Anion exchange membrane and preparation method therefor, and water electrolysis hydrogen production device

Abstract

The present application provides an anion exchange membrane, which comprises a support layer and a homogeneous layer located on one side of the support layer in the thickness direction. The homogeneous layer comprises an anion exchange resin and a plasticizer. The support layer comprises a porous substrate, and the anion exchange resin and the plasticizer which are filled in the porous substrate. The anion exchange resin comprises a compound represented by formula I. The plasticizer comprises N-ethyl-p-toluenesulfonamide.

Description

Anion exchange membranes and their preparation methods, and hydrogen production devices via water electrolysis.

[0001] This application claims priority to Chinese patent application No. 202510363320.1, filed on March 25, 2025, China National Intellectual Property Administration; Chinese patent application No. 202511074057.0, filed on July 31, 2025, China National Patent Office; and Chinese patent application No. 202610079650.2, filed on January 20, 2026, the entire contents of which are incorporated herein by reference. Technical Field

[0002] This application relates to the field of hydrogen production technology through water electrolysis, specifically to an anion exchange membrane and its preparation method, and an apparatus for hydrogen production through water electrolysis. Background Technology

[0003] Anion exchange membranes (AEMs) are core components of alkaline battery chemical devices. Their core function is to conduct hydroxide ions from the cathode to the anode while blocking the conduction of gases, electrons, and other impurities between the anode and cathode. Anion exchange membranes used in water electrolysis hydrogen production devices need to have high ionic conductivity, high mechanical stability, and low gas permeability.

[0004] When AEMs are applied in specific fields, especially those requiring high hydrogen output pressure, they operate in a single-sided pressure environment of 3MPa-5MPa. This scenario places stringent demands on the mechanical stability and gas permeability of the AEMs. Introducing physical reinforcement structures (such as a support mesh) can optimize the mechanical stability of AEMs. However, the filling of the anion exchange resin within the support mesh, as well as the position of the support mesh within the AEM, affects its pressure resistance and ion conductivity. When the anion exchange resin cannot effectively fill the support mesh, resulting in voids within the support mesh, the pressure resistance and ion conductivity of the AEM will significantly decrease. Furthermore, introducing physical reinforcement structures also increases costs. To save costs, a single-sided coating method is often used. Invention Overview

[0005] When using single-sided coating, the anion exchange resin solution cannot completely fill the support network, resulting in a large number of unfilled pores in the support layer after film formation. This significantly increases the sheet resistivity of AEMs and severely affects their performance. At the same time, since the support network is difficult to be located in the center of the anion exchange resin solution, the drying rate of the anion exchange resin varies in different layers during the drying process. Under stress, the prepared AEMs are prone to edge curling, and may even cause incompletely dried material to fall off, seriously affecting the thickness uniformity of AEMs and thus significantly impacting their performance.

[0006] This application provides an anion exchange membrane, including a support layer and a homogeneous layer located on one side of the support layer in its thickness direction. The homogeneous layer includes anion exchange resin and a plasticizer, and the support layer includes a porous substrate and anion exchange resin and plasticizer filled in the porous substrate. The anion exchange resin includes a compound represented by Formula I: Formula I; in Formula I, A1, A2, and A3 are independently selected from substituted or unsubstituted aryl groups, C is a group containing a carbonyl group, D is a group containing a piperidinone group, E is a group containing a quinine cyclic ketone group, 0≤x≤1, 0≤y≤1, 0≤z≤1, x+y+z=1, and n is an integer between 10 and 1,000,000. The plasticizer includes N-ethyl-p-toluenesulfonamide. The porous substrate material includes at least one selected from polyetheretherketone, polyphenylene sulfide, polyphenylene sulfone, polyethersulfone, polypropylene, polyethylene, polyethylene terephthalate, polytetrafluoroethylene, expanded polytetrafluoroethylene, and liquid crystal polymers. The anion exchange membrane provided in the embodiments of this application includes a support layer and a homogenization layer. The porous substrate in the support layer can improve the mechanical strength and pressure resistance of the anion exchange membrane. The anion exchange resin includes compounds of Formula I, and the plasticizer includes N-ethyl-p-toluenesulfonamide. Through the interaction between the anion exchange resin and the plasticizer, the filling effect of the anion exchange resin in the porous substrate is ensured, reducing the risk of pores and bubbles in the porous substrate, ensuring the uniformity and consistency of the anion exchange membrane, and reducing the film resistivity. Simultaneously, the anion exchange membrane provided in this application reduces costs by setting a homogenizing layer on one side of the support layer. Furthermore, during the preparation process, the interaction between the anion exchange resin and the plasticizer increases the interaction force with the base membrane, effectively alleviating the edge warping phenomenon caused by stress generated during drying shrinkage, ensuring the thickness uniformity of the anion exchange membrane, improving the yield, and guaranteeing the overall performance of the anion exchange membrane. In other words, the anion exchange membrane provided in this application has good mechanical strength and pressure resistance, reduces film resistivity, ensures uniform thickness throughout, and exhibits excellent overall performance. It has a low preparation cost and is suitable for large-scale production applications.

[0007] This application also provides a method for preparing an anion exchange membrane, comprising: dispersing anion exchange resin and a plasticizer in a solvent to obtain an anion exchange resin solution; attaching a porous substrate to the surface of a base membrane; coating the anion exchange resin solution onto the surface of the porous substrate opposite to the base membrane, so that the anion exchange resin solution fills the porous structure of the porous substrate and covers the surface of the porous substrate; drying to form a support layer and a homogeneous layer; and peeling it off from the surface of the base membrane to obtain an anion exchange membrane. The anion exchange resin includes compounds represented by Formula I: Formula I; in Formula I, A1, A2, and A3 are independently selected from substituted or unsubstituted aryl groups, C is a group containing a carbonyl group, D is a group containing a piperidinone group, E is a group containing a quinine cyclic ketone group, 0≤x≤1, 0≤y≤1, 0≤z≤1, x+y+z=1, and n is an integer between 10 and 1,000,000. The plasticizer includes N-ethyl-p-toluenesulfonamide. The porous substrate material includes at least one of polyetheretherketone, polyphenylene sulfide, polyphenylene sulfone, polyethersulfone, polypropylene, polyethylene, polyethylene terephthalate, polytetrafluoroethylene, expanded polytetrafluoroethylene, and liquid crystal polymers. The anion exchange membrane preparation method provided in this application involves dispersing anion exchange resin as shown in Formula I with a plasticizer including N-ethyl-p-toluenesulfonamide in a solvent to obtain an anion exchange resin solution. The plasticizer weakens the interactions between the anion exchange resin molecular chains, enhances molecular chain mobility, improves the surface tension of the anion exchange resin solution, and increases its fluidity, thereby improving the filling effect of the anion exchange resin solution in porous substrates, ensuring uniform filling, reducing pores and bubble defects, and lowering sheet resistivity. Simultaneously, the plasticizer including N-ethyl-p-toluenesulfonamide also enhances the interaction with the base membrane, ensuring the adhesion between the support layer and homogenization layer and the base membrane, mitigating edge warping during the casting and drying process of the anion exchange resin solution, preventing edge detachment, and improving the thickness uniformity of the anion exchange membrane. This application embodiment, through a single-sided coating process, reduces the material cost of the anion exchange membrane while ensuring a good filling effect in porous substrates and reducing the risk of edge warping through the synergistic effect of the plasticizer and anion exchange resin, thus improving the overall performance of the anion exchange membrane and making it suitable for large-scale production applications.

[0008] This application also provides a water electrolysis hydrogen production device, including the anion exchange membrane described above, and / or anion exchange membrane prepared by the method described above. The water electrolysis hydrogen production device provided in this application, by employing the anion exchange membrane described above, can ensure stability and improve overall performance. Attached Figure Description

[0009] Figure 1 is a schematic diagram of the longitudinal section structure of the anion exchange membrane provided in an embodiment of this application;

[0010] Figure 2 is a schematic diagram of the longitudinal section structure of the anion exchange membrane provided in the embodiment of this application.

[0011] Explanation of reference numerals in the attached figures:

[0012] 10. Support layer; 20. Homogeneous layer; 21. First homogeneous layer; 22. Second homogeneous layer. Embodiments of the present invention

[0013] In this application, unless otherwise expressly specified and limited, "above" or "below" a second feature can include direct contact between the first and second features, or contact between the first and second features through another feature between them. Furthermore, the terms "first" and "second" are used for descriptive distinction and have no particular meaning.

[0014] In a first aspect, as shown in Figures 1 and 2, an embodiment of this application provides an anion exchange membrane, including a support layer 10 and a homogeneous layer 20 located on at least one side in the thickness direction X of the support layer 10. The homogeneous layer 20 includes anion exchange resin, and the support layer 10 includes a porous substrate and anion exchange resin filled in the porous substrate.

[0015] The anion exchange resin includes the compound shown in Formula I:

[0016] Formula I;

[0017] In Formula I, A1, A2 and A3 are independently selected from substituted or unsubstituted aryl groups, C is a group containing a carbonyl group, D is a group containing a piperidinone group, E is a group containing a quinine cyclic ketone group, 0≤x≤1, 0≤y≤1, 0≤z≤1, x+y+z=1, and n is an integer between 10 and 1000000.

[0018] The porous substrate material includes at least one of polyetheretherketone (PEEK), polyphenylene sulfide (PPS), polyphenylene sulfone (PPSU), polyethersulfone (PES), polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), expanded polytetrafluoroethylene (ePTFE), and liquid crystal polymer (LCP).

[0019] The anion exchange resin includes the compound shown in Formula I, which ensures that the anion exchange membrane has high ionic conductivity, reduces internal resistance, and improves the efficiency of hydrogen production through water electrolysis. The porous matrix in the support layer 10 provides good support, improving the mechanical properties and pressure resistance of the anion exchange membrane. Through the selection of materials for the anion exchange resin and the porous substrate, the anion exchange resin and the porous substrate can have good affinity, allowing the anion exchange resin to fully fill the pores of the porous substrate, making the homogeneous layer 20 and the support layer 10 a whole, and enabling the anion exchange membrane to maintain high ionic conductivity. That is, the anion exchange membrane provided in this application embodiment can have both high ionic conductivity and good pressure resistance, enabling the anion exchange membrane to meet the high pressure requirements while ensuring water electrolysis efficiency and achieving long-term stable operation.

