阅读说明：本技术 一种有序化碱性阴离子材料及其制备方法、一种阴离子交换膜燃料电池 (Ordered alkaline anion material, preparation method thereof and anion exchange membrane fuel cell ) 是由 于书淳 刘飞磊 徐敏祥 周佩 周媛媛 魏加强 于 2021-07-08 设计创作，主要内容包括：本发明属于燃料电池技术领域,尤其涉及一种有序化碱性阴离子材料及其制备方法、一种阴离子交换膜燃料电池。本发明提供的有序化碱性阴离子材料的制备方法,包括以下步骤：将4,5-二甲基-1-乙烯基咪唑和卤代烷烃溶解进行亲核取代反应,得到乙烯基咪唑类两亲离子液体；将所述乙烯基咪唑类两亲离子液体在水中进行自组装,形成有序化液晶体系,将所述有序化液晶体系在紫外光下进行原位光聚合反应,得到有序化聚离子液体材料；将所述有序化聚离子液体材料与强碱溶液混合进行离子交换,得到所述有序化碱性阴离子材料,实现了有序化碱性阴离子交换膜电导率与膜强度、稳定性的平衡,同时具有高的OH～(-)传输效率和碱稳定性。(The invention belongs to the technical field of fuel cells, and particularly relates to an ordered alkaline anion material, a preparation method thereof and an anion exchange membrane fuel cell. The preparation method of the ordered basic anion material provided by the invention comprises the following steps: dissolving 4, 5-dimethyl-1-vinylimidazole and halogenated alkane for nucleophilic substitution reaction to obtain vinylimidazole amphiphilic ionic liquid; amphiphilic the vinylimidazolesSelf-assembling ionic liquid in water to form an ordered liquid crystal system, and carrying out in-situ photopolymerization on the ordered liquid crystal system under ultraviolet light to obtain an ordered polyion liquid material; mixing the ordered polyion liquid material with a strong base solution for ion exchange to obtain the ordered alkaline anion material, so that the balance of the conductivity of the ordered alkaline anion exchange membrane, the strength and the stability of the membrane is realized, and the ordered alkaline anion exchange membrane has high OH ‑ Transport efficiency and base stability.)

1. A method for preparing an ordered basic anionic material is characterized by comprising the following steps:

dissolving 4, 5-dimethyl-1-vinylimidazole and halogenated alkane for nucleophilic substitution reaction to obtain vinylimidazole amphiphilic ionic liquid;

self-assembling the vinyl imidazole amphiphilic ionic liquid in water to form an ordered liquid crystal system, and carrying out in-situ photopolymerization on the ordered liquid crystal system under ultraviolet light to obtain an ordered polyion liquid material;

and carrying out ion exchange on the ordered polyion liquid material and a strong base solution to obtain the ordered alkaline anion material.

2. The method of claim 1, wherein the haloalkane is C_12～16A halogenated alkane.

3. The method according to claim 1 or 2, wherein the ratio of the amounts of the 4, 5-dimethyl-1-vinylimidazole and the haloalkane is 1 (1.1-2).

4. The preparation method according to claim 1, wherein the temperature of the nucleophilic substitution reaction is 60-80 ℃, the time of the nucleophilic substitution reaction is 36-48 h, and the nucleophilic substitution reaction is performed in a protective gas atmosphere.

5. The preparation method according to claim 1, wherein the mass percentage of the vinylimidazole amphiphilic ionic liquid in water is 50-85%.

6. The method according to claim 1 or 5, wherein the self-assembly temperature is 25 to 40 ℃ and the self-assembly time is 30 to 50 days.

7. The method according to claim 1, wherein the time for the in-situ photopolymerization is 0.5-2 h.

8. The preparation method according to claim 1, wherein the molar concentration of the strong alkali solution is 1-5 mol/L; the time of the ion exchange is 36-48 h, and the ion exchange is carried out in a vacuum environment.

9. An ordered basic anion exchange material prepared by the preparation method of any one of claims 1 to 8.

10. An anion exchange membrane fuel cell, wherein the membrane for an anion exchange membrane fuel cell is the ordered basic anion exchange material according to claim 9.

Technical Field

The invention belongs to the technical field of fuel cells, and particularly relates to an ordered alkaline anion material, a preparation method thereof and an anion exchange membrane fuel cell.

