond, -NH-, -C(=O)-, -CH=CH-, -C≡C-, -CH2-, -(CH2)2-, -C(CH3)2-, -C(CF3)2-, -C(=O)O-, -OC(=O)-, -C(=O)NH-, or -NH C(=O)-; n is an independent integer representing any integer from 0 to 5; m is an integer representing any integer from 1 to 5.

5. The separator as claimed in claim 1, wherein the Y1 is a divalent group represented by formula (7), formula (8) or formula (9): (7)， (8)， (9)， in, L2 can be used to independently represent -O-, -S-, -SO2-, single bond, -NH-, -C(=O)-, -CH=CH-, -C≡C-, -CH2-, -(CH2)2-, -C(CH3)2-, -C(CF3)2-, -C(=O)O-, -OC(=O)-, -C(=O)NH-, or -NH. C(=O)-; R4 is a straight-chain or branched hydrocarbon group or phenyl group with 1 to 6 carbon atoms, which can be independently represented by -H, -F, -CF3, -SO3H, -PO3H2, -COOH, -OH; R5 is a straight-chain or branched hydrocarbon group or phenyl group with 1 to 6 carbon atoms, which can be independently represented by -H, -F, -CF3, -SO3H, -PO3H2, -COOH, -OH; R6 and R7 are straight-chain or branched hydrocarbon groups with 1 to 9 carbon atoms; n represents any integer from 0 to 5.

6. The separator membrane as claimed in claim 1, wherein, Compared to the unhydrolyzed membrane, this separator has an ionic conductivity that is more than 10% higher.

7. The separator as described in claim 1, wherein the elongation at break is greater than 10%.

8. The separator as claimed in claim 1, having a thickness of 0.1 micrometers to 100 micrometers.

9. The separator as claimed in claim 1, wherein the resin membrane further comprises a filler material, the content of which is greater than 0 parts by weight and not more than 60 parts by weight relative to 100 parts by weight of the resin membrane.

10. The separator as claimed in claim 9, wherein the filler material is selected from flame retardants, hydrophilic materials composed of acidic and alkaline substances, ceramic oxides, lithium salts, organic acids, ionic liquids, or any combination thereof.

11. The separator of claim 1, wherein the resin membrane is formed of a composition comprising the non-hydrolyzable organic polymer; the hydrolyzable organic polymer; and, if necessary, an organic solvent.

12. A composite membrane comprising the separator membrane as claimed in claim 1.

13. A battery comprising: Anode layer; Cathode layer; and The separator as described in any one of claims 1 to 11 is disposed between the anode layer and the cathode layer.

14. The battery of claim 13, comprising a fuel cell, a flow battery, or a lithium battery.

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