Micellar polyionic liquid ion exchange membrane, method for preparing the same, and fuel cell

Abstract

The application provides a kind of micellar polyionic liquid ion exchange membrane and its preparation method and fuel cell, belong to fuel cell technical field.The micellar polyionic liquid ion exchange membrane is formed by polymerization of vinyl imidazole sulfonate ionic liquid phase, polar solvent phase, additive, and the mass ratio of the vinyl imidazole sulfonate, polar solvent and additive is 1: (0.01~5): (0.001~1).The ion exchange membrane is rich in positive charge at the phase boundary surface due to the micellar phase separation characteristics, which provides good OH ‑ ion transport site, and provides good ion conductivity for anion exchange membrane fuel cell.Meanwhile, the dense phase separation structure effectively inhibits the fuel penetration.The method and process used to prepare the ion exchange membrane are simple and operable, and are suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of battery assembly preparation, and particularly relates to a micellar polyionic liquid ion exchange membrane, a preparation method thereof and a fuel cell. BACKGROUND

[0002] As a clean energy device capable of directly and efficiently converting chemical energy into electrical energy, fuel cells have the advantages of zero pollution, high energy density and fast start-up speed, and show a broad application prospect in the fields of new energy vehicles, distributed power generation and portable electronic devices. Among them, the anion exchange membrane, as one of the core components of the fuel cell, not only plays a key role in separating the fuel and the oxidant and preventing the direct mixing of the two to cause side reactions, but also needs to provide an efficient transmission channel for OH - and other anions, and its performance directly determines the output power, energy conversion efficiency and long-term stability of the fuel cell, thus becoming one of the core focuses of current fuel cell technology research and development.

[0003] However, the existing anion exchange membrane still faces core technical bottlenecks, which seriously restricts the industrialization process of the fuel cell. The traditional anion exchange membrane generally has a “trade-off” contradiction between ion conductivity and fuel barrier property: in order to improve the ion conduction performance, the ion group content in the membrane usually needs to be increased, but this will cause the swelling degree of the membrane to increase and the structural stability to decrease, thereby intensifying the penetration of fuels such as methanol and hydrogen, causing the “fuel crossover” problem and significantly reducing the efficiency of the cell. In order to solve the above problems, researchers try to optimize the structure and performance of the membrane through strategies such as molecular design, blending modification and nanocomposite, among which polyionic liquid materials become one of the ideal candidate materials for anion exchange membranes due to their high ionic conductivity, good chemical stability and excellent film-forming property and mechanical strength of the polymer. However, the existing polyionic liquid-based anion exchange membranes are mostly prepared by homogeneous polymerization, and the ion transmission channels in the membrane are dispersed and disordered, which is difficult to form a continuous and efficient ion conduction path, and the improvement of ion conductivity is limited; at the same time, the homogeneous structure lacks effective microphase separation characteristics, and the fuel barrier performance is not improved well.

[0004] Therefore, it is of great significance to develop a polyionic liquid-based anion exchange membrane preparation technology that can construct an ordered ion transmission channel, simultaneously realize high ion conductivity and excellent fuel barrier property, and has good chemical stability and mechanical property, for breaking through the performance bottleneck of the current fuel cell and promoting its industrial application. It is also a key technical problem to be solved in the field. SUMMARY

[0005] The application aims to provide a micellar polyionic liquid ion exchange membrane, a preparation method thereof and a fuel cell. The method and process for preparing the ion exchange are simple and easy to operate, and are suitable for industrial production.

[0006] To achieve the above object, the application adopts the following technical solutions:

[0007] In a first aspect, the application provides a micellar polyionic liquid ion exchange membrane, comprising a polyionic liquid and a polar solvent.

[0008] The chemical structure of the polyionic liquid is shown in the following formula (1):

[0009]

[0010] wherein R is a C1-C16 alkyl chain; a=1~20, b=1~20; n:m:p=(0.01~0.3):(0.01~0.3):1; X - has a structure of any one of the following formulas (2)-(8):

[0011] .

[0012] wherein the polar solvent is selected from one of water, glycerol, methanol, ethanol, butanol, propanol, ethylene glycol, acetic acid, dichloromethane, trichloromethane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, ethylene carbonate, propylene carbonate, diethyl carbonate, and methyl ethyl carbonate.

[0013] In a second aspect, the application provides a preparation method of a micellar polyionic liquid ion exchange membrane, comprising:

[0014] The mass ratio of the vinyl imidazole sulfonate, the polar solvent, and the additive is adjusted to construct a micellar phase separation structure ionic liquid premix, which is uniformly mixed under ultrasonic and centrifuged to remove bubbles to obtain a mixed material slurry; the mass ratio of the vinyl imidazole sulfonate, the polar solvent, and the additive is 1:(0.01~5):(0.001~1); wherein the vinyl imidazole sulfonate comprises vinyl imidazole sulfonate monomers, a vinyl imidazole sulfonate aqueous phase crosslinking agent, and a vinyl imidazole sulfonate oil phase crosslinking agent in a mass ratio of 1:(0.01~0.3):(0.01~0.3).

[0015] The mixed material slurry after degassing is uniformly coated on a support substrate to form a thin film and undergo a polymerization reaction to obtain a micellar polyionic liquid ion exchange membrane.

[0016] As a further improvement of the application, the additive is a thermal initiator, a photo initiator, a radiation initiator, or a microwave initiator.

[0017] As a further improvement of the application, the polymerization reaction conditions are as follows: the reaction temperature is 0-75℃, the reaction irradiation conditions are ultraviolet light, visible light, or microwave irradiation, and the reaction time is 1 minute-12 hours.

[0018] As a further improvement of the present application, the mixture after defoaming is uniformly coated on the support substrate, in particular, by using a method of blade coating, pressure coating or roller coating.