[0020] In some embodiments, the homogenizing layer 20 includes at least one of a first homogenizing layer 21 and a second homogenizing layer 22. The first homogenizing layer 21 and the second homogenizing layer 22 are respectively disposed on opposite sides of the support layer 10 in its thickness direction X. That is, the support layer 10 is covered between the first homogenizing layer 21 and the second homogenizing layer 22, which improves the mechanical strength and pressure resistance of the anion exchange membrane, and enhances the ion conductivity of the anion exchange membrane by having anion exchange resin on both sides.

[0021] In some embodiments, the anion exchange membrane includes a first homogeneous layer 21, a porous substrate, and a second homogeneous layer 22 sequentially stacked. Both the first homogeneous layer 21 and the second homogeneous layer 22 contain anion exchange resin, and the porosity of the porous substrate is 50% to 70%. For example, the porosity of the porous substrate can be 50%, 55%, 60%, 65%, 70%, 75%, 80%, etc.

[0022] In this application, by introducing a porous substrate as a reinforcing layer, the anion exchange membrane can maintain good mechanical properties and dimensional stability under operating conditions. By controlling the porosity of the porous substrate, the anion exchange membrane can possess good mechanical properties and ion conductivity. Simultaneously, the first homogeneous layer 21 and the second homogeneous layer 22 on both sides of the porous substrate can give the anion exchange membrane good gas barrier properties. Porosity is the percentage of the pore area on the porous substrate to the total area of ​​the mesh fabric.

[0023] In some embodiments, the anion exchange resins in the first homogeneous layer 21 and the second homogeneous layer 22 are of the same type. Thus, using the same anion exchange resin in the first homogeneous layer 21 and the second homogeneous layer 22 can improve the coupling effect between them, weaken the separation phenomenon at the bilayer interface, and thereby improve the mechanical properties of the anion exchange membrane.

[0024] In some embodiments, the anion exchange resin includes one of polyarylpiperidine polymers, polyarylenepiperidine polymers, polyarylquinine polymers, and polybenzopyrazole polymers. This allows the anion exchange membrane to have low surface resistance, thereby improving both its electrochemical performance and its gas barrier properties.

[0025] In some embodiments, the ion exchange capacity (IEC) of the anion exchange resin is 1.8 mmol / g to 4.0 mmol / g, for example, it can be 1.8 mmol / g, 2.0 mmol / g, 2.2 mmol / g, 2.4 mmol / g, 2.6 mmol / g, 2.8 mmol / g, 3.0 mmol / g, 3.2 mmol / g, 3.4 mmol / g, 3.6 mmol / g, 3.8 mmol / g, 4.0 mmol / g, etc. This allows the anion exchange membrane to possess high ion conductivity.

[0026] In some embodiments, the porous substrate is composed of multiple interwoven warp and weft threads. The distance between two adjacent warp threads is 100μm to 200μm, for example, 100μm, 110μm, 120μm, 130μm, 140μm, 150μm, 160μm, 170μm, 180μm, 190μm, 200μm, etc. The distance between two adjacent weft threads is also 100μm to 200μm, for example, 100μm, 110μm, 120μm, 130μm, 140μm, 150μm, 160μm, 170μm, 180μm, 190μm, 200μm, etc. This improves the mechanical properties of the anion exchange membrane. The combined effect of the distance between the warp threads and the porosity gives the anion exchange membrane good mechanical and ion conductivity properties.

[0027] In some embodiments, the degradation temperature of the porous substrate is ≥120°C. This expands the application scenarios of anion exchange membranes and ensures good stability during application.

[0028] In some embodiments, the contact angle of the porous substrate with pure water is ≤150°. This improves the electrochemical performance of the anion exchange membrane. The porous substrate also possesses a certain degree of hydrophilicity, which enhances the hydrophilicity of the anion exchange membrane. When used in an aqueous environment, the better the overall hydrophilicity of the anion exchange membrane, the better its electrochemical performance.

[0029] In some embodiments, a method for preparing anion exchange composite membrane is provided, comprising:

[0030] A homogeneous slurry and a porous substrate are provided. The homogeneous slurry is disposed on both sides of the porous substrate to form a first homogeneous layer 21 and a second homogeneous layer 22, thereby obtaining an anion exchange membrane. The homogeneous slurry contains anion exchange resin.

[0031] In some embodiments, the method for preparing a homogeneous slurry includes the following steps:

[0032] Anion exchange resin and solvent are provided, mixed and heated, then filtered and centrifuged to remove bubbles, to obtain a membrane slurry.

[0033] In some embodiments, the heating temperature is 60°C to 100°C, for example, 60°C, 70°C, 80°C, 90°C, 100°C, etc., and the heating time is 1 hour to 6 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, etc. This allows the anion exchange resin to be fully dissolved in the solvent.

[0034] In some embodiments, the solid content of the homogeneous layer slurry is 15%wt to 25%wt. This allows the homogeneous layer slurry to effectively form a film on a porous substrate, and the thickness of the homogeneous layer can be controlled. The solid content of the homogeneous layer slurry affects its viscosity, thereby enabling it to have good film-forming properties.

[0035] In some embodiments, the viscosity of the homogeneous slurry is 5000 mPa.s@25℃ to 48000 mPa.s@25℃, for example, it can be 5000 mPa.s@25℃, 10000 mPa.s@25℃, 15000 mPa.s@25℃, 20000 mPa.s@25℃, 25000 mPa.s@25℃, 30000 mPa.s@25℃, 35000 mPa.s@25℃, 40000 mPa.s@25℃, 45000 mPa.s@25℃, 48000 mPa.s@25℃, etc.

[0036] In some embodiments, the solvent includes one or more of dimethyl sulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0037] In some embodiments, the porous substrate is a porous substrate obtained by immersion treatment with an alcohol solvent. The alcohol solvent is a polar solvent and readily volatile. This prevents the alcohol solvent from remaining in the porous substrate, while simultaneously improving the free energy of the porous substrate surface, enhancing the wetting and filling effect of the anion exchange resin on the porous substrate, thereby improving the composite effect of the porous substrate and the homogeneous layer, enhancing the gas barrier properties of the anion exchange membrane, and reducing potential oil and impurities.

[0038] In some embodiments, the soaking time is 6h to 24h, for example, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, etc.

[0039] In some embodiments, the alcohol solvent includes one or more of methanol, ethanol, and isopropanol.

[0040] In some embodiments, a homogeneous slurry is disposed on both sides of a porous substrate to form a first homogeneous layer 21 and a second homogeneous layer 22, including:

[0041] A substrate is provided, and a homogeneous slurry is disposed on the substrate to obtain a first wet film layer;

[0042] One side surface of the porous substrate is bonded to the side of the first wet film layer away from the substrate to obtain a first composite, the first composite comprising a porous substrate and a first wet film layer.

[0043] The first composite attached to the substrate surface is subjected to a first drying treatment, and then a homogeneous slurry is applied to the other side surface of the porous substrate to form a second wet film layer. Then, a second drying is performed to form a first homogeneous layer 21 and a second homogeneous layer 22.

[0044] In this application, a homogeneous slurry layer is deposited on a substrate, which can be achieved by scraping. A second wet film layer is formed by depositing the homogeneous slurry layer on the other side surface of the porous substrate, which can be done by coating the homogeneous slurry layer onto the other side surface of the porous substrate. Since the porous substrate is a porous material, by depositing the homogeneous slurry layer on the substrate and then bonding it to the porous substrate to form a first wet film layer on one side surface of the mesh, the bonding effect between the porous substrate and the homogeneous slurry layer can be improved. Compared with directly coating the slurry onto the porous substrate, the probability of slurry dripping from the pores of the porous substrate can be reduced. The substrate can be a PET polyester film, which is removed after the anion exchange membrane is prepared.

[0045] In some embodiments, the temperature of the first drying is 40°C to 60°C, for example, it can be 40°C, 42°C, 44°C, 46°C, 48°C, 50°C, 52°C, 54°C, 56°C, 58°C, 60°C, etc., and the drying time is 5 min to 50 min, for example, it can be 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, etc.

[0046] In some embodiments, the second drying process includes drying at 40°C~60°C for 1-2 hours, at 70°C~90°C for 2-3 hours, and at 60°C~80°C for 1-2 hours sequentially. This ensures good film formation of the homogeneous layer. Excessively high initial drying temperatures can lead to rapid drying of the homogeneous layer surface, resulting in an orange peel effect.

[0047] In some embodiments, as shown in FIG1, the anion exchange membrane includes a support layer 10 and a homogeneous layer 20 located on one side of the support layer 10 in the thickness direction. The homogeneous layer 20 includes anion exchange resin and a plasticizer, and the support layer 10 includes a porous substrate and anion exchange resin and plasticizer filled in the porous substrate.

[0048] The anion exchange resin includes the compound shown in Formula I:

[0049] Formula I;

[0050] In Formula I, A1, A2 and A3 are independently selected from substituted or unsubstituted aryl groups, C is a group containing a carbonyl group, D is a group containing a piperidinone group, E is a group containing a quinine cyclic ketone group, 0≤x≤1, 0≤y≤1, 0≤z≤1, x+y+z=1, and n is an integer between 10 and 1000000.

[0051] Plasticizers include N-ethyl-p-toluenesulfonamide. The porous substrate material includes at least one of polyetheretherketone (PEEK), polyphenylene sulfide (PPS), polyphenylene sulfone (PPSU), polyethersulfone (PES), polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), expanded polytetrafluoroethylene (ePTFE), and liquid crystal polymer (LCP).

