Composite hybrid ionic membrane and preparation method thereof

Abstract

The invention relates to the technical field of hybrid ionic membranes, in particular to a composite hybrid ionic membrane and a preparation method thereof.The preparation method includes the following steps that S1, membrane liquid is prepared, and raw materials of the membrane liquid include ethylene-butylene copolymer, chlorobenzene, anhydrous zinc chloride, chloromethyl butyl ether, N, N-dimethylformamide, butylated hydroxytoluene and MIL-101 (Cr). According to the preparation method disclosed by the invention, the polytetrafluoroethylene fiber is subjected to chlorosulfonation reaction by treating the polytetrafluoroethylene fiber, and a sulfonic acid group can be introduced into the polytetrafluoroethylene fiber through chlorosulfonation, so that the surface energy and hydrophilicity of the polytetrafluoroethylene fiber are effectively improved; the polytetrafluoroethylene fiber can have good interface bonding force with membrane liquid, so that the membrane liquid and a membrane layer are effectively combined, after hot-pressing polymerization treatment, ethylene-butylene copolymer chain segments actively move and are mutually interspersed and combined at high temperature, more physical entanglement points are formed, and the strength performance of the composite hybrid ionic membrane is effectively improved.

Description

Technical Field

[0001] The present invention relates to the technical field of hybrid ion membranes, in particular to a composite hybrid ion membrane and a preparation method thereof. Background Art

[0002] Ion membrane is a polymer film with selective ion transport function. Its performance will directly affect the production process and production efficiency of its core component. It is widely used in electrochemical industry, energy storage, water treatment and other fields.

[0003] In the prior art, ion membranes have the problem of poor mechanical strength. When subjected to stress during use, they are prone to swelling and cracking, which shortens the service life of the ion membrane. Based on this, the present invention provides a composite hybrid ion membrane and a preparation method thereof. Summary of the Invention

[0004] The purpose of the present invention is to provide a composite hybrid ion membrane and a preparation method thereof. The composite hybrid ion membrane prepared by the present invention not only has good strength performance, but also has excellent low resistance performance, which effectively improves the performance of the composite hybrid ion membrane.

[0005] To achieve the above object, the present invention provides the following technical solutions: A method for preparing a composite hybrid ion membrane comprises the following steps: S1: membrane solution preparation, wherein the raw materials of the membrane solution include ethylene-butene copolymer, chlorobenzene, anhydrous zinc chloride, chloromethyl butyl ether, N,N-dimethylformamide, butylated hydroxytoluene, and MIL-101 (Cr); S2: Preparation of support layer, the support layer uses polytetrafluoroethylene fiber as raw material; S3: Preparation of base film: the support layer obtained in S2 is immersed in the membrane solution obtained in S1 for immersion treatment, the temperature of the membrane solution is 60-80%, and the immersion time is 10-30 minutes to obtain a base film; S4: preparing a base film, performing a hot pressing polymerization treatment on the base film obtained in S3, with a hot pressing temperature of 100-300° C. and a pressure of 10-20 MPa to obtain a base film; S5: preparing a treatment solution, wherein the raw materials of the treatment solution include polydimethyldiallyl ammonium chloride, deionized water, polyvinyl alcohol, and glutaraldehyde; S6: ionization reaction treatment, the base membrane obtained in S4 is immersed in the treatment solution obtained in S5 for ionization reaction treatment, the treatment time is 8 to 12 hours, and a composite hybrid ion membrane is obtained.

[0006] Furthermore, the method for preparing the membrane liquid is as follows: ethylene-butene copolymer is added to a flask, chlorobenzene is added to the flask, a magnetic stirrer is connected to stir under 80-85°C water bath conditions, the magnetic stirrer is set to 300-400r / min, constant temperature stirring is carried out for 1.5-2h, the temperature is lowered to 40°C, anhydrous zinc chloride and chloromethyl butyl ether are added in sequence, the temperature is set to 40-44°C, the magnetic stirrer is set to 500-600r / min, constant temperature stirring is carried out for 4-6h, and the obtained product Methanol is added to the mixture and treated with a Soxhlet extractor for 20 to 24 hours. The obtained product is vacuum dried at 60 to 65°C for 4 to 6 hours to obtain a powder. The powder and N,N-dimethylformamide are added to a water bath at 60 to 65°C. At the same time, a magnetic stirrer is connected and the speed is set to 400 to 500 r / min. The mixture is stirred at a constant temperature for 2 to 3 hours. Then, butylated hydroxytoluene and MIL-101 (Cr) are added and the mixture is stirred at a constant temperature for 20 to 30 minutes to obtain a membrane liquid.