[0019] As a further improvement of the present application, the polar solvent is selected from one of water, glycerol, methanol, ethanol, butanol, propanol, ethylene glycol, acetic acid, dichloromethane, trichloromethane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, ethylene carbonate, propylene carbonate, diethyl carbonate and methyl ethyl carbonate.

[0020] As a further improvement of the present application, the vinyl imidazole sulfonate monomer is selected from any one of 1-vinyl-3-n-hexylimidazole 1-methyl sulfonate, 1-vinyl-3-n-hexylimidazole 1-vinyl sulfonate, 1-vinyl-3-n-hexylimidazole 1-cyclopropyl sulfonate, 1-vinyl-3-n-hexylimidazole 1-phenyl sulfonate, 1-vinyl-3-n-hexylimidazole 1-bromomethyl sulfonate, 1-vinyl-3-n-hexylimidazole 4-methyl benzene sulfonate, 1-vinyl-3-n-hexylimidazole 4-bromobenzene sulfonate.

[0021] The vinyl imidazole sulfonate aqueous phase crosslinking agent is selected from any one of 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24- octaoxa-hexacosyl}oxy)imidazole bis (1-methyl sulfonate), 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24-octaoxa-hexacosyl}oxy)imidazole bis (1-vinyl sulfonate), 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24-octaoxa-hexacosyl}oxy)imidazole bis (1-phenyl sulfonate), 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24-octaoxa-hexacosyl}oxy)imidazole bis (4-methyl benzene sulfonate), 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24-octaoxa-hexacosyl}oxy)imidazole bis (4-bromobenzene sulfonate).

[0022] The vinyl imidazole sulfonate oil phase crosslinking agent is selected from any one of the following: 3-vinyl-1-[11-(3-vinylimidazolyl)undecyl]imidazole bis(1-methyl sulfonate); 3-vinyl-1-[11-(3-vinylimidazolyl)undecyl]imidazole bis(1-vinyl sulfonate); 3-vinyl-1-[11-(3-vinylimidazolyl)undecyl]imidazole bis(1-phenyl sulfonate); 3-vinyl-1-[11-(3-vinylimidazolyl)undecyl]imidazole bis(4-methyl phenyl sulfonate); 3-vinyl-1-[11-(3-vinylimidazolyl)undecyl]imidazole bis(4-bromophenyl sulfonate).

[0023] As a further improvement of the present application, the support substrate is selected from polyethylene terephthalate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer, polycarbonate, polyurethane, phenolic resin, polytetrafluoroethylene, polyvinylidene fluoride, polyether sulfone;

[0024] The support substrate pressure ranges from 5 N / m to 30 N / m.

[0025] In a third aspect, the present application provides a fuel cell comprising a fuel cell anion exchange membrane, wherein the fuel cell anion exchange membrane is prepared from the micellar polyionic liquid ion exchange membrane.

[0026] Compared with the prior art, the present application has the following advantages:

[0027] The traditional anion exchange membrane has a "trade-off" contradiction between ion conductivity and fuel barrier property, and the existing polyionic liquid-based membrane is limited in performance improvement due to disordered ion transport channels and lack of effective phase separation, which restricts the industrialization of fuel cells. The present application constructs a micellar phase separation structure, which makes the interface surface in the membrane rich in positive charges, provides sufficient transport sites to ensure high ion conductivity, and effectively inhibits fuel penetration by the dense phase separation structure, thereby breaking through the technical bottleneck of traditional membranes, greatly improving the output power and energy conversion efficiency of fuel cells, and meeting the performance requirements of core components. - The micellar polyionic liquid ion exchange membrane is formed by polymerization of a vinyl imidazole sulfonate ionic liquid phase, a polar solvent phase and an additive, and the mass ratio of the vinyl imidazole sulfonate, the polar solvent and the additive is 1: (0.01-5): (0.001-1). The ion exchange membrane is rich in positive charges at the interface surface due to the micellar phase separation characteristics, which provides good OH - ion transport sites, and provides good ion conductivity for anion exchange membrane fuel cells. At the same time, the dense phase separation structure effectively inhibits the penetration of fuel.

[0028] The preparation process has more advantages: the premix is dissolved by ultrasonic, centrifugal defoaming, and then prepared, mature methods such as scraping coating and pressure coating are adopted for coating, the support substrate such as PET and PP is used to assist film forming during polymerization, the reaction temperature is mild, the time is flexible, the parameters such as light intensity and wavelength are easy to adjust, the repeatability is high, and the industrial production is suitable; and the prepared membrane has reliable performance verified by the alternating current impedance method, and can be stably used as a fuel cell diaphragm, thereby providing key component support for fuel cell industrialization. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 It is a physical diagram of the micellar polyionic liquid ion exchange membrane;

[0030] Figure 2 It is a scanning electron microscope image of the micellar polyionic liquid ion exchange membrane;

[0031] Figure 3 It is a scanning electron microscope image of the micellar polyionic liquid ion exchange membrane;

[0032] Figure 4 It is a Fourier infrared absorption spectrum of the micellar polyionic liquid ion premix and the ion exchange membrane;

[0033] Figure 5 It is an ion conductivity test diagram of the micellar polyionic liquid ion exchange membrane examples 1-3;

[0034] Figure 6 It is a schematic diagram of the assembly structure of the micellar polyionic liquid ion exchange membrane. DETAILED DESCRIPTION

[0035] In order to make the technical problems, technical schemes and beneficial effects to be solved in the application more clear and obvious, the application will be further described in detail in combination with examples. It should be understood that the specific examples described herein are only used to explain the application, and are not used to limit the application.

[0036] In the application, the term "and / or" describes the association relationship of the associated objects, which means that there can be three kinds of relationships, for example, A and / or B can mean that A exists alone, A and B exist together, and B exists alone. Wherein A and B can be singular or plural. The character " / " generally represents that the front and rear associated objects are in an "or" relationship.