Background

The Alkaline Anion Exchange Membrane Fuel Cell (AAEMFC) can greatly reduce the cost of the fuel cell due to the use of non-noble metal catalyst, and thus becomes a new hot spot in the field of fuel cells, but the performance of the AAEMFC has a certain gap with the performance of the current proton exchange membrane fuel cell. The performance of an Alkaline Anion Exchange Membrane (AAEM) as a key material of the AAEMFCE directly determines the output performance of the battery, so that the development of a high-performance AAEM material is important for improving the performance of the AAEMFCE.

However, there is a significant conflict between conductivity and stability of AAEM materials. Due to OH^-Mobility of less than H⁺Therefore, to obtain higher conductivity, the AAEM material usually needs higher ion exchange capacity, however, this will result in too high water absorption (water swelling ratio) of the AAEM material, and decrease of mechanical strength, and further decrease of effective ion concentration in the membrane, which is not good for OH^-The conduction of the AAEM material can be inhibited by modifying the structure of the AAEM material through compounding and crosslinking, but the improvement of the ionic conductivity is often influenced.

Research shows that the liquid crystal structure formed by self-assembly of the surface active ionic liquid has phase separation at the molecular level, and the hydrophilic region can be OH^-The hydrophobic domain may effectively inhibit swelling of the membrane. However, most of currently prepared anion exchange membranes based on ionic liquid self-assembly liquid crystal structures use imidazole cationic ionic liquids, but the membranes prepared from imidazole cationic ionic liquids have poor stability.

Disclosure of Invention

In view of the above, the invention provides an ordered alkaline anion material, a preparation method thereof and an anion exchange membrane fuel cell.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a preparation method of an ordered alkaline anion material, which comprises the following steps:

dissolving 4, 5-dimethyl-1-vinylimidazole and halogenated alkane for nucleophilic substitution reaction to obtain vinylimidazole amphiphilic ionic liquid;

self-assembling the vinyl imidazole amphiphilic ionic liquid in water to form an ordered liquid crystal system, and carrying out in-situ photopolymerization on the ordered liquid crystal system under ultraviolet light to obtain an ordered polyion liquid material;

and mixing the ordered polyion liquid material with a strong base solution for ion exchange to obtain the ordered basic anion material.

Preferably, the haloalkane is C_12～16A halogenated alkane.

Preferably, the mass ratio of the 4, 5-dimethyl-1-vinyl imidazole to the halogenated alkane is 1 (1.1-2).

Preferably, the temperature of the nucleophilic substitution reaction is 60-80 ℃, the time of the nucleophilic substitution reaction is 36-48 h, and the nucleophilic substitution reaction is carried out in a protective gas atmosphere.

Preferably, in an ionic liquid aqueous solution obtained by mixing the vinylimidazole amphiphilic ionic liquid and water, the mass percentage of the vinylimidazole amphiphilic ionic liquid is 50-85%.

Preferably, the self-assembly temperature is 25-40 ℃, and the self-assembly time is 30-50 days.

Preferably, the time of the in-situ photopolymerization is 0.5-2 h.

Preferably, the molar concentration of the strong alkali solution is 1-5 mol/L; the time of the ion exchange is 36-48 h, and the ion exchange is carried out in a vacuum environment.

The invention provides an ordered alkaline anion material prepared by the preparation method in the technical scheme.

The invention provides an anion exchange membrane fuel cell, and a diaphragm for the anion exchange membrane fuel cell is the ordered alkaline anion exchange material in the technical scheme.