[0007] Furthermore, the mass ratio of ethylene-butene copolymer and chlorobenzene is 1: (8-10), the mass of anhydrous zinc chloride is 8-10% of the mass of ethylene-butene copolymer, the mass of chloromethyl butyl ether is 40-45% of the mass of chloromethyl butyl ether, the mass of methanol is 40-50 times the mass of ethylene-butene copolymer, the mass ratio of powder and N,N-dimethylformamide is 1: (4-5), the mass ratio of butylated hydroxytoluene and MIL-101 (Cr) is 1: (6-8), and the mass of butylated hydroxytoluene is 15-20% of the mass of powder.

[0008] Furthermore, MIL-101 (Cr) was pretreated before preparing the membrane liquid. The pretreatment method was as follows: MIL-101 (Cr) was added to a tube furnace, and under a nitrogen atmosphere, the temperature was set to 3-5°C / min and raised to 140-150°C, and kept warm for 2-2.5 hours. Then, the heating rate was set to 4-6°C / min, and the temperature was raised to 240-260°C, and kept warm for 3-4 hours to complete the pretreatment.

[0009] Furthermore, the method for preparing the support layer is as follows: the polytetrafluoroethylene fiber is immersed in ethanol, ultrasonically cleaned for 20 to 30 minutes, then washed with deionized water, sent to an oven, and dried at 50 to 60°C for 3 to 4 hours. The obtained product is immersed in the mixed liquid, and under nitrogen protection, the temperature is set at 60 to 70°C for 3 to 4 hours. The polytetrafluoroethylene fiber that has been immersed is taken out, and the polytetrafluoroethylene fiber that has been immersed, chlorosulfonic acid, and dichloroethane are added to a beaker and mixed. The mixture is treated in an ice water bath for 40 to 50 minutes, and then the water bath is heated to 50 to 60°C and reacted for 2 to 3 hours. The obtained product is rinsed with ethanol and deionized water in sequence to obtain the support layer.

[0010] Furthermore, the mixed liquid is prepared by mixing styrene, toluene, ethanol, and benzoyl peroxide, and the mass ratio of styrene, toluene, ethanol, and benzoyl peroxide is 1: (0.6-0.8): (4-6): (0.01-0.02).

[0011] Furthermore, the mass ratio of the polytetrafluoroethylene fiber, chlorosulfonic acid, and dichloroethane that has completed the soaking treatment is 1: (4-5): (10-12).

[0012] Furthermore, the method for preparing the treatment liquid is: polydimethyldiallylammonium chloride and 50-60°C deionized water are added to a mixer, the mixer is set to 80-120r / min and stirred for 1-2h, then polyvinyl alcohol and glutaraldehyde are added, and the stirring is set to 200-300r / min for 40-60min. The obtained product is filtered, and the filter membrane particle size is 0.5μm to obtain a treatment liquid.

[0013] Furthermore, the mass ratio of polydimethyldiallylammonium chloride to deionized water is 1:(15-20), the mass of polyvinyl alcohol is 1-3% of the mass of deionized water, and the mass of glutaraldehyde is 0.4-0.8% of the mass of deionized water.

[0014] Compared with the prior art, the present invention has the following beneficial effects: 1. In the present invention, chlorosulfonation reaction is caused to occur in the polytetrafluoroethylene fiber by treating the polytetrafluoroethylene fiber. Chlorosulfonation can introduce sulfonic acid groups into the polytetrafluoroethylene fiber, effectively improving the surface energy and hydrophilicity of the polytetrafluoroethylene fiber. In subsequent treatment, the polytetrafluoroethylene fiber can have good interfacial bonding with the membrane liquid, so that the membrane liquid and the membrane layer are effectively combined. After the hot press polymerization treatment, the high temperature causes the ethylene-butene copolymer chain segments to move actively and interpenetrate and combine with each other, forming more physical entanglement points, which effectively improves the strength performance of the composite hybrid ion membrane.