[0037] In this application, "at least one" means one or more, and "multiple" means two or more. "At least one of the following" or similar expressions means any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can mean a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.

[0038] It should be understood that the size of the sequence number of the above-mentioned processes in various embodiments of the present application does not mean the order of execution, and part or all of the steps can be executed in parallel or in sequence, and the execution order of the processes should be determined according to their functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0039] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "an" and "the" used in the embodiments of the present application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0040] The weight of the related components mentioned in the specification of the embodiments of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of each component, therefore, as long as the content of the related components in the specification of the embodiments of the present application is enlarged or reduced in proportion, it is within the scope disclosed in the specification of the embodiments of the present application. Specifically, the mass in the specification of the embodiments of the present application can be µg, mg, g, kg, etc. mass units well known in the chemical industry.

[0041] The terms "first", "second" are only for the purpose of description, and are used to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. For example, without departing from the scope of the embodiments of the present application, the first XX can also be called the second XX, and similarly, the second XX can also be called the first XX. Therefore, the features limited by "first" and "second" can explicitly or implicitly include one or more of the features.

[0042] The content studied in the present application is as follows:

[0043] (I) Design and optimization of micellar polyionic liquid material system

[0044] Core raw material screening and ratio determination: screening suitable ethylene imidazole sulfonate raw materials, including monomers, water phase crosslinking agent and oil phase crosslinking agent; monomer selection 1- ethylene-3-n-hexyl imidazole series sulfonate (such as 1- ethylene-3-n-hexyl imidazole 1-methyl sulfonate, 4-methyl benzene sulfonate, etc.), to ensure the combination of hydrophilic and hydrophobic groups to promote phase separation; water phase crosslinking agent selection 3- ethylene imidazole bisulfonate containing polyoxa chain (such as 3- ethylene-1- ({26-[(3- ethylene imidazole) oxy]-3, 6, 9, 12, 15, 18, 21, 24- octa-oxa-hexacosyl-1-yl} oxy) imidazole bisulfonate), to enhance the stability of water phase micro zone crosslinking; oil phase crosslinking agent selection 3- ethylene imidazole bisulfonate containing long alkyl chain (such as 3- ethylene-1- [11- (3- ethylene imidazole) undecyl] imidazole bisulfonate), to strengthen the oil phase skeleton support. Through experimental optimization, the mass ratio of the three is 1: (0.01-0.3): (0.01-0.3), and the mass ratio of ethylene imidazole sulfonate, polar solvent (water / glycerol / ethanol, etc.), additive (photoinitiator 184, etc.) is determined as 1: (0.01-5): (0.001-1), to ensure the spontaneous formation of stable micellar phase separation structure.

[0045] Polyionic liquid chemical structure regulation: according to the target performance requirements, the chemical structure parameters of polyionic liquid are regulated, the alkyl chain R is selected in the range of C1-C16, the hydrophobicity is optimized to adjust the size of the phase zone; the structure general formula a=1~20, b=1~20 is controlled, the proportion of hydrophilic and hydrophobic segments is adjusted; the copolymer unit ratio n: m: p= (0.01-0.3): (0.01-0.3): 1 is determined, the ion group distribution is optimized; the sulfonate anion X - in formulas (2)-(8) is selected, the ion transmission capacity is enhanced, and finally the three-dimensional structure of "water phase ion conduction zone-oil phase structure support zone-interface charge enrichment zone" is formed.

[0046] (B) Development of micellar ion exchange membrane preparation process

[0047] Micellar premix preparation process: ultrasonic mixing-centrifugal defoaming synergistic process is developed-ethylene imidazole sulfonate, polar solvent and additive are added to the centrifugal tube, ultrasonic mixing is carried out in water bath ultrasonic at 300-500W power for 20-30 minutes, to ensure that the raw materials are completely dissolved and spontaneously form micellar phase separation structure; then centrifugation is carried out at 3000-10000 rpm for 3-5 minutes, to completely remove the bubbles in the premix, avoid pore defects after membrane forming, and obtain uniform and stable micellar ionic liquid premix.

[0048] Membrane formation and polymerization process optimization: optimize coating and polymerization process parameters - select polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE) and other support substrates, use blade coating method (knife gap control at 200-300 μm) or pressure coating method (pressure 5-30 N / m) to uniformly coat the premix on the substrate; the polymerization stage uses ultraviolet light (wavelength 250-365 nm, light intensity 10-150 mW / cm²) or visible light irradiation, controls the reaction temperature at 25-75°C, the reaction time at 1-30 minutes, ensures that the micellar structure is completely fixed during the polymerization process, and forms a self-supporting film; after polymerization, the substrate is removed by warm water immersion or mechanical peeling method, and a micellar polyionic liquid ion exchange membrane is obtained.

[0049] (Three) Membrane performance test and application adaptation verification

[0050] Membrane basic performance test: establish a comprehensive performance test system - use scanning electron microscopy (SEM) to observe the microstructure of the membrane and verify the micellar phase separation characteristics (require uniform size and close-packed distribution of phase regions); detect the reaction conversion rate of polymerizable functional groups (v C=C , 1660-1680 cm -1 ) by Fourier transform infrared spectroscopy (FT-IR) to ensure complete polymerization; test the ion conductivity by alternating current impedance method (apply 10 mV alternating current signal, sweep frequency range 1 Hz-1 MHz), test the swelling degree by weighing method, test the mechanical strength by universal testing machine, and test the fuel permeation coefficient by permeation cell method.

[0051] Fuel cell application verification: assemble the developed micellar ion exchange membrane into a fuel cell - fix the membrane at the electrolyte membrane of the fuel cell, place platinum electrodes on both sides, add 1 mol / L KOH electrolyte, test the polarization curve and power density curve of the cell by electrochemical workstation, evaluate the improvement effect of the membrane on the output performance of the cell, conduct 1000 hours of continuous operation test, monitor the attenuation of cell voltage and current, verify the long-term stability of the membrane, and ensure that the fuel cell meets the actual application requirements.