[0052] The anion exchange membrane provided in this application includes a support layer 10 and a homogenizing layer 20. The porous substrate in the support layer 10 improves the mechanical strength and pressure resistance of the anion exchange membrane. The anion exchange resin includes a compound of Formula I, and the plasticizer includes N-ethyl-p-toluenesulfonamide. Through the interaction between the anion exchange resin and the plasticizer, the filling effect of the anion exchange resin in the porous substrate is ensured, reducing the risk of pores and bubbles in the porous substrate, ensuring the uniformity and consistency of the anion exchange membrane formation, and reducing the surface resistivity of the film. Simultaneously, the anion exchange membrane provided in this application, by setting the homogenizing layer 20 on one side of the support layer 10, can reduce costs. Furthermore, during the preparation process, the interaction between the anion exchange resin and the plasticizer increases the interaction force with the base membrane, effectively alleviating the edge warping phenomenon caused by stress due to drying shrinkage during the drying process of the anion exchange membrane, ensuring the thickness uniformity of the anion exchange membrane, improving the yield, and guaranteeing the overall performance of the anion exchange membrane. In other words, the anion exchange membrane provided in this application has good mechanical strength and pressure resistance, and can reduce the film surface resistance and ensure uniform thickness throughout, so that the anion exchange membrane has excellent comprehensive performance, low preparation cost, and is suitable for large-scale production and application.

[0053] Specifically, N-ethyl-p-toluenesulfonamide can reduce the intermolecular forces of anion exchange resin and increase the interchain spacing, allowing the anion exchange resin to fully fill the pore structure of the porous substrate. Furthermore, the increased interchain spacing of the anion exchange resin by N-ethyl-p-toluenesulfonamide also helps reduce ion migration resistance, and its polar groups (such as sulfonamide groups) also participate in ion transport, improving ion conductivity. The high porosity and high mechanical strength of the porous substrate form a support layer 10, improving the overall mechanical strength and structural stability of the anion exchange membrane while providing sufficient filling space for the anion exchange resin. Utilizing the affinity between the porous substrate, the anion exchange resin, and the plasticizer, the filling effect of the anion exchange resin in the porous substrate is ensured, ion conductivity is maintained, and surface resistivity is reduced.

[0054] In some embodiments, the mass ratio of anion exchange resin to plasticizer in the homogeneous layer 20 is 1:(0.05-0.6).

[0055] By keeping the mass ratio of anion exchange resin and plasticizer in the homogeneous layer 20 within the above range, the synergistic effect between the anion exchange resin and plasticizer can be improved, ensuring good mechanical strength and pressure resistance, and ensuring uniform thickness throughout.

[0056] For example, in the homogeneous layer 20, the mass ratio of anion exchange resin to plasticizer can be 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5 or 1:0.6.

[0057] In some embodiments, the mass ratio of anion exchange resin to plasticizer in the support layer 10 is 1:(0.05-0.6).

[0058] By keeping the mass ratio of anion exchange resin and plasticizer in the support layer 10 within the above-mentioned range, the synergistic effect between the anion exchange resin and the plasticizer can be improved, the bonding and filling performance between the anion exchange resin and the porous substrate can be improved, the film formation uniformity of the anion exchange membrane can be guaranteed, and good mechanical strength and pressure resistance can be guaranteed.

[0059] For example, in the support layer 10, the mass ratio of anion exchange resin to plasticizer can be 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5 or 1:0.6.

[0060] It should be noted that the mass ratio of anion exchange resin to plasticizer refers to the mass ratio of dry matter.

[0061] In some embodiments, the thickness of the support layer 10 is 5 μm-200 μm.

[0062] By keeping the thickness of the support layer 10 within the aforementioned range, the mechanical strength and flexibility of the anion exchange membrane can be balanced, and the filling effect of the anion exchange resin in the support layer 10 can be ensured. Pores and bubbles in the support layer 10 can be reduced, thereby lowering the film-forming surface resistance of the anion exchange membrane and ensuring the ion conduction effect.

[0063] For example, the thickness of the support layer 10 can be 5μm, 10μm, 20μm, 30μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm, 100μm, 110μm, 120μm, 130μm, 140μm, 150μm, 160μm, 170μm, 180μm, 190μm or 200μm.

[0064] In some embodiments, the thickness of the homogeneous layer 20 is 10 μm-100 μm.

[0065] By ensuring that the thickness of the homogeneous layer 20 is within the aforementioned range, the ion conduction migration distance can be effectively shortened, the surface resistance can be reduced, and the ion conduction efficiency can be improved. Furthermore, the risk of edge warping during the drying process of the homogeneous layer 20 can be effectively reduced, ensuring the thickness uniformity of the anion exchange membrane and controlling the material and production costs of the anion exchange membrane.

[0066] For example, the thickness of the homogeneous layer 20 can be 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm.

[0067] In some embodiments, the porosity of the porous substrate is 30%-90%.

[0068] In some embodiments, the pore size in the porous substrate ranges from 20 μm to 200 μm.

[0069] By ensuring that the porosity and pore size of the porous substrate are within the aforementioned range, the mechanical strength of the porous substrate and the filling effect of the anion exchange resin can be balanced, enabling the anion exchange membrane to possess both high pressure resistance and high ionic conductivity.

[0070] For example, the porosity of the porous substrate can be 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90%, and the pore size in the porous substrate can be 20μm, 30μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm, 100μm, 110μm, 120μm, 130μm, 140μm, 150μm, 160μm, 170μm, 180μm, 190μm, or 200μm.

[0071] In some embodiments, the porosity of the porous substrate is 50%-70%. By controlling the porosity of the porous substrate, the anion exchange membrane can have good mechanical properties and ion conduction properties.

[0072] In some embodiments, the porous substrate includes at least one of woven fabric, nonwoven fabric, and porous polymer layer.

[0073] Woven fabrics possess high tensile strength and mechanical properties, along with a low coefficient of thermal expansion, which enhances the mechanical properties and pressure resistance of anion exchange membranes. Their porous structure allows anion exchange resin to fill the pores, ensuring the ionic conductivity of the membrane. Non-woven fabrics, with their high porosity and good flexibility, facilitate the filling of anion exchange resin, improving both the mechanical properties and ionic conductivity of the membrane. Porous polymer layers offer a controllable pore structure, allowing for customized porosity and pore size, and exhibit high affinity for anion exchange resins. This enhances both the mechanical strength and pressure resistance of the anion exchange membrane while maintaining its ionic conductivity.

[0074] In some embodiments, the anion exchange resin comprises a compound as shown in Formula II:

[0075] Formula II;

[0076] In Formula II, R1 and R3 are each independently selected from one of the following: hydrogen, a substituted or unsubstituted alkyl chain with 1-10 carbon atoms, a group containing heteroatoms, and a substituted or unsubstituted polycyclic structure; R2 is selected from at least one of a substituted or unsubstituted polycyclic structure and a substituted or unsubstituted alkyl chain, and the number of substituted or unsubstituted polycyclic structures in R2 is 0-10; R4, R5, R6, R7, and R8 are each independently selected from one of the following: hydrogen, fluorine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, and a substituted or unsubstituted aromatic group; Z1 - and Z2 - Selected independently from OH - Cl - ,Br - HCO3 - NO3 - CF3COO - CH3COO - and R0SO3 - At least one of the following: wherein R0 is selected from methyl, ethyl, vinyl, cyclopropyl, trifluoromethyl, phenyl, tolyl, nitrophenyl and benzyl.

[0077] Anion exchange resins include compounds as shown in Formula II, which have high ionic conductivity and good wetting properties. They exhibit good synergistic effects with plasticizers including N-ethyl-p-toluenesulfonamide, improving their affinity with porous substrates. This allows the anion exchange resin to fully fill the pores of the porous substrate, ensuring the ionic conductivity of the anion exchange membrane and reducing its sheet resistance.

[0078] In some embodiments, A1, A2, and A3 are each independently selected from at least one of biphenyl, p-terphenyl, m-terphenyl, p-tetraphenyl, diphenylmethane, triphenylmethane, 9,10-benzophenanthrene, tetraphenylmethane, tripterene, 9,9'-spirodifluorene, 9,9'-bicarbazole, 2,2'-bi-9,9'-spirobi[9Hfluorene], 4,4-bis(9-carbazole)biphenyl, triphenylamine, 9,9'-bifluorene, 9,9'-diphenylfluorene, 9,9'-dimethylfluorene, and 1,3,5-triphenylbenzene.

[0079] By independently selecting A1, A2, and A3 from the aforementioned groups, the ion transport channels of the anion exchange membrane can be optimized, the ion exchange capacity can be enhanced, the film-forming properties of the polymer can be improved, and the mechanical strength and chemical stability of the anion exchange membrane can be guaranteed.

[0080] In some embodiments, C is selected from at least one of butanedione, trifluoroacetone, and hydroxyacetone.

[0081] By including at least one of butanedione, trifluoroacetone, and hydroxyacetone in the carbonyl group (C), a stable cross-linked network can be formed, which improves the mechanical strength and chemical corrosion resistance of the anion exchange membrane, optimizes the ion transport performance of the anion exchange membrane, and improves the wetting performance, thus helping to achieve full filling and tight bonding of the anion exchange resin to the porous substrate.

[0082] In some embodiments, D is selected from compounds of any one of formulas 1-14;

[0083]

[0084]

[0085] .

[0086] By making the structure of D (containing a piperidone group) as shown in any one of Formulas 1-14, the stability of the anion exchange resin can be improved, and it can help to form a high-efficiency ion transport channel, achieve low activation energy transport, and ensure the mechanical properties of the anion exchange membrane.

[0087] In some embodiments, E is selected from compounds of any one of formulas 15-17:

[0088] .

[0089] By making the structure of E (containing a quinine cyclic ketone group) as shown in any one of Formulas 15-17, it can resist OH. - The nucleophilic attack ensures the stability of the anion exchange membrane, forms a through-hole ion channel, improves ion transport efficiency, and ensures the mechanical properties of the anion exchange membrane.