[0015] 2. In the present invention, by adding MIL-101 (Cr) to the preparation system, during the pretreatment of MIL-101 (Cr), step-by-step temperature increase can remove water molecules in the pores of MIL-101 (Cr), making the active sites of MIL-101 (Cr) effectively available and enhancing its structural stability. MIL-101 (Cr) can play a filling and supporting role in the material, improving the stability of ion transport. Chloromethyl butyl ether can cooperate with polydimethyldiallylammonium chloride to form fixed cationic sites, ensuring the continuity of the ion migration path, thereby achieving the purpose of reducing resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The invention proposes a flow chart of a composite hybrid ion membrane and a preparation method thereof. DETAILED DESCRIPTION

[0017] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0018] It should be noted that the raw materials used in the following examples are all commercially available raw materials. Example

[0019] S1: Preparation of membrane solution. The raw materials of the membrane solution include ethylene-butene copolymer, chlorobenzene, anhydrous zinc chloride, chloromethyl butyl ether, N,N-dimethylformamide, butylated hydroxytoluene, and MIL-101 (Cr). The method for preparing the membrane liquid is as follows: ethylene-butene copolymer is added to a flask, chlorobenzene is added to the flask, and a magnetic stirrer is connected to stir the flask under 85°C water bath conditions, the magnetic stirrer is set to 400r / min, and the constant temperature stirring is carried out for 2h, the temperature is lowered to 40°C, anhydrous zinc chloride and chloromethyl butyl ether are added in sequence, the temperature is set to 44°C, the magnetic stirrer is set to 600r / min, and the constant temperature stirring is carried out for 6h, methanol is added to the obtained product, and a Soxhlet extractor is used for 24h, and the obtained product is vacuum dried at 65°C for 6h to obtain a powder, the powder and N,N-dimethylformamide are added to a water bath pot, the water bath temperature is 65°C, and a magnetic stirrer is connected at the same time. The speed of the reactor was set to 500 r / min, and the mixture was stirred at a constant temperature for 3 hours. Then, butylated hydroxytoluene and MIL-101 (Cr) were added, and the mixture was stirred at a constant temperature for 30 minutes to prepare a membrane solution, wherein the mass ratio of ethylene-butene copolymer to chlorobenzene was 1:10, the mass of anhydrous zinc chloride was 10% of the mass of ethylene-butene copolymer, the mass of chloromethyl butyl ether was 45% of the mass of chloromethyl butyl ether, the mass of methanol was 50 times the mass of ethylene-butene copolymer, the mass ratio of powder to N,N-dimethylformamide was 1:5, the mass ratio of butylated hydroxytoluene to MIL-101 (Cr) was 1:8, and the mass of butylated hydroxytoluene was 20% of the mass of powder; MIL-101 (Cr) was pretreated before preparing the membrane solution. The pretreatment method was as follows: MIL-101 (Cr) was added to a tube furnace and heated to 150°C at a rate of 5°C / min under a nitrogen atmosphere, and kept warm for 2.5 hours. Then, the heating rate was set at 6°C / min to 260°C, and kept warm for 4 hours to complete the pretreatment. S2: Preparation of support layer, the support layer uses polytetrafluoroethylene fiber as raw material; The method for preparing the support layer is as follows: the polytetrafluoroethylene fiber is immersed in ethanol, ultrasonically cleaned for 30 minutes, then washed with deionized water, sent to an oven, set the oven at 60°C for drying for 4 hours, the obtained product is immersed in the mixed solution, set at 70°C for reaction for 4 hours under nitrogen protection, the polytetrafluoroethylene fiber that has completed the soaking treatment is taken out, the polytetrafluoroethylene fiber that has completed the soaking treatment, chlorosulfonic acid, and dichloroethane are added to a beaker and mixed, and treated in an ice water bath for 50 minutes, then the water bath is heated to 60°C and reacted for 3 hours, and the obtained product is rinsed with ethanol and deionized water in sequence to prepare the support layer, wherein the mixed solution is prepared by mixing styrene, toluene, ethanol, and benzoyl peroxide, the mass ratio of styrene, toluene, ethanol, and benzoyl peroxide is 1:0.8:6:0.02, and the mass ratio of the polytetrafluoroethylene fiber that has completed the soaking treatment, chlorosulfonic acid, and dichloroethane is 1:5:12; S3: Preparation of base film: the support layer obtained in S2 is immersed in the membrane solution obtained in S1 for immersion treatment. The temperature of the membrane solution is 80%, and the immersion time is 30 minutes to obtain a base film; S4: preparing a base film, performing a hot pressing polymerization treatment on the base film obtained in S3, with a hot pressing temperature of 300° C. and a pressure of 20 MPa to obtain a base film; S5: preparing a treatment solution, wherein the raw materials of the treatment solution include polydimethyldiallyl ammonium chloride, deionized water, polyvinyl alcohol, and glutaraldehyde; The method for preparing the treatment liquid is as follows: polydimethyldiallyl ammonium chloride and 60°C deionized water are added to a mixer, the mixer is set at 120 r / min and stirred for 2 hours, polyvinyl alcohol and glutaraldehyde are then added, and the mixer is set at 300 r / min and stirred for 60 minutes. The resulting product is filtered, and the filter membrane particle size is 0.5 μm to prepare the treatment liquid, wherein the mass ratio of polydimethyldiallyl ammonium chloride to deionized water is 1:20, the mass of polyvinyl alcohol is 3% of the mass of deionized water, and the mass of glutaraldehyde is 0.8% of the mass of deionized water; S6: ionization reaction treatment, the base membrane obtained in S4 is immersed in the treatment solution obtained in S5 for ionization reaction treatment, the treatment time is 12 hours, and a composite hybrid ion membrane is obtained. Example