[0052] Based on the above analysis, the first object of the application is to provide a micellar polyionic liquid ion exchange membrane, which comprises a polyionic liquid and a polar solvent. The polar solvent is selected from one of water, glycerol, methanol, ethanol, butanol, propanol, ethylene glycol, acetic acid, dichloromethane, trichloromethane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, ethylene carbonate, propylene carbonate, diethyl carbonate and methyl ethyl carbonate.

[0053] Among them, the chemical structure of the polyionic liquid is as shown in the following formula (1):

[0054]

[0055] wherein R is a C1-C16 alkyl chain. a=1~20, b=1~20. n:m:p=(0.01~0.3):(0.01~0.3):1. Anion X - are of the following formula (2)-(8):

[0056]

[0057] The second object of the present application is to provide a preparation method of a micellar polyionic liquid ion exchange membrane, comprising:

[0058] 1) Preparation of micellar ionic liquid premix. By adjusting the mass ratio of vinyl imidazole sulfonate, polar solvent and additive, a micellar phase separation structure ionic liquid premix is constructed.

[0059] wherein the polyionic liquid ion exchange membrane is composed of vinyl imidazole sulfonate ionic liquid phase, polar solvent phase and additive polymerization, and the mass ratio of the vinyl imidazole sulfonate, polar solvent and additive is 1:(0.01~5):(0.001~1).

[0060] Specifically, the additive is a thermal initiator, a photo initiator, a radiation initiator, or a microwave initiator. The polymerization reaction conditions are: the polymer monomer, polar solvent and initiator are mixed uniformly under ultrasonic, and centrifuged to remove bubbles. The bubble-removed mixture slurry is uniformly coated into a thin film by scraping, pressing or rolling, and then subjected to polymerization reaction, the reaction temperature is 0-75℃, the reaction irradiation conditions are ultraviolet light, visible light or microwave irradiation, and the reaction time is 1 minute-12 hours.

[0061] Specifically, the reaction temperature is 0-65℃, and the reaction time is 1 hour-12 hours. The reaction temperature is 25-75℃, and the reaction time is 6 hours-12 hours. The reaction temperature is 40-75℃, and the reaction time is 3 hours-10 hours. The reaction temperature is 20-55℃, and the reaction time is 1 minute-1 hour. The reaction temperature is 0℃, and the reaction time is 12 hours. The reaction temperature is 25℃, and the reaction time is 10 hours. The reaction temperature is 45℃, and the reaction time is 5 hours. The reaction temperature is 65℃, and the reaction time is 50 minutes.

[0062] wherein the vinyl imidazole sulfonate ionic liquid and the polar solvent are uniformly mixed in a mass ratio of 1:(0.01~5), the ionic liquid forms a micellar phase separation structure, and the micellar structure is solidified by polymerization solidification method.

[0063] Preferably, the mass ratio of the vinyl imidazole sulfonate, the polar solvent and the additive in step 1) is 1 : (0.01 ~ 5) : (0.001 ~ 1). Further preferably, the mass ratio of the vinyl imidazole sulfonate, the polar solvent and the additive is 1 : (0.5 ~ 2) : (0.001 ~ 0.01). Further preferably, the mass ratio of the vinyl imidazole sulfonate, the polar solvent and the additive is 1 : (0.5 ~ 1.5) : (0.005 ~ 0.01).

[0064] Preferably, the polar solvent is selected from water, glycerol, methanol, ethanol, butanol, propanol, ethylene glycol, acetic acid, dichloromethane, trichloromethane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, ethylene carbonate, propylene carbonate, diethyl carbonate and methyl ethyl carbonate.

[0065] Preferably, the vinyl imidazole sulfonate includes a vinyl imidazole sulfonate monomer, a vinyl imidazole sulfonate aqueous phase crosslinking agent and a vinyl imidazole sulfonate oil phase crosslinking agent. The mass ratio of the vinyl imidazole sulfonate monomer, the vinyl imidazole sulfonate aqueous phase crosslinking agent and the vinyl imidazole sulfonate oil phase crosslinking agent is 1 : (0.01 ~ 0.3) : (0.01 ~ 0.3).

[0066] Further preferably, the vinyl imidazole sulfonate monomer is selected from the following molecules: 1-vinyl-3-n-hexylimidazole 1-methyl sulfonate; 1-vinyl-3-n-hexylimidazole 1-vinyl sulfonate; 1-vinyl-3-n-hexylimidazole 1-cyclopropyl sulfonate; 1-vinyl-3-n-hexylimidazole 1-phenyl sulfonate; 1-vinyl-3-n-hexylimidazole 1-bromomethyl sulfonate; 1-vinyl-3-n-hexylimidazole 4-methyl benzene sulfonate; 1-vinyl-3-n-hexylimidazole 4-bromobenzene sulfonate.

[0067] Further preferably, the aqueous phase crosslinker of the vinyl imidazole sulfonate salt is selected from the following molecules: 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24- octaoxa hexacosyl}oxy)imidazole bis (1-methylsulfonate); 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24- octaoxa hexacosyl}oxy)imidazole bis (1-vinylsulfonate); 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24- octaoxa hexacosyl}oxy)imidazole bis (1-phenylsulfonate); 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24- octaoxa hexacosyl}oxy)imidazole bis (4-methylbenzenesulfonate); 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24- octaoxa hexacosyl}oxy)imidazole bis (4-bromobenzenesulfonate).