[0090] Secondly, this application also provides a method for preparing anion exchange membrane, comprising:

[0091] An anion exchange resin and a plasticizer are dispersed in a solvent to obtain an anion exchange resin solution.

[0092] A porous substrate is attached to the surface of a base membrane, and an anion exchange resin solution is coated on the side of the porous substrate away from the base membrane so that the anion exchange resin solution fills the porous structure of the porous substrate and covers the surface of the porous substrate. After drying, a support layer 10 and a homogeneous layer 20 are formed. The solution is then peeled off from the surface of the base membrane to obtain an anion exchange membrane.

[0093] The anion exchange resin includes the compound shown in Formula I:

[0094] Formula I;

[0095] In the formula, A1, A2 and A3 are independently selected from substituted or substituted aryl groups, C is a group containing a carbonyl group, D is a group containing a piperidinone group, E is a group containing a quinine cyclic ketone group, 0≤x≤1, 0≤y≤1, 0≤z≤1, x+y+z=1, and n is an integer between 10 and 1000000.

[0096] Plasticizers include N-ethyl-p-toluenesulfonamide;

[0097] The porous substrate material includes at least one of polyetheretherketone, polyphenylene sulfide, polyphenylene sulfone, polyethersulfone, polypropylene, polyethylene, polyethylene terephthalate, polytetrafluoroethylene, expanded polytetrafluoroethylene, and liquid crystal polymer.

[0098] The method for preparing the anion exchange membrane provided in this application involves dispersing anion exchange resin as shown in Formula I with a plasticizer including N-ethyl-p-toluenesulfonamide in a solvent to obtain an anion exchange resin solution. The plasticizer weakens the interactions between the molecular chains of the anion exchange resin, enhances molecular chain mobility, improves the surface tension of the anion exchange resin solution, and increases its fluidity, thereby improving the filling effect of the anion exchange resin solution in a porous substrate, ensuring uniform filling, reducing pores and bubble defects, and lowering sheet resistivity. Simultaneously, the plasticizer including N-ethyl-p-toluenesulfonamide also enhances the interaction with the base membrane, ensuring the adhesion between the support layer 10 and the homogenous layer 20 and the base membrane, alleviating edge warping during the casting and drying process of the anion exchange resin solution, preventing edge detachment, and improving the thickness uniformity of the anion exchange membrane. This application, through a single-sided coating process, reduces the material cost of the anion exchange membrane while ensuring a good filling effect in a porous substrate and reducing the risk of edge warping through the synergistic effect of the plasticizer and anion exchange resin, thus improving the overall performance of the anion exchange membrane and making it suitable for large-scale production applications.

[0099] In some embodiments, the solid content of the anion exchange resin solution is 10%-60%.

[0100] By ensuring that the solid content in the anion exchange resin solution is within the above-mentioned range, it is possible to guarantee that the anion exchange resin solution has good fluidity, improve the coating effect, and enable the anion exchange resin to fill the porous substrate, thereby ensuring the ion conductivity of the formed anion exchange membrane.

[0101] For example, the solid content of the anion exchange resin solution can be 10%, 20%, 30%, 40%, 50%, or 60%.

[0102] In some embodiments, the plasticizer in the anion exchange resin solution is 1%-10% by mass.

[0103] By ensuring that the mass percentage of plasticizer in the anion exchange resin solution is within the above-mentioned range, the synergistic effect between the plasticizer and the anion exchange resin can be enhanced while maintaining the proportion of anion exchange resin and improving ion conductivity.

[0104] For example, the mass percentage of plasticizer in the anion exchange resin solution can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%.

[0105] In some embodiments, the viscosity of the anion exchange resin solution at 25°C is 500 mPa·s-80000 mPa·s.

[0106] By keeping the viscosity of the anion exchange resin solution within the above-mentioned range, the affinity between the anion exchange resin solution and the porous matrix can be improved, allowing the anion exchange resin to fully wet the pores of the porous substrate and form a good bond.

[0107] For example, the viscosity of the anion exchange resin solution at 25°C can be 500 mPa·s, 1000 mPa·s, 1500 mPa·s, 2000 mPa·s, 2500 mPa·s, 3000 mPa·s, 3500 mPa·s, 4000 mPa·s, 4500 mPa·s, 5000 mPa·s, 5500 mPa·s, 6000 mPa·s, 6500 mPa·s, 7000 mPa·s, 7500 mPa·s, or 8000 mPa·s.

[0108] In some embodiments, the method for preparing the anion exchange resin solution includes:

[0109] Anion exchange resin and plasticizer are dispersed in a solvent and filtered through a 2000-20000 mesh filter membrane to obtain anion exchange resin solution.

[0110] Filtration can remove large particles of impurities from the anion exchange resin solution, reduce defects in the anion exchange membrane, improve the uniformity of the anion exchange membrane, help optimize ion transport channels, improve ion conductivity, and enhance the stability of the anion exchange membrane.

[0111] In some embodiments, the solvent includes at least one selected from dimethyl sulfoxide, tetrahydrofuran, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, and anhydrous ethanol.

[0112] The solvents described above have good solubility for anion exchange resins and plasticizers, and have low boiling points, which improves the solvent evaporation and film formation rate.

[0113] Thirdly, this application also provides an electrolytic water hydrogen production apparatus, including the anion exchange membrane as described above, and / or anion exchange membrane prepared by the method described above.

[0114] The water electrolysis hydrogen production device provided in this application has all the beneficial effects of the anion exchange membrane as described above, which will not be repeated here.

[0115] The embodiments of this application are further illustrated below with reference to specific examples. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of this application. Experimental methods in the following embodiments that do not specify specific conditions are generally performed according to the conditions recommended by the manufacturer.

[0116] Example 1

[0117] An anion exchange membrane, the preparation method of which includes:

[0118] (1) Aromatic compounds and carbonyl compounds were subjected to hydroxyalkylation under superacid catalysis. After the reaction was completed, they were mixed with dimethyl sulfoxide. After mixing, a quaternizing agent was added, and the mixture was stirred and heated to 70°C for 24 h to obtain polyarylpiperidine polymer resin (ion exchange capacity (IEC) of 1.8 mmol / g~4.0 mmol / g).

[0119] (2) Weigh 15g of polyarylepiperidine polymer resin and mix it with 65g of dimethyl sulfoxide. Dissolve the mixture at 80°C, filter, centrifuge and degas to obtain a homogeneous slurry with a solid content of 16wt% and a viscosity of 8100mPa.s@25°C.

[0120] (3) Soak the PEEK mesh in ethanol at room temperature for 24 hours, then remove and set aside for use;

[0121] (4) The homogeneous slurry is scraped onto a flat PET substrate to obtain a coating with a thickness of 60 μm. Then, a 40 μm thick PEEK mesh (with an opening rate of 60%) is laid flat on the coating surface and dried at 50°C for 30 min. Then, a coating with a thickness of 80 μm is coated on the PEEK mesh surface. Then, the mesh is dried at 60°C for 2 h, 80°C for 3 h, and 70°C for 1 h in sequence to obtain an ion exchange membrane with a thickness of 100 μm (the mesh is 40 μm thick, and the thickness of the two membrane layers on both sides of the mesh is 30 μm).

[0122] Example 2

[0123] This embodiment is basically the same as Embodiment 1, except that in this embodiment, the polyarylpiperidine polymer resin is replaced with polyarylpiperidine polymer resin, and the viscosity of the homogeneous layer slurry is 8200 mPa.s@25℃.

[0124] Example 3

[0125] This embodiment is basically the same as Embodiment 1, except that in this embodiment, the polyarylpiperidine polymer resin is replaced with polyarylquinine polymer resin, the amount of dimethyl sulfoxide is 70g, the solid content of the homogenized layer slurry is 15wt%, and the viscosity of the homogenized layer slurry is 6400mPa.s@25℃.

[0126] Example 4

[0127] This embodiment is basically the same as Embodiment 1, except that the polyarylpiperidine polymer resin is replaced with polyarylquinine polymer resin, and the solid content of the homogenized layer slurry is 17wt%, and the viscosity of the homogenized layer slurry is 9300mPa.s@25℃.

[0128] Example 5

[0129] This embodiment is basically the same as Embodiment 1, except that the mesh thickness in this embodiment is 80μm.

[0130] Example 6

[0131] This embodiment is basically the same as embodiment 1, except that the mesh thickness in this embodiment is 20μm.

[0132] Example 7

[0133] This embodiment is basically the same as Embodiment 1, except that the thicknesses of the two film layers on both sides of the mesh in this embodiment are 10μm and 50μm, respectively.

[0134] Example 8

[0135] This embodiment is basically the same as Embodiment 1, except that the thicknesses of the two homogeneous layers on both sides of the mesh in this embodiment are 20μm and 40μm, respectively.

[0136] Example 9

[0137] This embodiment is basically the same as Embodiment 1, except that the porosity of the mesh in this embodiment is 50%.

[0138] Example 10

[0139] This embodiment is basically the same as Embodiment 1, except that the porosity of the mesh in this embodiment is 70%.

[0140] Example 11

[0141] This embodiment is basically the same as Embodiment 1, except that the solid content of the homogeneous slurry in this embodiment is 15.1wt% and the viscosity is 5000mPa.s@25℃.

[0142] Example 12

[0143] This embodiment is basically the same as Embodiment 1, except that the solid content of the homogeneous slurry in this embodiment is 24.0 wt% and the viscosity is 48000 mPa.s@25℃.

[0144] Example 13

[0145] This embodiment is basically the same as Embodiment 1, except that the thickness of the two homogeneous layers on both sides of the mesh in this embodiment is 40μm.

[0146] Example 14

[0147] This embodiment is basically the same as Embodiment 1, except that the solid content of the homogeneous slurry in this embodiment is 25.7wt% and the viscosity is 55000mPa.s@25℃.