The invention provides a preparation method of an ordered alkaline anion material, which comprises the following steps: dissolving 4, 5-dimethyl-1-vinylimidazole and halogenated alkane for nucleophilic substitution reaction to obtain vinylimidazole amphiphilic ionic liquid; self-assembling the vinyl imidazole amphiphilic ionic liquid in water to form an ordered liquid crystal system, and then carrying out in-situ photopolymerization on the ordered liquid crystal system under ultraviolet light to obtain an ordered polyion liquid material; and mixing the ordered polyion liquid material and a strong base solution for ion exchange to obtain the ordered basic anion material. In the invention, 4, 5-dimethyl-1-vinylimidazole and haloalkane carry out nucleophilic substitution reaction to obtain polymerizable imidazole amphiphilic ionic liquid substituted at C4 and C5, and the polymerizable imidazole amphiphilic ionic liquid has good alkali-resistant stability; when the imidazole amphiphilic ionic liquid is in water, self-assembly is carried out on hydrophilic groups and hydrophobic groups to obtain an ordered structure, double-bond functional groups in an ordered liquid crystal system undergo in-situ polymerization under the irradiation of ultraviolet light to obtain an ordered polyion liquid material retaining the microscopic ordered structure of the liquid crystal, and halide ions in the ordered polyion liquid material are exchanged into hydroxide ions through ion exchange to finally obtain the ordered alkaline anion material; the ordered alkaline anionic material is obtained by self-assembly polymerization of imidazole amphiphilic ionic liquid, a highly ordered liquid crystal microstructure is constructed in the membrane by self-assembly of hydrophilic groups and hydrophobic groups in the amphiphilic ionic liquid, a hydrophilic-hydrophobic water phase separation structure in the membrane is strengthened, a highly ordered ion transmission channel is formed, and the ordered alkaline-resistant alkaline-stable anionic material has the advantages of alkali resistance, stability and stabilityQualitative, realizes the balance of the conductivity, the mechanical strength and the stability of the ordered alkaline anion material, and has high OH^-Transport efficiency and base stability.

Detailed Description

The invention provides a preparation method of an ordered alkaline anion exchange membrane, which comprises the following steps:

dissolving 4, 5-dimethyl-1-vinylimidazole and halogenated alkane for nucleophilic substitution reaction to obtain vinylimidazole amphiphilic ionic liquid;

self-assembling the vinyl imidazole amphiphilic ionic liquid in water to form an ordered liquid crystal system, and carrying out in-situ photopolymerization on the ordered liquid crystal system under ultraviolet light to obtain an ordered polyion liquid material;

and mixing the ordered polyion liquid material with a strong base solution for ion exchange to obtain the ordered basic anion material.

In the present invention, the starting materials are all commercially available products well known to those skilled in the art, unless otherwise specified.

The invention dissolves 4, 5-dimethyl-1-vinylimidazole and halogenated alkane for nucleophilic substitution reaction (hereinafter referred to as first nucleophilic substitution reaction) to obtain the vinylimidazole amphiphilic ionic liquid.

In the present invention, the polar organic solvent for dissolving 4, 5-dimethyl-1-vinylimidazole and haloalkane is preferably methanol and/or acetonitrile, more preferably methanol, and in the present invention, when the polar organic solvent is preferably a mixed solvent of methanol and acetonitrile, the present invention has no special requirement on the specific ratio of the two solvents.

The polar organic solvent used for dissolving in the preparation method provided by the invention is preferably methanol and/or acetonitrile, and raw materials with high toxicity are not used, so that the preparation method is safe and environment-friendly.

The invention has no special requirements on the dosage of the polar organic solvent, and can realize the complete dissolution of the 4, 5-dimethyl-1-vinyl imidazole and the halogenated alkane.

In the present invention, the method for preparing 4, 5-dimethyl-1-vinylimidazole preferably comprises the steps of:

4, 5-dimethylimidazole, vinyl acetate and a catalyst are mixed to carry out an affinity substitution reaction (hereinafter referred to as a second nucleophilic substitution reaction) to obtain the 4, 5-dimethyl-1-vinylimidazole.

In the invention, the catalyst is preferably trifluoroacetic acid and/or mercury acetate, more preferably trifluoroacetic acid and mercury acetate, and the mass ratio of the trifluoroacetic acid to the mercury acetate is preferably (1-2): 1, and more preferably 1.55: 1.

In the invention, the mass ratio of the 4, 5-dimethylimidazole to the vinyl acetate is preferably 1 (3.5-4), and more preferably 1: 3.9.

In the invention, the mass ratio of the 4, 5-dimethylimidazole to the catalyst is preferably (1-1.5): 1, and more preferably 1.45: 1.

In the invention, a polymerization inhibitor is preferably added when the 4, 5-dimethylimidazole, the vinyl acetate and the catalyst are mixed, and in the invention, the polymerization inhibitor is used for inhibiting the vinyl acetate from generating intramolecular polymerization reaction; in the invention, the polymerization inhibitor is preferably hydroquinone, and the mass of the polymerization inhibitor accounts for 0.1-0.15% of the mass of the vinyl acetate, and more preferably 0.12-0.14%.