[0068] Further preferably, the aqueous phase crosslinker of the vinyl imidazole sulfonate salt is selected from the following molecules: 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24- octaoxa hexacosyl}oxy)imidazole bis (1-methylsulfonate); 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24- octaoxa hexacosyl}oxy)imidazole bis (1-vinylsulfonate); 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24- octaoxa hexacosyl}oxy)imidazole bis (1-phenylsulfonate); 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24- octaoxa hexacosyl}oxy)imidazole bis (4-methylbenzenesulfonate); 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24- octaoxa hexacosyl}oxy)imidazole bis (4-bromobenzenesulfonate).

[0069] Preferably, the preparation method of the micellar ionic liquid premix is that the vinyl imidazole sulfonate monomer, the aqueous phase crosslinker of the vinyl imidazole sulfonate salt, and the oil phase crosslinker of the vinyl imidazole sulfonate salt are mixed in a centrifuge tube in a certain proportion, and completely dissolved in ultrasonic, and the premix is defoamed in a centrifuge at a speed of 3000-10000 rpm to obtain the micellar ionic liquid premix. Preferably, the speed can also be 3000-6000 rpm, 3000-8000 rpm, 4000-10000 rpm, 6000-10000 rpm, 5000-8000 rpm, 3000 rpm, 60000 rpm, 100000 rpm, etc.

[0070] 2) Preparation of the micellar polyionic liquid ion exchange membrane. The micellar polyionic liquid ion exchange membrane is prepared by coating the micellar polyionic liquid pre-mixture on the substrate / mold, initiating and polymerizing.

[0071] Preferably, in step 2), the specific preparation method of the micellar polyionic liquid ion exchange membrane is as follows: the micellar polyionic liquid pre-mixture prepared in step 1) is uniformly coated on the supporting substrate film, another layer of supporting substrate film is pressed on the uniformly coated substrate under a certain pressure, and polymerization is carried out under the irradiation of ultraviolet light or visible light with a certain light intensity for 1-30 min. After polymerization is completed, the supporting substrate film is removed to obtain the micellar polyionic liquid ion exchange membrane.

[0072] Further preferably, the supporting substrate is selected from polyethylene terephthalate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer, polycarbonate, polyurethane, phenolic resin, polytetrafluoroethylene, polyvinylidene fluoride, polyether sulfone.

[0073] Further preferably, the pressure of the supporting substrate is in the range of 5 N / m-30 N / m. Preferably, the pressure can also be 5 N / m-20 N / m, 8 N / m-30 N / m, 15 N / m-30 N / m, 10 N / m-20 N / m, 20 N / m-30 N / m, 5 N / m, 10 N / m, 15 N / m, 20 N / m, 30 N / m, etc.

[0074] Further preferably, the irradiation wavelength of the ultraviolet light / visible light is selected from 250-800 nm, and the light intensity of the ultraviolet light / visible light is selected from 10-150 mW / cm 2 . Preferably, it can also be 10-100 mW / cm 2 , 100-150 mW / cm 2 , 80-150 mW / cm 2 , 100-120 mW / cm 2 , 50-100 mW / cm 2 , 10 mW / cm 2 , 40 mW / cm 2 , 100 mW / cm 2 , 110 mW / cm 2 , 120 mW / cm 2 , 140 mW / cm 2 , 150 mW / cm 2 .

[0075] 3) Performance test of the micellar ion exchange membrane. The micellar ion exchange membrane is clamped on an ion conduction testing instrument for testing.

[0076] Preferably, the specific method for testing the performance of the micellar ion exchange film in step 3) is as follows: the micellar polyionic liquid ion exchange film obtained in step 2) is fixed at the fuel cell electrolytic cell diaphragm, two platinum electrodes are placed in the two chambers of the fuel cell electrolytic cell, 1 mol / L KOH solution is added, an electrochemical workstation is used to apply a 10 mV alternating signal, the frequency sweeping range is 1 Hz-1 MHz, the impedance spectrum is obtained, the film resistance is calculated through the Nyquist diagram, and then the conductivity is calculated according to σ=L / (R×S).

[0077] Based on the above scheme, the principle of the present application is that in the micellar ionic liquid premix, the vinyl imidazole sulfonate, the polar solvent and the additive will spontaneously form a phase separation structure: water phase microzone: because the sulfonate group of the vinyl imidazole sulfonate has strong hydrophilicity, it will preferentially combine with the polar solvent (such as water) to form a water phase microzone rich in ionic groups (mainly responsible for ion conduction); oil phase microzone: the imidazole ring of the vinyl imidazole has certain hydrophobicity, which will aggregate in the polar solvent to form a relatively hydrophobic oil phase microzone (mainly providing mechanical support and structural skeleton); interface zone: monomer molecules (containing vinyl, imidazole ring and sulfonate) may be distributed at the oil-water interface, having both hydrophilic / hydrophobic properties. At this time, the water phase crosslinking agent (more hydrophilic, such as multifunctional vinyl imidazole sulfonate containing more sulfonate or hydrophilic groups) will preferentially dissolve and enrich in the water phase microzone, and crosslinking reaction occurs with the monomers in the water phase; the oil phase crosslinking agent (more hydrophobic, such as multifunctional vinyl imidazole sulfonate containing long-chain alkyl or multiple imidazole rings) is more easily dissolved in the oil phase microzone and crosslinked with the monomers in the oil phase. This “targeted crosslinking” makes the distribution of crosslinking points highly matched with the phase separation structure of the micelles, forming a “water phase crosslinking network-oil phase crosslinking network” interpenetrating double network structure.