[0148] Example 15

[0149] This embodiment is basically the same as embodiment 1, except that step (3) in this embodiment is:

[0150] A 40μm thick PEEK mesh was immersed in a homogenized slurry. After the homogenized slurry adhered to the mesh, it was removed and dried sequentially at 60℃ for 2 hours, 80℃ for 3 hours, and 70℃ for 1 hour to obtain an ion exchange membrane with a thickness of 100μm.

[0151] Comparative Example 1

[0152] This comparative example is basically the same as Example 1, except that step (3) in this comparative example is:

[0153] The homogeneous slurry was coated onto a flat PET substrate with a coating thickness of 160 μm. It was then dried sequentially at 60℃ for 2 h, 80℃ for 3 h, and 70℃ for 1 h to obtain an ion exchange homogeneous membrane with a thickness of 100 μm.

[0154] Comparative Example 2

[0155] This comparative example is basically the same as Example 6, except that step (3) in this comparative example is:

[0156] The homogeneous slurry was coated onto a PET substrate with a 20μm PEEK mesh, resulting in a coating thickness of 160μm. The coating was then dried sequentially at 60℃ for 2 hours, 80℃ for 3 hours, and 70℃ for 1 hour to obtain an ion exchange membrane with a thickness of 80μm.

[0157] Comparative Example 3

[0158] This embodiment is basically the same as Embodiment 1, except that the porosity of the mesh in this embodiment is 90%.

[0159] Test example: The performance of the anion exchange composite membranes obtained in the examples and comparative examples was tested, and the test data are shown in Table 1.

[0160] 1. Mechanical performance testing

[0161] Test Method: Refer to GB / T 1447-2005, Tensile Properties Test Method for Fiber Reinforced Plastics. Under constant temperature and humidity conditions of 23℃±2℃ and 50%±10%, measure the thickness and width of the anion exchange membrane. Place the anion exchange membrane in the test fixture. Different tensile speeds can be used to determine the tensile strength and elongation at break, selected within the range of 50 mm / min to 200 mm / min. For each tensile speed, a separate anion exchange membrane should be applied. After the anion exchange membrane breaks, read the corresponding load value.

[0162] a. Tensile strength: The ratio of the maximum load that an anion exchange membrane can withstand when it breaks under pure tensile force to the width of the membrane material being stretched. It is divided into transverse and longitudinal tensile strength and is used to evaluate the mechanical strength of the membrane.

[0163] b. Elongation at break: The ratio of the distance between the two points at break to the original length under the maximum load before the anion exchange membrane breaks. It represents the maximum deformation a basic membrane can withstand before breaking, indicating the membrane's flexibility.

[0164] 2. Swelling performance test

[0165] Test method: Cut the anion exchange membrane into 2cm×4cm pieces, place them in 1M KOH solution, change the alkali three times, and test the swelling performance in deionized water at 80℃.

[0166] 3. Electrolysis of water application test

[0167] An anion exchange membrane was fabricated as a membrane electrode with an active area of ​​80 cm². 2 The cathode nickel-molybdenum alloy loading is 1.0 mg / cm³. 2 The nickel ferrite loading at the anode is 1.2 mg / cm³. 2 Then, they are assembled into a single-cell electrolyzer. Under the condition of 60℃, the positive and negative electrodes are connected, and the polarization performance and sheet resistance of the anion exchange membrane are tested by an electrochemical workstation.

[0168] a. Polarization performance: Using an electrochemical workstation, select the linear voltammetry (LSV) mode, with a current testing range typically 0-80V (based on 80cm). 2 (Definition of active area). Information such as potential and current curves is obtained through testing, and further information processing yields the polarization performance.

[0169] b. Sheet resistance: Using an electrochemical workstation, select the AC impedance test (EIS) mode to test and obtain information such as high-frequency impedance, and then further process the information to obtain the sheet resistance.

[0170] Table 1

[0171]

[0172] Note: In Example 15, the membrane material prepared by the single immersion process had pits on the membrane surface; in Comparative Example 2, the composite homogeneous layer and the mesh separated during short-term testing.

[0173] As can be seen from Table 1:

[0174] Compared with Examples 1 to 4, the test results of anion exchange membranes made from different anion exchange resins are similar, which means that the preparation process of this application has universality and can respond to the composite needs of different anion exchangers.

[0175] Compared to Examples 1, 5, and 6, with increasing mesh thickness, the anion exchange membrane exhibits higher tensile strength and lower swelling ratio, but also higher sheet resistance and higher polarization performance. This indicates that a thicker mesh results in better mechanical properties but poorer electrochemical performance for the anion exchange membrane.

[0176] Compared to Examples 1, 7, and 8, the test results of the anion exchange membranes were similar under the same anion exchange membrane thickness conditions. This indicates that the thickness fluctuations of the first and second homogeneous layers have no significant impact on the material properties. Compared to Example 13, Examples 13 exhibited higher tensile strength, higher elongation at break, and lower swelling ratio, but also higher sheet resistivity and polarization performance. This demonstrates that different anion exchange membrane thicknesses have a significant impact on mechanical and electrochemical properties; thicker membranes generally result in better mechanical properties but poorer electrochemical properties.

[0177] Compared with Examples 1, 9, 10 and Comparative Example 3, the mechanical and electrochemical properties of Examples 1, 9, and 10 are similar. The tensile strength and elongation at break of Example 14 are significantly lower than those of Examples 1, 9, and 10. The swelling ratio of Comparative Example 3 is significantly higher than that of Examples 1, 9, and 10. The sheet resistivity and polarization performance of Comparative Example 3 are slightly lower than those of Examples 1, 9, and 10. It can be seen that, for the same anion exchange membrane thickness, a porosity of 50-70% has no significant effect on electrochemical performance but a weak effect on mechanical properties. When the porosity is 90%, the electrochemical performance is slightly improved, but the mechanical properties of the membrane material are significantly reduced.

[0178] Compared with Examples 1, 11, 12 and 14, the sheet resistance and polarization performance of Example 14 are significantly higher. This is because the excessively high viscosity results in poor wetting and composite effect of the anion exchange resin, and there may be more voids in the anion exchange membrane, which increases the mass transfer resistance and ultimately leads to a deterioration in the electrochemical performance of the anion exchange membrane.

[0179] Compared with Examples 1 and 15, the anion exchange membrane prepared by the two-coating process in Example 1 has higher sheet resistance and polarization performance. In addition, the anion exchange membrane prepared by the one-immersion process has pits on the membrane surface, which is caused by the loss of slurry in the mesh pores during the drying stage. Furthermore, the thickness uniformity of the anion exchange membrane is poor.

[0180] Compared with Comparative Example 1, under the same conditions of anion exchange resin and anion exchange membrane thickness, the tensile strength of Example 1 is much greater than that of Comparative Example 1, indicating that the anion exchange membrane in Example 1 exhibits superior mechanical properties. The swelling rate of Example 1 is much smaller than that of Comparative Example 1, which means that the anion exchange membrane in Example 1 has excellent dimensional stability and can overcome the deformation problem during the application stage. The sheet resistivity and polarization performance of Example 1 and Comparative Example 1 are similar, indicating that the anion exchange membrane under the process of this application can still maintain electrochemical performance comparable to that of the homogeneous membrane in Comparative Example 1.

[0181] Compared with Comparative Example 2, the mechanical properties of Example 6 are similar under the two composite processes, but Example 6 shows better dimensional stability (lower swelling rate). This is mainly attributed to the difference in the binding effect of the support layer (mesh) on the homogeneous layer. An excessively thick homogeneous layer weakens the binding effect of the support layer, thus failing to effectively control the swelling of the anion exchange membrane. In addition, Comparative Example 2 showed separation between the homogeneous layer and the mesh during short-term testing. An excessively thick homogeneous layer on one side exacerbates the separation of the two phases.

[0182] Example 16

[0183] (1) Take 15g of QAPPT (a copolymer of p-terphenyl and N-methyl-4-piperidinone) resin and mix it with 90mL of dimethyl sulfoxide. Heat and stir in an 80℃ water bath for 6h until completely dissolved to obtain a resin solution with a viscosity of 630mPa·s and a solid content of 12% at 25℃.

[0184] (2) The resin solution obtained in step (1) is filtered through a 20,000-mesh PPS membrane to obtain a resin solution after removing impurities.

[0185] (3) The resin solution obtained in step (2) is coated on a flat PET substrate to obtain a first resin solution coating with a coating thickness of 200 μm;

[0186] (4) A PEEK mesh with a thickness of 40 μm, a pore size of 120 μm, and a porosity of 65% is laid flat on the surface of the first resin solution coating obtained in step (3) and pre-dried at 50°C for 30 min to form a support layer 10.

[0187] (5) The resin solution obtained in step (2) is coated onto the support layer 10 obtained in step (4), the coating thickness is 550 μm, and then dried at 60°C for 4 h to obtain an anion exchange membrane, wherein the thickness of the anion exchange membrane is 120 ± 5 μm.

[0188] The structure of QAPPT is shown below:

[0189] .

[0190] Example 17

[0191] (1) Take 15g of QAPPT (a copolymer of p-terphenyl and N-methyl-4-piperidinone) resin and mix it with 60mL of dimethyl sulfoxide. Heat and stir in an 80℃ water bath for 6h until completely dissolved to obtain a resin solution with a viscosity of 8200mPa·s and a solid content of 16.8% at 25℃.

[0192] (2) The resin solution obtained in step (1) is filtered through a 20,000-mesh PPS membrane to obtain a resin solution after removing impurities.

[0193] (3) The resin solution obtained in step (2) is coated on a flat PET substrate to obtain a first resin solution coating with a coating thickness of 150 μm;

[0194] (4) A PPS mesh with a thickness of 60 μm, a pore size of 120 μm, and a porosity of 70% is laid flat on the surface of the first resin solution coating obtained in step (3) and pre-dried at 50°C for 30 min to form a support layer 10.

[0195] (5) The resin solution obtained in step (2) is coated onto the support layer 10 obtained in step (4), the coating thickness is 400 μm, and then dried at 60°C for 4 h to obtain an anion exchange membrane, wherein the thickness of the anion exchange membrane is 120 ± 5 μm.