The invention has no special requirements on the specific implementation mode of the 4, 5-dimethylimidazole, the vinyl acetate and the catalyst during mixing or the 4, 5-dimethylimidazole, the vinyl acetate, the catalyst and the polymerization inhibitor, and the substances are mixed uniformly.

In the invention, the temperature of the second nucleophilic substitution reaction is preferably 60-80 ℃, more preferably 35-70 ℃, and the time of the second nucleophilic substitution reaction is preferably 2-6 h, more preferably 3-5 h.

In the present invention, the equation for the second nucleophilic substitution reaction is shown in formula I:

according to the invention, the reaction system obtained by the second nucleophilic substitution reaction is preferably subjected to post-treatment to obtain the 4, 5-dimethyl-1-vinylimidazole. In the present invention, the post-treatment preferably comprises: removing unreacted vinyl acetate, dissolving, neutralizing and extracting in sequence to obtain an organic phase with a target product 4, 5-dimethyl-1-vinyl imidazole solution, drying the organic phase and removing the extractant.

The invention preferably removes unreacted vinyl acetate by distillation under reduced pressure; the invention has no special requirements on the specific implementation mode of the reduced pressure distillation; after the unreacted vinyl acetate is removed, the solid product after the ethyl acetate is removed is preferably dissolved and neutralized, in the invention, the dissolved and neutralized solid product is preferably dissolved in the saturated sodium bicarbonate for neutralization reaction until the pH value of the neutralized solution is 7-8, and the catalyst in the first nucleophilic substitution reaction is preferably removed through the dissolved and neutralized solid product; according to the invention, the solution after the neutralization reaction is preferably extracted to obtain a water phase and an organic phase, wherein the organic phase contains a target product 4, 5-dimethyl-1-vinyl imidazole; the extracting agent for extraction is preferably diethyl ether or dichloromethane, and in the invention, the extraction frequency is preferably 3-5 times; the invention has no special requirement on the dosage of the extraction solvent in each extraction, and the invention preferably detects the content of the target product in the water phase by thin-layer chromatography (TLC) when the target product 4, 5-dimethyl-1-vinyl imidazole is not in the water phase; the present invention preferably combines the organic phases of each extraction. The target product 4, 5-dimethyl-1-vinyl imidazole is extracted into an organic phase by extraction, the organic phase containing the target product is dried, and the drying agent is anhydrous magnesium sulfate; the invention preferably removes the extractant by reduced pressure distillation, and the invention has no special requirements on the specific implementation mode of the reduced pressure distillation and can remove the extractant cleanly.

In the present invention, the halogenated alkane is preferably C_12～16A haloalkane, preferably a bromoalkane, more preferably a 1-bromoalkane; the halogenated alkane is more preferably C_12～16Brominated alkanes inIn a specific embodiment of the present invention, the halogenated alkane is preferably one or more of 1-bromododecane, 1-bromotridecane, 1-bromotetradecane, 1-bromopentadecane and 1-bromohexadecane, more preferably 1-bromododecane and/or 1-bromotetradecane; in the present invention, when the halogenated alkane is preferably two or more of the above substances, the present invention has no particular requirement on the compounding ratio of the specific substances.

In the present invention, the ratio of the amounts of the 4, 5-dimethyl-1-vinylimidazole and the haloalkane is preferably 1 (1.1 to 2), more preferably 1 (1.5 to 1.8).

In the invention, the temperature of the first nucleophilic substitution reaction is preferably 60-80 ℃, and more preferably 65-75 ℃; the time of the first nucleophilic substitution reaction is preferably 36-48 h, and more preferably 40-42 h; the first nucleophilic substitution reaction is carried out in a protective gas atmosphere, preferably an inert gas or nitrogen.

In a specific embodiment of the present invention, the equation for the first nucleophilic substitution reaction is shown in formula II:

in the invention, n in the formula II is preferably a positive integer of 12-16.

The invention preferably carries out post-treatment on the reaction system obtained by the first nucleophilic substitution reaction to obtain the vinylimidazole amphiphilic ionic liquid; in the present invention, the post-treatment preferably comprises: removing the polar organic solvent, recrystallizing and drying in sequence.