[0078] The water phase microzone forms a stable three-dimensional network through a water phase crosslinking agent, and the sulfonate groups (ion exchange sites) are concentrated in the water phase, which can maintain continuous ion conduction channels and ensure high ion conductivity; the oil phase microzone forms a more rigid crosslinked network through an oil phase crosslinking agent, which acts as the "skeleton" of the membrane, significantly improving the mechanical strength (such as tensile resistance and tear resistance) and dimensional stability (reducing swelling deformation) of the membrane. The stability of the phase separation structure of the micellar type is easily destroyed during polymerization due to monomer diffusion and solvent evaporation. Two kinds of crosslinking agents "lock" the water phase and oil phase microzones respectively: the water phase crosslinking agent fixes the size and distribution of the water phase, avoiding the breakage of ion channels; the oil phase crosslinking agent stabilizes the oil phase skeleton, preventing the collapse of the phase separation structure. Finally, the microstructure of the membrane (such as phase zone size and ion channel continuity) is controllable and stable. By adjusting the ratio of monomers to two kinds of crosslinking agents (1:(0.01~0.3):(0.01~0.3)), the crosslinking density of the water phase and oil phase can be controlled respectively: enhancing the stability of the water phase network, reducing the swelling degree, while maintaining the ion conductivity; improving the mechanical strength and solvent resistance (such as resistance to organic phase erosion) of the membrane; this "partition regulation" can flexibly adapt to different application scenarios (such as high conductivity demand or high stability demand). The double network crosslinking structure reduces the free movement of polymer chains, reducing the structural degradation of the membrane due to swelling, shrinkage or chemical erosion during long-term use: water phase crosslinking avoids the loss of ion groups or the dissolution of water phase microzones; oil phase crosslinking prevents brittle fracture of the membrane during dry-wet cycling, prolonging the service life. This combination of "monomer + water phase crosslinking agent + oil phase crosslinking agent" is essentially achieved through "structure matching crosslinking" to realize the "functional partition strengthening" of the micellar type polyionic liquid membrane - both the water phase microzone efficiently conducts ions and the oil phase microzone stably supports the structure, ultimately balancing ion conductivity, mechanical properties and stability. It is a typical design idea of "structure determines performance" in the preparation of micellar ion exchange membranes.

[0079] More specifically, the vinyl imidazole sulfonate contains monomers, water phase crosslinking agents and oil phase crosslinking agents, which are based on structure matching and phase zone targeting, and through precise matching of the phase separation structure of the micellar type premix, the synergistic effect of "partition polymerization-network interpenetration" is achieved. The three components (monomers, water phase crosslinking agents and oil phase crosslinking agents) of the vinyl imidazole sulfonate have controllable hydrophilic and hydrophobic differences, which is the basis for their partition distribution in the micellar system: vinyl imidazole sulfonate monomers: usually single functional group structure (containing 1 vinyl polymerization site), there are hydrophilic sulfonate groups (-SO3 - M + , M +hydrophobic imidazole ring (and possible short-chain alkyl substituents), thus possessing both hydrophilicity / hydrophobicity, and can be distributed in the aqueous phase, the oil phase, and the interface between the two phases, as the "basic unit" of polymerization. The aqueous phase crosslinking agent of vinyl imidazole sulfonate: is a multifunctional structure (containing 2 or more vinyl polymerization sites), and the hydrophilicity is enhanced by introducing more sulfonate groups or polar substituents (such as hydroxyl, short-chain ether group), so that it is more easily dissolved and enriched in the aqueous microzone of the micelle (formed by the aggregation of polar solvents and hydrophilic groups, which is the core area of ion conduction). The oil phase crosslinking agent of vinyl imidazole sulfonate: is also a multifunctional structure (containing 2 or more vinyl polymerization sites), but the hydrophilicity is reduced and the hydrophobicity is enhanced by increasing the long-chain alkyl substituents (such as C4-C 12 alkyl) on the imidazole ring or reducing the proportion of sulfonate, so that it is more easily enriched in the oil microzone of the micelle (formed by the aggregation of hydrophobic groups, which is the core area of membrane skeleton support). The combination of the three components realizes the "synchronous crosslinking and separate strengthening" of the aqueous phase and the oil phase through differential polymerization activity (all vinyl groups have free radical polymerization activity, ensuring synchronous reaction) and phase zone compatibility (each is dissolved and reacted in the target phase zone, avoiding cross-phase zone interference): both the aqueous phase network efficiently retains ion conduction sites, and the oil phase network stably supports the structure, ultimately ensuring that the membrane has both high ion conductivity and excellent mechanical properties. Through structure regulation to achieve the phase zone targeted distribution of components, and then through partition crosslinking to construct a double network matching the phase separation structure, finally balance the function (ion conduction) and structure (mechanical stability) of the membrane.

[0080] The content of the application will be described in detail below in combination with specific examples.

[0081] Example 1

[0082] First, 2 g of 1-vinyl-3-n-hexyl imidazole 1-methyl sulfonate, 0.2 g of 3-vinyl-1-({26-[(3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24-octaoxa hexacosyl}oxy) imidazole bis(1-methyl sulfonate), 0.2 g of 3-vinyl-1-[11-(3-vinylimidazolyl)undecyl]imidazole bis(1-methyl sulfonate), 0.02 g of photoinitiator 184 and 1.3 g of water were placed in a centrifuge tube, ultrasonicated in a water bath ultrasonic for 30 min, and the uniformly mixed pre-mixture was centrifuged at a speed of 8000 rpm for 5 min to obtain a micellar ionic liquid pre-mixture.

[0083] Secondly, 2 g of the micellar ionic liquid pre-mixture was uniformly coated on a PET substrate film, and then a layer of PET substrate film was covered on the uniformly coated plane at a pressure of 8 N / m. The pressed micellar ionic liquid pre-mixture was irradiated under a 365 nm surface light source at a power of 50 mW / cm2 The polymerization was initiated by light intensity for 30 min, and the polymer film in the interlayer was removed to obtain a micelle-type polyionic liquid ion exchange membrane.