[0020] S1: Preparation of membrane solution. The raw materials of the membrane solution include ethylene-butene copolymer, chlorobenzene, anhydrous zinc chloride, chloromethyl butyl ether, N,N-dimethylformamide, butylated hydroxytoluene, and MIL-101 (Cr). The method for preparing the membrane liquid is as follows: ethylene-butene copolymer is added to a flask, chlorobenzene is added to the flask, and a magnetic stirrer is connected to stir the flask in a water bath at 83°C. The magnetic stirrer is set to 350r / min and the temperature is kept constant for 1.7h. The temperature is then lowered to 40°C, and anhydrous zinc chloride and chloromethyl butyl ether are added in sequence. The temperature is set to 42°C, the magnetic stirrer is set to 550r / min, and the temperature is kept constant for 5h. Methanol is added to the obtained product and a Soxhlet extractor is used for 22h. The obtained product is vacuum dried at 63°C for 5h to obtain a powder. The powder and N,N-dimethylformamide are added to a water bath at 63°C and a magnetic stirrer is connected at the same time. The speed of the reactor was set to 450 r / min, and the mixture was stirred at a constant temperature for 2.5 hours. Then, butylated hydroxytoluene and MIL-101 (Cr) were added, and the mixture was stirred at a constant temperature for 25 minutes to prepare a membrane solution, wherein the mass ratio of ethylene-butene copolymer to chlorobenzene was 1:9, the mass of anhydrous zinc chloride was 9% of the mass of ethylene-butene copolymer, the mass of chloromethyl butyl ether was 43% of the mass of chloromethyl butyl ether, the mass of methanol was 45 times the mass of ethylene-butene copolymer, the mass ratio of powder to N,N-dimethylformamide was 1:4.5, the mass ratio of butylated hydroxytoluene to MIL-101 (Cr) was 1:7, and the mass of butylated hydroxytoluene was 18% of the mass of powder; MIL-101 (Cr) was pretreated before preparing the membrane solution. The pretreatment method was as follows: MIL-101 (Cr) was added to a tube furnace and heated to 145°C at a rate of 4°C / min under a nitrogen atmosphere, and kept warm for 2.3 hours. Then, the heating rate was set at 5°C / min to 250°C, and kept warm for 3.5 hours to complete the pretreatment. S2: Preparation of support layer, the support layer uses polytetrafluoroethylene fiber as raw material; The method for preparing the support layer is as follows: the polytetrafluoroethylene fiber is immersed in ethanol, ultrasonically cleaned for 25 minutes, then washed with deionized water, sent to an oven, and dried at 55°C for 3.5 hours. The obtained product is immersed in a mixed solution, and under nitrogen protection, the temperature is set to 65°C for reaction for 3.5 hours. The polytetrafluoroethylene fiber that has completed the soaking treatment is taken out, and the polytetrafluoroethylene fiber that has completed the soaking treatment, chlorosulfonic acid, and dichloroethane are added to a beaker and mixed, and treated in an ice water bath for 45 minutes. After that, the water bath is heated to 55°C and reacted for 2.5 hours. The obtained product is rinsed with ethanol and deionized water in sequence to obtain the support layer, wherein the mixed solution is prepared by mixing styrene, toluene, ethanol, and benzoyl peroxide, the mass ratio of styrene, toluene, ethanol, and benzoyl peroxide is 1:0.7:5:0.015, and the mass ratio of the polytetrafluoroethylene fiber that has completed the soaking treatment, chlorosulfonic acid, and dichloroethane is 1:4.5:11; S3: Preparation of base film: the support layer obtained in S2 is immersed in the membrane solution obtained in S1 for immersion treatment. The temperature of the membrane solution is 70%, and the immersion time is 20 minutes to obtain a base film; S4: preparing a base film, performing a hot pressing polymerization treatment on the base film obtained in S3, with a hot pressing temperature of 200° C. and a pressure of 15 MPa to obtain a base film; S5: preparing a treatment solution, wherein the raw materials of the treatment solution include polydimethyldiallyl ammonium chloride, deionized water, polyvinyl alcohol, and glutaraldehyde; The method for preparing the treatment liquid is as follows: polydimethyldiallyl ammonium chloride and 55°C deionized water are added to a mixer, and the mixer is set to 100 r / min and stirred for 1.5 hours. Then, polyvinyl alcohol and glutaraldehyde are added, and the mixer is set to 250 r / min and stirred for 50 minutes. The resulting product is filtered, and the filter membrane particle size is 0.5 μm to prepare the treatment liquid, wherein the mass ratio of polydimethyldiallyl ammonium chloride to deionized water is 1:18, the mass of polyvinyl alcohol is 2% of the mass of deionized water, and the mass of glutaraldehyde is 0.6% of the mass of deionized water; S6: ionization reaction treatment, the base membrane obtained in S4 is immersed in the treatment solution obtained in S5 for ionization reaction treatment, the treatment time is 10 hours, and a composite hybrid ion membrane is obtained. Example