[0196] Example 18

[0197] (1) Take 15g of QAPPT (a copolymer of p-terphenyl and N-methyl-4-piperidinone) resin and mix it with 60mL of dimethyl sulfoxide. Heat and stir in an 80℃ water bath for 6h until completely dissolved to obtain a resin solution with a viscosity of 8200mPa·s and a solid content of 16.8% at 25℃.

[0198] (2) The resin solution obtained in step (1) is filtered through a 20,000-mesh PPS membrane to obtain a resin solution after removing impurities.

[0199] (3) The resin solution obtained in step (2) is coated on a flat PET substrate to obtain a first resin solution coating with a coating thickness of 150 μm;

[0200] (4) A PEEK mesh with a thickness of 40 μm, a pore size of 120 μm, and a porosity of 65% is laid flat on the surface of the first resin solution coating obtained in step (3) and pre-dried at 50°C for 30 min to form a support layer 10.

[0201] (5) The resin solution obtained in step (2) is coated onto the support layer 10 obtained in step (4), the coating thickness is 400 μm, and then dried at 60°C for 4 h to obtain an anion exchange membrane, wherein the thickness of the anion exchange membrane is 120 ± 5 μm.

[0202] Example 19

[0203] (1) Take 15g of QAPPT (a copolymer of p-terphenyl and N-methyl-4-piperidinone) resin and mix it with 60mL of dimethyl sulfoxide. Heat and stir in an 80℃ water bath for 6h until completely dissolved to obtain a resin solution with a viscosity of 8200mPa·s and a solid content of 16.8% at 25℃.

[0204] (2) The resin solution obtained in step (1) is filtered through a 20,000-mesh PPS membrane to obtain a resin solution after removing impurities.

[0205] (3) The resin solution obtained in step (2) is coated on a flat PET substrate to obtain a resin solution coating with a coating thickness of 550 μm;

[0206] (4) A PEEK mesh with a thickness of 40 μm, a pore size of 120 μm, and a porosity of 65% is laid flat on the surface of the first resin solution coating obtained in step (3) and dried at 60°C for 4 h to obtain an anion exchange membrane, wherein the thickness of the anion exchange membrane is 120 ± 5 μm.

[0207] Example 20

[0208] (1) Take 15g of QAPPT (a copolymer of p-terphenyl and N-methyl-4-piperidinone) resin and mix it with 60mL of dimethyl sulfoxide. Heat and stir in an 80℃ water bath for 6h until completely dissolved to obtain a resin solution with a viscosity of 8200mPa·s and a solid content of 16.8% at 25℃.

[0209] (2) The resin solution obtained in step (1) is filtered through a 20,000-mesh PPS membrane to obtain a resin solution after removing impurities.

[0210] (3) A PEEK mesh with a thickness of 40 μm, a pore size of 120 μm, and a porosity of 65% is laid flat on the flat PET substrate to obtain a support layer;

[0211] (4) The resin solution obtained in step (2) is coated on the side of the support layer obtained in step (3) away from the PET substrate to obtain a resin solution coating with a thickness of 550 μm. The coating is dried at 60°C for 4 h to obtain an anion exchange membrane with a thickness of 120 ± 5 μm.

[0212] Example 21

[0213] (1) Take 15g of QAPPT (a copolymer of p-terphenyl and N-methyl-4-piperidinone) resin and mix it with 60mL of dimethyl sulfoxide. Heat and stir in an 80℃ water bath for 6h until completely dissolved to obtain a resin solution with a viscosity of 8200mPa·s and a solid content of 16.8% at 25℃.

[0214] (2) The resin solution obtained in step (1) is filtered through a 20,000-mesh PPS membrane to obtain a resin solution after removing impurities.

[0215] (3) The resin solution obtained in step (2) is coated on a flat PET substrate to obtain a first resin solution coating with a coating thickness of 150 μm;

[0216] (4) A PEEK mesh with a thickness of 100 μm, a pore size of 200 μm, and a porosity of 70% is laid flat on the surface of the first resin solution coating obtained in step (3), and pre-drying at 50°C for 30 min to form a support layer 10.

[0217] (5) The resin solution obtained in step (2) is coated onto the support layer 10 obtained in step (4), the coating thickness is 350 μm, and then dried at 60°C for 4 h to obtain an anion exchange membrane, wherein the thickness of the anion exchange membrane is 120 ± 5 μm.

[0218] Example 22

[0219] (1) Take 15g of QAFMPPT (9,9-dimethylfluorene, a binary copolymer of terphenyl and N-methyl-4-piperidinone) resin and mix it with 45mL of dimethyl sulfoxide. Heat and stir in an 80℃ water bath for 6h until completely dissolved to obtain a resin solution with a viscosity of 4500mPa·s and a solid content of 25.1% at 25℃.

[0220] (2) The resin solution obtained in step (1) is filtered through a 20,000-mesh PPS membrane to obtain a resin solution after removing impurities.

[0221] (3) The resin solution obtained in step (2) is coated on a flat PET substrate to obtain a first resin solution coating with a coating thickness of 150 μm;

[0222] (4) A PEEK mesh with a thickness of 40 μm, a pore size of 120 μm, and a porosity of 65% is laid flat on the surface of the first resin solution coating obtained in step (3) and pre-dried at 50°C for 30 min to form a support layer 10.

[0223] (5) The resin solution obtained in step (2) is coated onto the support layer 10 obtained in step (4), the coating thickness is 350 μm, and then dried at 60°C for 4 h to obtain an anion exchange membrane, wherein the thickness of the anion exchange membrane is 120 ± 5 μm.

[0224] The structure of QAFMPPT is shown below:

[0225] .

[0226] Comparative Example 4

[0227] (1) Take 15g of polyarylene ether structure resin (chemical structure shown in the figure below) and mix it with 60mL of dimethyl sulfoxide. Heat and stir in an 80℃ water bath for 6h until completely dissolved to obtain a resin solution with a viscosity of 6300mPa·s and a solid content of 19.7% at 25℃.

[0228] (2) The resin solution obtained in step (1) is filtered through a 20,000-mesh PPS membrane to obtain a resin solution after removing impurities.

[0229] (3) The resin solution obtained in step (2) is coated on a flat PET substrate to obtain a first resin solution coating with a coating thickness of 150 μm;

[0230] (4) A PEEK mesh with a thickness of 40 μm, a pore size of 120 μm, and a porosity of 65% is laid flat on the surface of the first resin solution coating obtained in step (3) and pre-dried at 50°C for 30 min to form a support layer 10.

[0231] (5) The resin solution obtained in step (2) is coated onto the support layer 10 obtained in step (4), the coating thickness is 400 μm, and then dried at 60°C for 4 h to obtain an anion exchange membrane, wherein the thickness of the anion exchange membrane is 120 ± 5 μm.

[0232] The structural formula of polyarylene ether resin is shown below:

[0233] .

[0234] Comparative Example 5

[0235] (1) Take 15g of QAPPT (a copolymer of p-terphenyl and N-methyl-4-piperidinone) resin and mix it with 60mL of dimethyl sulfoxide. Heat and stir in an 80℃ water bath for 6h until completely dissolved to obtain a resin solution with a viscosity of 8200mPa·s and a solid content of 16.8% at 25℃.

[0236] (2) The resin solution obtained in step (1) is filtered through a 20,000-mesh PPS membrane to obtain a resin solution after removing impurities.

[0237] (3) The resin solution obtained in step (2) is coated on a flat PET substrate to obtain a resin solution coating with a coating thickness of 550 μm; and dried at 60°C for 5 h to obtain an anion exchange membrane with a thickness of 120 ± 5 μm.

[0238] The methods for testing the viscosity and solid content of the resin solutions in Examples 1-7 and Comparative Examples 1-2 are as follows:

[0239] Viscosity: Take approximately 10 mL of the solution to be tested into the barrel, place the barrel in the testing chamber of the viscosity analyzer, select the appropriate rotor and test range according to the material viscosity, place the rotor into the resin solution in the barrel, and adjust the volume of the resin solution in the barrel until the solution just completely submerges the rotor. Then start the test at 25±0.5℃. After the instrument reading stabilizes, the displayed reading is the viscosity of the resin solution.

[0240] Solid content: Place the asbestos pad on the tray of the solid content tester. After the instrument automatically zeroes, take 0.6g-0.7g of the solution to be tested and spread it evenly on the asbestos pad. Then close the instrument cover and start the test. After the instrument automatically heats up and completes the test, the displayed reading is the solid content of the resin solution.

[0241] The tensile strength, elongation at break, and water electrolysis performance of the anion exchange membranes in Examples 16-22 and Comparative Examples 4-5 were tested. The tensile strength and elongation at break were tested according to GB / T 20042.3-2009. Under conditions of 25±2℃ and 50±5% relative humidity, the prepared anion exchange membranes were cut into dumbbell shapes, 150mm long and 20mm wide, horizontally or vertically. The thickness was tested three times in the middle region of the sample, and the average thickness was recorded. The sample was then placed in a test fixture and tested at a tensile speed of 50mm / min. After the sample broke, the corresponding load value was recorded. For horizontal or vertical cutting methods, separate samples should be used for each method. The water electrolysis performance was tested using a single chamber with an active area of ​​80cm². 2 A total of 6 chambers were used, employing a nickel ferrite anode-Pt / C cathode catalytic system. A 1M KOH solution at 60℃ was used as the electrolyte, and the system was continuously operated for 500 hours under a cathode pressure of 1.6 MPa. The polarization performance of the anion exchange membrane in the electrolyzer was tested after 500 hours of continuous operation. Gas collection and GC testing were performed on the anode-side produced gas to verify the hydrogen content data in the oxygen content of the material.