[0084] Example 2

[0085] First, 2 g of 1-vinyl-3-n-hexylimidazolium 4-methylbenzenesulfonate, 0.16 g of 3-vinyl-1-({26-[(3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24-octaoxahexadecane-1-yl}oxy)imidazolium bis(4-methylbenzenesulfonate), 0.2 g of 3-vinyl-1-[11-(3-vinylimidazolyl)undecyl]imidazolium bis(4-methylbenzenesulfonate), 0.02 g of photoinitiator 184 and 1.3 g of water were placed in a centrifuge tube and sonicated in a water bath for 30 min. The ultrasonically mixed premix was then centrifuged at 8000 rpm for 5 min to obtain a micellar ionic liquid premix.

[0086] Next, 2 g of micellar ionic liquid premix was uniformly coated onto a PTFE substrate film. Then, a layer of PTFE substrate film was applied to the uniformly coated surface under a pressure of 10 N / m. The compressed micellar ionic liquid premix was then subjected to a 365 nm surface light source at a pressure of 50 mW / cm². 2 The polymerization was initiated by light intensity for 30 min, and the polymer film in the interlayer was removed to obtain a micelle-type polyionic liquid ion exchange membrane.

[0087] Example 3

[0088] First, 2 g of 1-vinyl-3-n-hexylimidazolium-1-phenylsulfonate, 0.16 g of 3-vinyl-1-({26-[(3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24-octaoxahexadecane-1-yl}oxy)imidazolium bis(1-phenylsulfonate), 0.16 g of 3-vinyl-1-[11-(3-vinylimidazolyl)undecyl]imidazolium bis(1-phenylsulfonate), 0.02 g of photoinitiator 184 and 1.3 g of water were placed in a centrifuge tube and sonicated in a water bath for 30 min. The ultrasonically mixed premix was then centrifuged at 8000 rpm for 5 min to obtain a micelle-type ionic liquid premix.

[0089] Next, 2 g of micellar ionic liquid premix was uniformly coated onto a PET substrate film. Then, a layer of PET substrate film was applied to the uniformly coated surface under a pressure of 8 N / m. The pressed micellar ionic liquid premix was then subjected to a 365 nm surface light source at a pressure of 50 mW / cm². 2The polymer thin film in the interlayer is taken out after irradiation of the light intensity for 30 min, and a micellar polyionic liquid ion exchange membrane is obtained.

[0090] A third object of the present application provides a micellar polyionic liquid ion exchange membrane for use as a separator in a fuel cell.

[0091] Example 4

[0092] The present example provides a fuel cell comprising a fuel cell anion exchange membrane, wherein the fuel cell anion exchange membrane is based on the micellar polyionic liquid ion exchange membrane provided in Example 1.

[0093] Example 5

[0094] The present example provides a fuel cell comprising a fuel cell anion exchange membrane, wherein the fuel cell anion exchange membrane is based on the micellar polyionic liquid ion exchange membrane provided in Example 2.

[0095] Example 6

[0096] The present example provides a fuel cell comprising a fuel cell anion exchange membrane, wherein the fuel cell anion exchange membrane is based on the micellar polyionic liquid ion exchange membrane provided in Example 3.

[0097] Verify the technical effects of Examples 1 to 3:

[0098] Figure 1 The micellar polyionic liquid ion exchange membrane is a brownish yellow self-supporting membrane, which is suitable for fuel cell separator applications.

[0099] Scanning electron microscope micellar structure characterization: The micellar polyionic liquid ion exchange membranes in Examples 1-3 were freeze-dried and fractured, and the cross section was fixed on the sample stage with conductive glue. The sample was sprayed with gold, and the thickness of the sprayed gold was controlled at 10-20 nm. The sample stage was loaded into a scanning electron microscope, and a suitable observation area was found at a low magnification, and then the magnification was gradually increased, the acceleration voltage and working distance were adjusted to ensure good electron beam focusing. The scanning electron microscope images are shown in Figure 2 and Figure 3 showing a dense and stacked micellar structure. Figure 2 and Figure 3 The scanning electron microscope images of the micellar polyionic liquid ion exchange membrane show a dense and stacked micellar structure.

[0100] Fourier infrared absorption spectrum polymerization characterization: The premix and the polymerized micellar polyionic liquid ion exchange membrane of Examples 1-3 were tested by diffuse reflectance Fourier infrared absorption spectroscopy in the range of 700-4000 cm -1 The test results are shown inFigure 4 The figure shows. Figure 4 The figure shows the Fourier infrared absorption spectrum of the micellar polyionic liquid ion premix and the ion exchange membrane. According to the Fourier infrared absorption spectrum, the polymerizable functional group (v C=C is 1660-1680 cm -1 ) is fully polymerized, the densely stacked micellar structure is polymerized and fixed, effectively resisting the water swelling phenomenon of the membrane, and ensuring the stability of the polymer structure.

[0101] Ion conduction test: using a two-electrode or four-electrode system, platinum or stainless steel sheets are used as electrodes, the electrodes are fixed in a fuel cell electrolytic cell with a constant temperature bath, the temperature is controlled (such as 25°C) and kept stable, an alternating voltage (frequency usually 10 -2 ~10 6 Hz) is applied through an electrochemical workstation, impedance data at different frequencies are collected, and the solution resistance is fitted to obtain the ion conductivity, and the ion conductivity is calculated by the formula σ=L / (R A) according to the conductivity cell constant, where σ is the conductivity, L is the electrode spacing, R is the resistance, and A is the electrode area. The specific test results are shown in Figure 5 and Table 1 below.

[0102] Table 1

[0103]

[0104] Figure 5 The figure shows the ion conductivity test of the micellar polyionic liquid ion exchange membrane examples 1-3. According to the alternating current impedance data, the ion conductivity of examples 1-3 is in the range of 0.48-1.05 mS / cm.

[0105] It can be concluded from Table 1 that the test samples all have low surface resistance and high ion conductivity, among which the surface resistance of example 1 is as low as 22.0 Ω / cm, and the ion conductivity is as high as 1.05 mS / cm, and the ion transmission efficiency is outstanding. This performance advantage can effectively reduce the internal resistance of the fuel cell and improve the electrochemical conversion efficiency of the battery, providing strong support for the energy output and working stability of the fuel cell, and helping to promote its efficient application in the energy field.