[0021] S1: Preparation of membrane solution. The raw materials of the membrane solution include ethylene-butene copolymer, chlorobenzene, anhydrous zinc chloride, chloromethyl butyl ether, N,N-dimethylformamide, butylated hydroxytoluene, and MIL-101 (Cr). The method for preparing the membrane liquid is as follows: ethylene-butene copolymer is added to a flask, chlorobenzene is added to the flask, and a magnetic stirrer is connected to stir the flask under 80°C water bath conditions, the magnetic stirrer is set to 300r / min, and the constant temperature stirring is carried out for 1.5h, the temperature is lowered to 40°C, anhydrous zinc chloride and chloromethyl butyl ether are added in sequence, the temperature is set to 40°C, the magnetic stirrer is set to 500r / min, and the constant temperature stirring is carried out for 4h, methanol is added to the obtained product, and a Soxhlet extractor is used for 20h, and the obtained product is vacuum dried at 60°C for 4h to obtain a powder, the powder and N,N-dimethylformamide are added to a water bath pot, the water bath temperature is 60°C, and a magnetic stirrer is connected at the same time. The stirrer was set at a speed of 400 r / min and stirred at a constant temperature for 2 hours. Then, butylated hydroxytoluene and MIL-101 (Cr) were added and stirred at a constant temperature for 20 minutes to prepare a membrane solution, wherein the mass ratio of ethylene-butene copolymer to chlorobenzene was 1:8, the mass of anhydrous zinc chloride was 8% of the mass of ethylene-butene copolymer, the mass of chloromethyl butyl ether was 40% of the mass of chloromethyl butyl ether, the mass of methanol was 40 times the mass of ethylene-butene copolymer, the mass ratio of powder to N,N-dimethylformamide was 1:4, the mass ratio of butylated hydroxytoluene to MIL-101 (Cr) was 1:6, and the mass of butylated hydroxytoluene was 15% of the mass of powder; MIL-101 (Cr) was pretreated before preparing the membrane solution. The pretreatment method was as follows: MIL-101 (Cr) was added to a tube furnace and heated to 140°C at a rate of 3°C / min under a nitrogen atmosphere, and kept warm for 2 hours. Then, the heating rate was set at 4°C / min, and the temperature was raised to 240°C, and kept warm for 3 hours to complete the pretreatment. S2: Preparation of support layer, the support layer uses polytetrafluoroethylene fiber as raw material; The method for preparing the support layer is as follows: the polytetrafluoroethylene fiber is immersed in ethanol, ultrasonically cleaned for 20 minutes, then washed with deionized water, sent to an oven, set the oven at 50°C for drying for 3 hours, the obtained product is immersed in the mixed solution, set at 60°C for reaction for 3 hours under nitrogen protection, the polytetrafluoroethylene fiber that has completed the soaking treatment is taken out, the polytetrafluoroethylene fiber that has completed the soaking treatment, chlorosulfonic acid, and dichloroethane are added to a beaker and mixed, and treated in an ice water bath for 40 minutes, then the water bath is heated to 50°C and reacted for 2 hours, and the obtained product is rinsed with ethanol and deionized water in sequence to prepare the support layer, wherein the mixed solution is prepared by mixing styrene, toluene, ethanol, and benzoyl peroxide, the mass ratio of styrene, toluene, ethanol, and benzoyl peroxide is 1:0.6:4:0.01, and the mass ratio of the polytetrafluoroethylene fiber that has completed the soaking treatment, chlorosulfonic acid, and dichloroethane is 1:4:10; S3: Preparation of base film: the support layer obtained in S2 is immersed in the membrane solution obtained in S1 for immersion treatment. The temperature of the membrane solution is 60%, and the immersion time is 10 minutes to obtain a base film; S4: preparing a base film, performing a hot pressing polymerization treatment on the base film obtained in S3, with a hot pressing temperature of 100° C. and a pressure of 10 MPa to obtain a base film; S5: preparing a treatment solution, wherein the raw materials of the treatment solution include polydimethyldiallyl ammonium chloride, deionized water, polyvinyl alcohol, and glutaraldehyde; The method for preparing the treatment liquid is as follows: polydimethyldiallyl ammonium chloride and 50°C deionized water are added to a mixer, the mixer is set at 80 r / min and stirred for 1 hour, polyvinyl alcohol and glutaraldehyde are then added, and the mixer is set at 200 r / min and stirred for 40 minutes. The resulting product is filtered, and the filter membrane particle size is 0.5 μm to prepare the treatment liquid, wherein the mass ratio of polydimethyldiallyl ammonium chloride to deionized water is 1:15, the mass of polyvinyl alcohol is 1% of the mass of deionized water, and the mass of glutaraldehyde is 0.4% of the mass of deionized water; S6: ionization reaction treatment, the base membrane obtained in S4 is immersed in the treatment solution obtained in S5 for ionization reaction treatment, the treatment time is 8 hours, and a composite hybrid ion membrane is obtained.