[0242] The test results are shown in Table 2:

[0243] Table 2 Comparison of performance test results of anion exchange membranes in different embodiments

[0244]

[0245] As shown in Table 2, compared with Comparative Example 4, the physical and electrochemical properties of the anion exchange membranes in Examples 16-22 are significantly better than those in Comparative Example 4. This is mainly because Comparative Examples 16-21 are QAPPT resin systems and Example 22 is a QAFMPPT resin system. The resins contain both aryl groups and piperidinone groups, which can ensure that the anion exchange membrane has high ionic conductivity and reduce internal resistance. Comparative Example 4 is a polyaryl ether structure resin system, which does not contain piperidinone groups and has poor performance. Compared with Comparative Example 5, the electrochemical performance of the anion exchange membranes in Examples 16-22 and Comparative Example 5 is similar. However, the physical performance of the anion exchange membranes in Examples 16-22 is significantly better than that of the anion exchange resin in Comparative Example 5. This is mainly because a support layer 10 is provided in Examples 16-22. The porous matrix in the support layer 10 can provide good support, improve the mechanical properties and pressure resistance of the anion exchange membrane, and work well with the anion exchange resin.

[0246] The comparison between Examples 16-22 shows that when the resin solution viscosity is below 1000 mPa·s, the prepared material exhibits good oxygen-to-hydrogen performance, but the surface impedance is relatively high, corresponding to a higher cell voltage. This is suitable for scenarios where there is a high demand for oxygen-to-hydrogen but no significant requirement for electrochemical performance. When the resin solution viscosity is 8000 mPa·s, the material exhibits good electrochemical performance, but the oxygen-to-hydrogen ratio is relatively high. This is suitable for scenarios with higher requirements for electrochemical performance. In single-sided film formation, the lower single-sided film formation process offers the lowest process cost, but the film formation performance is inferior. The upper single-sided film formation process has a cost between the lower single-sided and double-sided film formation processes, and the film formation performance is good. Compared to PEEK mesh, PPS mesh shows a slight decrease in overall film formation performance, but its price is much lower than PEEK mesh, giving it a significant cost advantage.

[0247] Example 23

[0248] (1) Take 15g of QAPPT (a copolymer of p-terphenyl and N-methyl-4-piperidinone) resin and mix it with 60mL of dimethyl sulfoxide. Heat and stir in an 80℃ water bath for 6h until completely dissolved to obtain a resin solution with a viscosity of 11000mPa·s and a solid content of 17% at 25℃.

[0249] (2) Add N-ethyl-p-toluenesulfonamide to the resin solution at a mass percentage of 5%, and stir thoroughly at room temperature for 1 hour until completely dissolved to obtain a homogeneous resin solution;

[0250] (3) The resin solution obtained in step (2) is filtered through a 20,000-mesh PPS membrane to obtain a homogeneous resin solution after removing impurities;

[0251] (4) A PEEK mesh with a thickness of 40 μm, a pore size of 120 μm, and a porosity of 65% is laid flat on the surface of a PET substrate. The homogeneous resin solution obtained in step (3) is then coated on the surface of the PEEK mesh with a coating height of 550 μm. The membrane is then dried at 60°C for 4 hours to obtain an anion exchange membrane with a thickness of 120 ± 5 μm.

[0252] The structure of QAPPT is shown below:

[0253] .

[0254] Example 24

[0255] (1) Take 15g of QAPPT (a copolymer of p-terphenyl and N-methyl-4-piperidinone) resin and mix it with 60mL of dimethyl sulfoxide. Heat and stir in an 80℃ water bath for 6h until completely dissolved to obtain a resin solution with a viscosity of 11000mPa·s and a solid content of 17% at 25℃.

[0256] (2) Add N-ethyl-p-toluenesulfonamide to the resin solution at a mass percentage of 5%, and stir thoroughly at room temperature for 1 hour until completely dissolved to obtain a homogeneous resin solution;

[0257] (3) The resin solution obtained in step (2) is filtered through a 20,000-mesh PPS membrane to obtain a homogeneous resin solution after removing impurities;

[0258] (4) A PEEK mesh with a thickness of 40 μm, a pore size of 120 μm, and a porosity of 65% is laid flat on the surface of a PET substrate. The homogeneous resin solution obtained in step (3) is then coated on the surface of the PEEK mesh with a coating height of 800 μm. The membrane is then dried at 60°C for 4 hours to obtain an anion exchange membrane with a thickness of 180 ± 5 μm.

[0259] Example 25

[0260] (1) Take 15g of QAFMPPT (terphenyl, 9,9-dimethylfluorene and N-methyl-4-piperidinone binary copolymer) resin and mix it with 60mL of dimethyl sulfoxide. Heat and stir in an 80℃ water bath for 6h until completely dissolved to obtain a resin solution with a viscosity of 11000mPa·s and a solid content of 17% at 25℃.

[0261] (2) Add N-ethyl-p-toluenesulfonamide to the resin solution at a mass percentage of 5%, and stir thoroughly at room temperature for 1 hour until completely dissolved to obtain a homogeneous resin solution;

[0262] (3) The resin solution obtained in step (2) is filtered through a 20,000-mesh PPS membrane to obtain a homogeneous resin solution after removing impurities;

[0263] (4) A PEEK mesh with a thickness of 40 μm, a pore size of 120 μm, and a porosity of 65% is laid flat on the surface of a PET substrate. The homogeneous resin solution obtained in step (3) is then coated on the surface of the PEEK mesh with a coating height of 450 μm. The membrane is then dried at 60°C for 4 hours to obtain an anion exchange membrane with a thickness of 120 ± 5 μm.

[0264] The structure of QAFMPPT is shown below:

[0265] .

[0266] Example 26

[0267] (1) Take 15g of QAPPT (a copolymer of p-terphenyl and N-methyl-4-piperidinone) resin and mix it with 60mL of dimethyl sulfoxide. Heat and stir in an 80℃ water bath for 6h until completely dissolved to obtain a resin solution with a viscosity of 11000mPa·s and a solid content of 17% at 25℃.

[0268] (2) Add N-ethyl-p-toluenesulfonamide to the resin solution at a mass percentage of 1%, and stir thoroughly at room temperature for 1 hour until completely dissolved to obtain a homogeneous resin solution;

[0269] (3) The resin solution obtained in step (2) is filtered through a 20,000-mesh PPS membrane to obtain a homogeneous resin solution after removing impurities;

[0270] (4) A PEEK mesh with a thickness of 40 μm, a pore size of 120 μm, and a porosity of 65% is laid flat on the surface of a PET substrate. The homogeneous resin solution obtained in step (3) is then coated on the surface of the PEEK mesh with a coating height of 550 μm. The membrane is then dried at 60°C for 4 hours to obtain an anion exchange membrane with a thickness of 120 ± 5 μm.

[0271] Example 27

[0272] (1) Take 15g of QAPPT (a copolymer of p-terphenyl and N-methyl-4-piperidinone) resin and mix it with 60mL of dimethyl sulfoxide. Heat and stir in an 80℃ water bath for 6h until completely dissolved to obtain a resin solution with a viscosity of 11000mPa·s and a solid content of 17% at 25℃.

[0273] (2) Add N-ethyl-p-toluenesulfonamide to the resin solution at a mass percentage of 10%, and stir thoroughly at room temperature for 1 hour until completely dissolved to obtain a homogeneous resin solution;

[0274] (3) The resin solution obtained in step (2) is filtered through a 20,000-mesh PPS membrane to obtain a homogeneous resin solution after removing impurities;

[0275] (4) A PEEK mesh with a thickness of 40 μm, a pore size of 120 μm, and a porosity of 65% is laid flat on the surface of a PET substrate. The homogeneous resin solution obtained in step (3) is then coated on the surface of the PEEK mesh with a coating height of 550 μm. The membrane is then dried at 60°C for 4 hours to obtain an anion exchange membrane with a thickness of 120 ± 5 μm.

[0276] Comparative Example 6

[0277] The difference between this comparative example and Example 1 is that no plasticizer was added to the resin solution, while all other conditions remained the same as in Example 1.

[0278] Comparative Example 7

[0279] The difference between this comparative example and Example 1 is that N-ethyl-p-toluenesulfonamide is replaced with an equal amount of polyoxypropylene diamine, while all other conditions remain the same as in Example 1.

[0280] Comparative Example 8

[0281] The difference between this comparative example and Example 1 is that N-ethyl-p-toluenesulfonamide is replaced with an equal amount of epoxy fatty acid methyl ester, while all other conditions remain the same as in Example 1.

[0282] The viscosity and solid content of the resin solutions in Examples 23-27 and Comparative Examples 6-8 were tested, and the tensile strength, elongation at break, and electrolytic water performance of the prepared anion exchange membranes were also tested. The method for testing the resin solution viscosity was as follows: approximately 10 mL of the solution to be tested was placed in a barrel, which was then placed in the testing chamber of the viscosity analyzer. An appropriate rotor and testing range were selected based on the material viscosity. The rotor was then placed into the resin solution in the barrel, and the volume of the resin solution in the barrel was adjusted until the solution just completely submerged the rotor. The test was then started at 25±0.5℃. After the instrument reading stabilized, the displayed reading was the resin solution viscosity. The method for testing the resin solution solid content was as follows: an asbestos pad was placed above the tray of the solid content analyzer. After the instrument automatically zeroed, 0.6-0.7 g of the solution to be tested was taken and evenly coated onto the asbestos pad. The instrument top cover was then closed, and the test was started. After the instrument automatically heated and completed the test, the displayed reading was the resin solid content. The test methods for tensile strength and elongation at break are as follows: Referring to GB / T 20042.3-2009, under conditions of 25±2℃ and 50±5% relative humidity, the prepared anion exchange membrane is cut into dumbbell-shaped samples, 150mm long and 20mm wide, either horizontally or vertically. The thickness is tested three times in the middle region of the sample, and the average thickness is recorded. Subsequently, the sample is placed in a test fixture and tested at a tensile speed of 50mm / min. After the sample breaks, the corresponding load value is recorded. For horizontal or vertical cutting methods, separate samples should be used for each method. The test method for the electrolysis performance is as follows: Under conditions of 80cm² active area per chamber, a total of 6 chambers, a nickel ferrite anode-Pt / C cathode catalytic system, using 1M KOH solution at 60℃ as the electrolyte, and a cathode pressure of 1.6MPa, continuous operation for 500h is performed. The polarization performance of the anion exchange membrane in the electrolyzer is then tested after 500h of continuous operation. The gas produced on the anode side was collected and subjected to GC testing to verify the hydrogen content in the oxygen of the material.