The present invention preferably removes the polar organic solvent by distillation under reduced pressure; the invention has no special requirements on the specific implementation mode of the reduced pressure distillation; after removing the polar organic solvent, the present invention preferably recrystallizes the solid product from which the polar organic solvent was removed, and in the present invention, the recrystallization is preferably: dissolving the solid product in a recrystallization solvent for recrystallization, wherein the recrystallization solvent is preferably diethyl ether and/or ethyl acetate, and more preferably diethyl ether, the invention has no special requirements on the specific implementation process of recrystallization, and adopts the operation well known by the technical personnel in the field, and in the specific embodiment of the invention, the specific process of recrystallization is as follows: and dissolving the solid product in the recrystallization solvent, and cooling to separate out. The present invention preferably purifies the solid product by recrystallization; the recrystallization product is preferably dried, in the invention, the drying temperature is preferably 40-60 ℃, the drying time has no special requirement, and the recrystallization product is dried to constant weight.

After the vinyl imidazole amphiphilic ionic liquid is obtained, the vinyl imidazole amphiphilic ionic liquid is self-assembled in water to form an ordered liquid crystal system.

In the present invention, the water is preferably deionized water.

In the invention, the vinyl imidazole amphiphilic ionic liquid and water are mixed to obtain an ionic liquid aqueous solution, and the mass percentage content of the vinyl imidazole amphiphilic ionic liquid is preferably 50-85%, and more preferably 60-80%.

In the invention, the ionic liquid aqueous solution obtained by mixing the vinyl imidazole amphiphilic ionic liquid and water preferably further comprises a photoinitiator, and the photoinitiator is preferably used for initiating the in-situ photopolymerization reaction.

In the present invention, the photoinitiator is preferably one or more of 2-hydroxy-2-methyl propiophenone, 2-hydroxy-2-methyl-1-phenyl methanone and 1-hydroxy-cyclohexyl-phenyl methanone, more preferably 2-hydroxy-2-methyl propiophenone and/or 2-hydroxy-2-methyl-1-phenyl methanone, and in the present invention, when the photoinitiator is preferably two or more of the above substances, the present invention has no special requirement on the proportion relationship of the above specific substances.

In the invention, in the ionic liquid aqueous solution, the mass percentage of the photoinitiator is preferably 0.1-0.5%, and more preferably 0.2-0.4%.

In the invention, the self-assembly temperature is preferably 25-40 ℃, and more preferably 30-35 ℃; the self-assembly time is preferably 30 to 50 days, and more preferably 35 to 45 days.

In the present invention, the self-assembly is preferably carried out in a constant temperature and humidity chamber.

In the invention, the vinyl imidazole amphiphilic ionic liquid is self-assembled in water, wherein a hydrophilic group and a hydrophobic group are self-assembled to form an ordered structure.

After the ordered liquid crystal system is formed, the ordered liquid crystal system is subjected to in-situ photopolymerization under ultraviolet light to obtain the ordered polyion liquid material.

The wavelength of the ultraviolet light is not particularly required by the invention, and in the specific embodiment of the invention, the wavelength of the ultraviolet light is preferably 365 nm.

In the present invention, the time for the in-situ photopolymerization is preferably 0.5 to 2 hours, and more preferably 1 to 1.5 hours. The temperature of the in situ photopolymerization reaction is preferably at an internal room temperature.

In a specific embodiment of the present invention, the equation of the in-situ photopolymerization is shown as formula III:

in the present invention, the polymerization degree m of the in-situ photopolymerization reaction is preferably determined by the time of the photopolymerization.

The ordered polyion liquid material is obtained by carrying out polymerization reaction on a double bond structure in an ordered liquid crystal system through in-situ photopolymerization.

After the ordered polyion liquid material is obtained, the ordered polyion liquid material is mixed with a strong base solution for ion exchange to obtain the ordered alkaline anion material.

In the present invention, the strong alkali solution is preferably an alkali metal hydroxide solution, more preferably a KOH solution or a NaOH solution; the molar concentration of the strong alkali solution is preferably 1-5 mol/L, and more preferably 1.5-4 mol/L; in the present invention, the strong base solution is preferably a nitrogen saturated strong base solution to prevent oxidation of the ordered polyion liquid material by dissolved oxygen in the strong base solution.

The method has no special requirement on the dosage of the strong alkali solution, and can ensure that the ordered polyion liquid material can be completely immersed in the strong alkali solution after the ordered polyion liquid material is mixed with the strong alkali solution.

In the invention, the time of the ion exchange is preferably 36-48 h, and more preferably 40-45 h; the temperature of the ion exchange is preferably room temperature; the ion exchange is carried out in a vacuum environment, and the invention has no special requirement on the vacuum degree of the vacuum environment.