[0022] Comparative Example 1: The difference between this comparative example and Example 1 is that this comparative example does not contain chlorosulfonic acid.

[0023] Comparative Example 2: This comparative example differs from Example 1 in that: in this comparative example, MIL-101 (Cr) is not pretreated.

[0024] Comparative Example 3: This comparative example is different from Example 1 in that this comparative example does not contain MIL-101 (Cr).

[0025] Comparative Example 4: The difference between this comparative example and Example 1 is that in this comparative example, an equal amount of polytetrafluoroethylene fibers is used to replace the support layer.

[0026] Performance test: The composite hybrid ion membranes prepared in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4 were subjected to performance tests, and the test data obtained are recorded in the following table: In the performance test, the composite hybrid ion membranes prepared in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4 were cut into 5×5 cm membrane sheets, and tensile performance tests and resistance tests were performed respectively.

[0027] It can be seen that the strength performance of the composite hybrid ion membranes prepared in Comparative Examples 1, 2, 3, and 4 are all lower than those in Examples 1, 2, and 3, and the resistance data of the composite hybrid ion membranes prepared in Comparative Examples 1, 2, 3, and 4 are all higher than those in Examples 1, 2, and 3. This shows that: by treating the polytetrafluoroethylene fiber, a chlorosulfonation reaction occurs in the polytetrafluoroethylene fiber, and chlorosulfonation can introduce sulfonic acid groups into the polytetrafluoroethylene fiber, effectively improving the surface energy and hydrophilicity of the polytetrafluoroethylene fiber. In subsequent treatment, the polytetrafluoroethylene fiber can have a good interfacial bonding force with the membrane liquid, so that the membrane liquid and the membrane layer are effectively combined. After the hot press polymerization treatment, the high temperature causes the ethylene-butene copolymer chain segments to move actively and interpenetrate and combine with each other, forming more physical entanglement points, thereby effectively improving the strength performance of the composite hybrid ion membrane. By adding MIL-101 (Cr) to the preparation system, during the pretreatment of MIL-101 (Cr), step-by-step temperature increase can remove water molecules in the MIL-101 (Cr) pores, making the MIL-101 (Cr) active sites effectively available and enhancing its structural stability. MIL-101 (Cr) can play a filling and supporting role in the material, improving the stability of ion transport. Chloromethyl butyl ether can cooperate with polydimethyldiallylammonium chloride to form fixed cationic sites, ensuring the continuity of the ion migration path and achieving the purpose of reducing resistance.

[0028] By comparing and analyzing the relevant data in the table, it can be seen that the composite hybrid ion membrane prepared by the present invention not only has good strength performance, but also has excellent low resistance performance. This shows that the composite hybrid ion membrane provided by the present invention has a broader market prospect and is more suitable for promotion.

[0029] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0030] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to the specific embodiments described. Obviously, many modifications and variations are possible based on the content of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing a composite hybrid ion membrane, characterized in that: The following steps are involved: S1: membrane solution preparation, wherein the raw materials of the membrane solution include ethylene-butene copolymer, chlorobenzene, anhydrous zinc chloride, chloromethyl butyl ether, N,N-dimethylformamide, butylated hydroxytoluene, and MIL-101 (Cr); S2: Preparation of support layer, the support layer uses polytetrafluoroethylene fiber as raw material; S3: Preparation of base film: the support layer obtained in S2 is immersed in the membrane solution obtained in S1 for immersion treatment, the temperature of the membrane solution is 60-80%, and the immersion time is 10-30 minutes to obtain a base film; S4: preparing a base film, performing a hot pressing polymerization treatment on the base film obtained in S3, with a hot pressing temperature of 100-300° C. and a pressure of 10-20 MPa to obtain a base film; S5: preparing a treatment solution, wherein the raw materials of the treatment solution include polydimethyldiallyl ammonium chloride, deionized water, polyvinyl alcohol, and glutaraldehyde; S6: ionization reaction treatment, the base membrane obtained in S4 is immersed in the treatment solution obtained in S5 for ionization reaction treatment, the treatment time is 8 to 12 hours, and a composite hybrid ion membrane is obtained.

2. The method for preparing a composite hybrid ion membrane according to claim 1, wherein: The membrane liquid preparation method comprises the following steps: adding ethylene-butene copolymer to a flask, adding chlorobenzene to the flask, connecting a magnetic stirrer to stir the flask in a water bath at 80-85° C., setting the magnetic stirrer at 300-400 r / min, stirring the flask at a constant temperature for 1.5-2 hours, cooling the flask to 40° C., sequentially adding anhydrous zinc chloride and chloromethyl butyl ether, setting the temperature at 40-44° C., setting the magnetic stirrer at 500-600 r / min, stirring the flask at a constant temperature for 4-6 hours, and adding the resulting product. Methanol is treated with a Soxhlet extractor for 20 to 24 hours, and the resulting product is vacuum dried at 60 to 65°C for 4 to 6 hours to obtain a powder. The powder and N,N-dimethylformamide are added to a water bath at 60 to 65°C. At the same time, a magnetic stirrer is connected and the speed is set to 400 to 500 r / min. Constant temperature stirring is performed for 2 to 3 hours, and then butylated hydroxytoluene and MIL-101 (Cr) are added. Constant temperature stirring is continued for 20 to 30 minutes to obtain a membrane liquid.