[0283] The test results are shown in Table 3:

[0284] Table 3. Comparison of performance test results of anion exchange membranes in different embodiments

[0285]

[0286] As shown in Table 3, compared with Comparative Example 3, the viscosity of the resin solution in Examples 8-12 was significantly lower than that in Comparative Example 3 without plasticizer, while the tensile strength and elongation at break of the resulting anion exchange membranes were basically the same. Compared with Comparative Examples 4-5, when N-ethyl-p-toluenesulfonamide was replaced with an equal amount of other plasticizers, the viscosity of the resin solution increased significantly, and the tensile strength and elongation at break of the resulting anion exchange membranes decreased significantly.

[0287] The thickness uniformity and pressure holding performance of the anion exchange membranes in Examples 23-27 and Comparative Examples 6-8 were tested respectively. The thickness uniformity was tested by using an X-ray testing device to detect the membrane thickness online and recording the thickness range of a single batch. The pressure holding performance was tested by assembling the prepared anion exchange membrane in an electrolytic cell at a temperature of 25±2℃ and a relative humidity of 50±5%. The active area of ​​the anion exchange membrane was 160 cm². 2 Then, nitrogen gas at 3.0 MPa is introduced into the cathode side of the electrolytic cell, while the anode side is connected to the atmosphere. After the pressure on the cathode side stabilizes, the gas supply valve on the cathode side is closed to keep the entire cathode of the electrolytic cell in a sealed state. The electrolytic cell is then left to stand for 24 hours in this state, and the pressure change on the cathode side is recorded after 24 hours. The leakage rate is calculated based on the pressure change and the cathode volume.

[0288] The test results are shown in Table 4:

[0289] Table 4

[0290]

[0291] As shown in Table 4, compared with Comparative Example 6, the addition of N-ethyl-p-toluenesulfonamide plasticizer in Examples 23-27 significantly reduced the thickness variation, ensuring the thickness uniformity of the anion exchange membrane, and reducing defects such as pores and bubbles, resulting in a significant decrease in leakage rate. Compared with Comparative Examples 7-8, when N-ethyl-p-toluenesulfonamide was replaced with an equal amount of other plasticizers in Example 23, the thickness variation significantly increased, and the leakage rate also significantly improved, indicating that N-ethyl-p-toluenesulfonamide and the anion exchange resin exhibited a synergistic effect, producing unexpected technical benefits.

[0292] The anion exchange membranes in Examples 23-27 and Comparative Examples 6-8 were tested for their performance in water electrolysis. The test method was as follows: [The text abruptly ends here, so the translation stops as well.] 2 A nickel ferrite anode-Pt / C cathode catalytic system was used, with 1M KOH solution at 60℃ as the electrolyte and the cathode pressurized to 1.6 MPa for 500 hours of continuous operation. The polarization performance of the enhanced anion exchange membrane in the electrolyzer was tested after 500 hours of continuous operation. Gas collection and GC testing were performed on the anode-side produced gas to verify the hydrogen content data of the material's oxygen content.

[0293] The test results are shown in Table 5:

[0294] Table 5

[0295]

[0296] As can be seen from Table 5, compared with Comparative Examples 6-8, Examples 23-27 showed significantly improved polarization performance, reduced hydrogen content in oxygen, and significantly reduced surface reactance.

[0297] In summary, compared with Comparative Examples 6-8, Examples 23-27 of this application significantly reduce the viscosity of the resin solution, ensure the mechanical strength and stability of the anion exchange resin, significantly improve the thickness uniformity, reduce porosity and bubble defects, significantly reduce the surface resistivity, and significantly improve the performance of water electrolysis, producing unexpected technical effects.

Claims

1. An anion exchange membrane, comprising a support layer (10) and a homogeneous layer (20) located on one side of the support layer (10) in the thickness direction. The homogeneous layer (20) includes anion exchange resin and plasticizer, and the support layer (10) includes a porous substrate and the anion exchange resin and plasticizer filled in the porous substrate; in, The anion exchange resin comprises the compound shown in Formula I: Formula I; In Formula I, A1, A2 and A3 are independently selected from substituted or unsubstituted aryl groups, C is a group containing a carbonyl group, D is a group containing a piperidinone group, E is a group containing a quinine cyclic ketone group, 0≤x≤1, 0≤y≤1, 0≤z≤1, x+y+z=1, and n is an integer between 10 and 1000000. The plasticizer includes N-ethyl-p-toluenesulfonamide; The porous substrate is made of at least one of polyetheretherketone, polyphenylene sulfide, polyphenylene sulfone, polyethersulfone, polypropylene, polyethylene, polyethylene terephthalate, polytetrafluoroethylene, expanded polytetrafluoroethylene, and liquid crystal polymer.

2. The anion exchange membrane according to claim 1, wherein, In the homogeneous layer (20), the mass ratio of the anion exchange resin to the plasticizer is 1:(0.05-0.6); And / or, in the support layer (10), the mass ratio of the anion exchange resin to the plasticizer is 1:(0.05-0.6).

3. The anion exchange membrane according to claim 1 or 2, wherein, The thickness of the support layer (10) is 5μm-200μm; And / or, the thickness of the homogeneous layer (20) is 10μm-100μm.

4. The anion exchange membrane according to any one of claims 1-3, wherein, The porosity of the porous substrate is 30%-90%; And / or, the pore size range of the porous substrate is 20μm-200μm; And / or, the porous substrate includes at least one of woven fabric, nonwoven fabric, and porous polymer layer.

5. The anion exchange membrane according to any one of claims 1-4, wherein, The anion exchange resin comprises compounds as shown in Formula II: Formula II; In Formula II, R1 and R3 are each independently selected from one of the following: hydrogen, a substituted or unsubstituted alkyl chain with 1-10 carbon atoms, a group containing heteroatoms, and a substituted or unsubstituted polycyclic structure; R2 is selected from at least one of a substituted or unsubstituted polycyclic structure and a substituted or unsubstituted alkyl chain, and the number of substituted or unsubstituted polycyclic structures in R2 is 0-10; R4, R5, R6, R7, and R8 are each independently selected from one of the following: hydrogen, fluorine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, and a substituted or unsubstituted aromatic group; Z1 - and Z2 - Selected independently from OH - Cl - ,Br - HCO3 - NO3 - CF3COO - CH3COO - and R0SO3 - At least one of the following: wherein R0 is selected from methyl, ethyl, vinyl, cyclopropyl, trifluoromethyl, phenyl, tolyl, nitrophenyl and benzyl.

6. The anion exchange membrane according to any one of claims 1-5, wherein, A1, A2, and A3 are each independently selected from at least one of biphenyl, p-terphenyl, m-terphenyl, p-tetraphenyl, diphenylmethane, triphenylmethane, 9,10-benzophenanthrene, tetraphenylmethane, tripterene, 9,9'-spirodifluorene, 9,9'-bicarbazole, 2,2'-bi-9,9'-spirobis[9Hfluorene], 4,4-bis(9-carbazole)biphenyl, triphenylamine, 9,9'-bifluorene, 9,9'-diphenylfluorene, 9,9'-dimethylfluorene, and 1,3,5-triphenylbenzene; And / or, the C is selected from at least one of butanedione, trifluoroacetone and hydroxyacetone; And / or, the D is selected from compounds as described in any one of Formulas 1-14; ； And / or, the E is selected from any one of the compounds described in formulas 15-17: 。 7. A method for preparing an anion exchange membrane, comprising: An anion exchange resin and a plasticizer are dispersed in a solvent to obtain an anion exchange resin solution. A porous substrate is attached to the surface of a base membrane, and the anion exchange resin solution is coated on the surface of the porous substrate away from the base membrane, so that the anion exchange resin solution fills the porous structure of the porous substrate and covers the surface of the porous substrate. After drying, a support layer (10) and a homogeneous layer (20) are formed. The solution is then peeled off from the surface of the base membrane to obtain an anion exchange membrane. The anion exchange resin includes the compound represented by Formula I: Formula I; In the formula, A1, A2 and A3 are independently selected from substituted or substituted aryl groups, C is a group containing a carbonyl group, D is a group containing a piperidinone group, E is a group containing a quinine cyclic ketone group, 0≤x≤1, 0≤y≤1, 0≤z≤1, x+y+z=1, and n is an integer between 10 and 1000000. The plasticizer includes N-ethyl-p-toluenesulfonamide; The porous substrate is made of at least one of polyetheretherketone, polyphenylene sulfide, polyphenylene sulfone, polyethersulfone, polypropylene, polyethylene, polyethylene terephthalate, polytetrafluoroethylene, expanded polytetrafluoroethylene, and liquid crystal polymer.

8. The method for preparing the anion exchange membrane according to claim 7, wherein, The solid content of the anion exchange resin solution is 10%-60%; And / or, in the anion exchange resin solution, the plasticizer has a mass percentage of 1%-10%; And / or, the viscosity of the anion exchange resin solution at 25°C is 500 mPa·s-80000 mPa·s.

9. The method for preparing the anion exchange membrane according to claim 7 or 8, wherein, The method for preparing the anion exchange resin solution includes: The anion exchange resin and the plasticizer are dispersed in a solvent and filtered through a 2000-20000 mesh filter membrane to obtain the anion exchange resin solution.

10. The method for preparing the anion exchange membrane according to claim 9, wherein, The solvent includes at least one selected from dimethyl sulfoxide, tetrahydrofuran, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, and anhydrous ethanol.

11. An electrolytic water hydrogen production apparatus, comprising an anion exchange membrane as described in any one of claims 1-6, and / or an anion exchange membrane prepared by the method described in any one of claims 7-10.

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