The invention preferably carries out post-treatment on the product after ion exchange to obtain the ordered alkaline anionic material, wherein the post-treatment is preferably washing and drying; the invention has no special requirements on the specific implementation process of the drying, and the drying value of the membrane is constant.

The invention exchanges the halide ions in the ordered polyion liquid membrane into hydroxide ions through ion exchange.

In a specific embodiment of the present invention, the ion exchange equation is shown in formula VI:

the invention provides an ordered alkaline anion material prepared by the preparation method in the technical scheme.

In the invention, the molecular structure of the ordered basic anionic material is a product shown in a formula VI.

The ordered alkaline anion-exchange membrane provided by the invention is obtained by self-assembling and ordering the C4 and C5 substituted imidazole amphiphilic ionic liquid and polymerizing, and the OH is improved through a highly ordered ion transmission channel constructed by self-assembling the ionic liquid^-Ion(s)The transmission efficiency of (a); and the structures substituted by C4 and C5 positions obviously improve the alkali stability of the alkali anion material.

The invention provides an anion exchange membrane fuel cell, and a diaphragm for the anion exchange membrane fuel cell is the ordered alkaline anion exchange material in the technical scheme.

In the present invention, the ordered basic anion exchange material is preferably prepared into an ordered basic anion exchange membrane for use, and in a specific embodiment of the present invention, the preparation method of the ordered basic anion exchange membrane material according to the above technical scheme is adopted to prepare an ordered basic anion exchange membrane, except that the method comprises the following steps: replacing the ordered liquid crystal system with the ordered polyion liquid material by the following steps: and (3) forming the ordered liquid crystal system into a film, and then carrying out in-situ photopolymerization under ultraviolet light to obtain the ordered polyion liquid film.

The present invention has no special requirement on the specific implementation process of the film formation, and in the specific embodiment of the present invention, the ordered liquid crystal system is poured into a surface dish or a culture dish, and the film formation is performed on the bottom of the surface dish or the culture dish or the ordered liquid crystal system is pressed between two quartz plates or glass slides to form the film.

In the present invention, the electrode of the anion exchange membrane fuel cell is preferably a gas diffusion electrode, the cathode of the gas diffusion electrode is preferably Pt/C as a catalyst, and the cathode of the gas diffusion electrode is preferably oxygen; the anode of the gas diffusion electrode preferably takes PtRu/C as a catalyst, and the anode of the gas diffusion electrode preferably takes hydrogen; the relative humidity of the intake air of the gas diffusion electrode is preferably 100% RH, the flow rate of the hydrogen gas of the gas diffusion electrode is preferably 100mL/min, the flow rate of the oxygen gas of the gas diffusion electrode is preferably 200mL/min, and the back pressure on both sides of the cathode and the anode of the gas diffusion electrode is preferably 0.2 MPa.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

17.68g of 4, 5-dimethyl imidazole salt, 75mL of vinyl acetate, 4.8mL of trifluoroacetic acid, 4.75g of mercury acetate and 100mg of hydroquinone are mixed at 80 ℃ for carrying out an affinity substitution reaction for 6 hours; removing excessive ethyl acetate from the reaction solution through reduced pressure distillation, dissolving a solid product in a saturated sodium bicarbonate solution until the pH value of the neutralized solution is 7-8, then adding dichloromethane into the neutralized solution for extraction until a target product cannot be detected in a water phase through TLC, combining extracted organic phases, drying the organic phases with anhydrous magnesium sulfate, and removing the organic phases through reduced pressure distillation to obtain 4, 5-dimethyl-1-vinylimidazole;

dissolving 0.015mol of 4, 5-dimethyl-1-vinyl imidazole and 0.023mol of 1-bromohexadecane in methanol, refluxing for 36 hours at 60 ℃ in a nitrogen atmosphere, performing rotary evaporation on a reacted mixture to remove a methanol solvent, and recrystallizing a crude product in diethyl ether for 3 times to obtain the vinyl imidazole amphiphilic ionic liquid;

mixing 3g of vinyl imidazole amphiphilic ionic liquid, 1.95g of deionized water and 0.01g of 2-hydroxy-2-methyl propiophenone, placing the mixture at 40 ℃ for 30 days to perform self-assembly to form an ordered liquid crystal system, pouring the ordered liquid crystal system into a culture dish, coating the bottom of the culture dish to form a film, and irradiating the film formed by the ordered liquid crystal system for 30min at room temperature by using a 365nm ultraviolet light source to obtain an ordered polyion liquid film;