3. The method for preparing a composite hybrid ion membrane according to claim 2, wherein: The mass ratio of ethylene-butene copolymer and chlorobenzene is 1: (8-10), the mass of anhydrous zinc chloride is 8-10% of the mass of ethylene-butene copolymer, the mass of chloromethyl butyl ether is 40-45% of the mass of chloromethyl butyl ether, the mass of methanol is 40-50 times the mass of ethylene-butene copolymer, the mass ratio of powder and N,N-dimethylformamide is 1: (4-5), the mass ratio of butylated hydroxytoluene and MIL-101 (Cr) is 1: (6-8), and the mass of butylated hydroxytoluene is 15-20% of the mass of powder.

4. The method for preparing a composite hybrid ion membrane according to claim 2, wherein: MIL-101 (Cr) was pretreated before preparing the membrane liquid. The pretreatment method was as follows: MIL-101 (Cr) was added to a tube furnace, and under a nitrogen atmosphere, the temperature was set to 3-5°C / min and raised to 140-150°C, and kept warm for 2-2.5 hours. Then, the heating rate was set to 4-6°C / min, and the temperature was raised to 240-260°C, and kept warm for 3-4 hours to complete the pretreatment.

5. The method for preparing a composite hybrid ion membrane according to claim 1, wherein: The method for preparing the support layer is as follows: immersing polytetrafluoroethylene fiber in ethanol, ultrasonically cleaning for 20 to 30 minutes, then washing with deionized water, putting the fiber into an oven, setting the oven to 50 to 60° C. for drying for 3 to 4 hours, immersing the obtained product in a mixed solution, reacting at 60 to 70° C. for 3 to 4 hours under nitrogen protection, taking out the polytetrafluoroethylene fiber that has been immersed, adding the polytetrafluoroethylene fiber that has been immersed, chlorosulfonic acid, and dichloroethane into a beaker, mixing, and treating in an ice water bath for 40 to 50 minutes, then heating the water bath to 50 to 60° C. and reacting for 2 to 3 hours, and rinsing the obtained product with ethanol and deionized water in sequence to prepare the support layer.

6. The method for preparing a composite hybrid ion membrane according to claim 5, characterized in that: The mixed liquid is prepared by mixing styrene, toluene, ethanol and benzoyl peroxide, and the mass ratio of styrene, toluene, ethanol and benzoyl peroxide is 1: (0.6-0.8): (4-6): (0.01-0.02).

7. The method for preparing a composite hybrid ion membrane according to claim 5, characterized in that: The mass ratio of the polytetrafluoroethylene fiber, chlorosulfonic acid and dichloroethane after the soaking treatment is 1: (4-5): (10-12).

8. The method for preparing a composite hybrid ion membrane according to claim 1, wherein: The method for preparing the treatment liquid is as follows: polydimethyldiallylammonium chloride and 50-60°C deionized water are added to a mixer, the mixer is set to 80-120 r / min and stirred for 1-2 hours, then polyvinyl alcohol and glutaraldehyde are added, the mixer is set to 200-300 r / min and stirred for 40-60 minutes, the obtained product is filtered, the filter membrane particle size is 0.5 μm, and the treatment liquid is prepared.

9. The method for preparing a composite hybrid ion membrane according to claim 8, characterized in that: The mass ratio of polydimethyldiallylammonium chloride to deionized water is 1:(15-20), the mass of polyvinyl alcohol is 1-3% of the mass of deionized water, and the mass of glutaraldehyde is 0.4-0.8% of the mass of deionized water.

10. A composite hybrid ion membrane, characterized in that: The composite hybrid ion membrane is prepared by the preparation method of any one of claims 1 to 9.

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