and (2) soaking the ordered polyion liquid membrane in 1mol/LKOH solution for 36h under a vacuum condition, washing the residual KOH solution on the surface with deionized water, and drying to constant weight to obtain the ordered alkaline anion-exchange membrane. The small angle X-ray scattering (SAXS) curve of the ordered basic anion exchange membrane prepared in example 1 shows that the ratio of 1: the two scattering peaks of √ 3 correspond to the (100) and (110) crystal planes of the hexagonal liquid crystal phase.

Example 2

17.68g of 4, 5-dimethyl imidazole salt, 75mL of vinyl acetate, 4.8mL of trifluoroacetic acid, 4.75g of mercury acetate and 100mg of hydroquinone are mixed at 80 ℃ for carrying out an affinity substitution reaction for 6 hours; removing excessive ethyl acetate from the reaction solution through reduced pressure distillation, dissolving a solid product in a saturated sodium bicarbonate solution until the pH value of the neutralized solution is 7-8, then adding dichloromethane into the neutralized solution for extraction until a target product cannot be detected in a water phase through TLC, combining extracted organic phases, drying the organic phases with anhydrous magnesium sulfate, and removing the organic phases through reduced pressure distillation to obtain 4, 5-dimethyl-1-vinylimidazole;

dissolving 4, 5-dimethyl-1-vinylimidazole and 0.023mol of 1-bromohexadecane in methanol, refluxing for 36 hours at 60 ℃ in a nitrogen atmosphere, performing rotary evaporation on the reacted mixture to remove methanol solvent, and recrystallizing the crude product in diethyl ether for 3 times to obtain the vinylimidazole amphiphilic ionic liquid;

mixing 3g of vinyl imidazole amphiphilic ionic liquid, 0.6g of deionized water and 0.01g of 2-hydroxy-2-methyl propiophenone, placing the mixture at 40 ℃ for 30 days to perform self-assembly to form an ordered liquid crystal system, pouring the ordered liquid crystal system into a culture dish, coating the bottom of the culture dish to form a film, and irradiating the film formed by the ordered liquid crystal system for 30min at room temperature by using a 365nm ultraviolet light source to obtain an ordered polyion liquid film;

and soaking the ordered polyion liquid membrane in 1mol/LKOH solution for 36h under a vacuum condition, washing the residual KOH solution on the surface with deionized water, and drying to constant weight to obtain the ordered alkaline anion-exchange membrane. The small angle X-ray scattering (SAXS) curve of the ordered basic anion exchange membrane prepared in example 2 shows that the ratio of 1: 2, corresponding to the (100) and (200) crystal planes of the lamellar liquid crystal phase.

Test example

The ordered alkaline anion-exchange membrane prepared in example 1 is soaked in 1mol/L KOH at 60 ℃ for 300 hours, and the swelling ratio of the product is tested and is 4%, which shows that the ordered alkaline anion-exchange membrane prepared in the example of the invention has good dimensional stability in alkaline solution;

soaking the ordered alkaline anion-exchange membrane prepared in the example 1 in 1mol/L KOH at 60 ℃ for 300 hours, and testing the conductivity of the product before and after soaking, wherein the conductivity reduction rate is 7.4%; the ordered alkaline anion-exchange membrane prepared by the embodiment of the invention shows good conductivity stability of alkaline solution.

Example 3

The product prepared in the example 1 is used as a diaphragm of an alkaline anion exchange membrane fuel cell and assembled with a commercial gas diffusion electrode into a single cell, the performance of the cell is tested, under the condition of 60 ℃ full humidification (100% humidification), hydrogen and oxygen are heated and humidified in a humidification tank and then are introduced into the cell, the flow rates of the hydrogen and the oxygen are respectively fixed at 100mL/min and 200mL/min, when the back pressure at two sides is 0.2MPa, the open circuit voltage of the cell is up to 0.94V, which shows that the product membrane prepared in the example 1 has better gas barrier effect, and the highest power density of the cell reaches 50mW cm^-2The cell performance was good, indicating that the cell prepared in example 1 is suitable for use in an alkaline anion exchange membrane fuel cell.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.