[0106] Figure 6 The figure shows a schematic diagram of the assembly structure fragment of the micellar polyionic liquid ion exchange membrane, where the spherical structure is a densely packed spherical micellar structure, and the gray color is the cross-linking structure between the micelles. The micelles can form a continuous and efficient ion conduction channel to help the rapid transmission of ions to improve the electrochemical efficiency.

[0107] Example 7

[0108] First, 2 g of 1-vinyl-3-n-hexylimidazole 4-bromobenzenesulfonate, 0.6 g of 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24- octaoxa-hexacosyl}oxy)imidazole bis (4-bromobenzenesulfonate), 0.6 g of 3-vinyl-1- [11-(3-vinylimidazolyl)undecyl]imidazole bis (4-bromobenzenesulfonate), 2 g of photoinitiator 184 and 10 g of dichloromethane were put into a centrifuge tube, ultrasonic mixing was carried out in a water bath at 75°C for 50 min, and the ultrasonic mixed premix was centrifuged at a speed of 3000 rpm for 5 min to obtain a micellar ionic liquid premix.

[0109] Secondly, 2 g of the micellar ionic liquid premix was uniformly coated on a PET base film, and a layer of PET base film was covered on the uniformly coated plane at a pressure of 5 N / m, the micellar ionic liquid premix after pressing was irradiated with light at an intensity of 30 mW / cm 2 for 20 min under a 365 nm surface light source to initiate polymerization, and the polymer film in the sandwich was taken out to obtain a micellar polyionic liquid ion exchange film.

[0110] Example 8

[0111] First, 2 g of 1-vinyl-3-n-hexylimidazole 4-bromobenzenesulfonate, 0.6 g of 3-vinyl-1-({26-[ (3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24- octaoxa-hexacosyl}oxy)imidazole bis (4-bromobenzenesulfonate), 0.6 g of 3-vinyl-1- [11-(3-vinylimidazolyl)undecyl]imidazole bis (4-bromobenzenesulfonate), 2 g of photoinitiator 184 and 10 g of dichloromethane were put into a centrifuge tube, ultrasonic mixing was carried out in a water bath at 75°C for 50 min, and the ultrasonic mixed premix was centrifuged at a speed of 3000 rpm for 5 min to obtain a micellar ionic liquid premix.

[0112] Secondly, 2 g of the micellar ionic liquid premix was uniformly coated on a polyurethane base film, and a layer of PTFE base film was covered on the uniformly coated plane at a pressure of 5 N / m, the micellar ionic liquid premix after pressing was irradiated with light at an intensity of 50 mW / cm 2 for 30 min under a 365 nm surface light source to initiate polymerization, and the polymer film in the sandwich was taken out to obtain a micellar polyionic liquid ion exchange film.

[0113] Example 9

[0114] First, 2 g of 1-vinyl-3-n-hexylimidazole 1-cyclopropyl sulfonate, 0.3 g of 3-vinyl-1-({26-[(3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24-octaoxa-hexacosyl}oxy)imidazole bis(4-methylbenzenesulfonate), 0.3 g of 3-vinyl-1-[11-(3-vinylimidazolyl)undecyl]imidazole bis(4-methylbenzenesulfonate), 0.2 g of photoinitiator 184 and 5 g of methanol were placed in a centrifuge tube, ultrasonicated in a water bath at 9°C for 30 min, and the uniformly mixed pre-mixture was centrifuged at 4000 rpm for 6 min to obtain a micellar ionic liquid pre-mixture.

[0115] Second, 2 g of the micellar ionic liquid pre-mixture was uniformly coated on a polycarbonate base film, and a PET base film was then overlaid on the uniformly coated plane at a pressure of 6 N / m. The micellar ionic liquid pre-mixture after pressing was irradiated with light at an intensity of 20 mW / cm 2 for 30 min under a 365 nm surface light source to initiate polymerization. The polymer thin film in the sandwich was removed to obtain a micellar polyionic liquid ion exchange membrane.

[0116] The micellar polyionic liquid ion exchange membrane prepared by Examples 7-9 was used as a fuel cell anion exchange membrane, and verification showed that the performance advantage of the micellar polyionic liquid ion exchange membrane could effectively reduce the internal resistance of the fuel cell and improve the electrochemical conversion efficiency of the cell, providing strong support for the energy output and working stability of the fuel cell and helping to promote its efficient application in the energy field.

[0117] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A micellar polyionic liquid ion exchange membrane, characterized by, The polyionic liquid and the polar solvent are mixed uniformly at a mass ratio of 1: (0.01-5), the ionic liquid forms a micellar phase separation structure, and the micellar structure is solidified by a method of polymerization and solidification; The chemical structure of the polyionic liquid is shown in the following formula (1): wherein R is a C1-C16 alkyl chain; a = 1-20, b = 1-20; n:m:p = (0.01-0.3):(0.01-0.3):1; X - having a structure according to any one of formulae (2)-(8): The ionic conductivity is 0.48-1.05 mS / cm.

2. A method for preparing a micelle-type polyionic liquid ion exchange membrane, used to prepare the micelle-type polyionic liquid ion exchange membrane according to claim 1, characterized in that, The preparation method comprises the following steps: The mass ratio of the vinyl imidazole sulfonate, the polar solvent and the additive is adjusted to construct a micellar phase separation structure ionic liquid premix, the micellar phase separation structure ionic liquid premix is mixed uniformly under ultrasonic, and the mixture slurry is obtained by centrifugal degassing; the mass ratio of the vinyl imidazole sulfonate, the polar solvent and the additive is 1: (0.01-5): (0.001-1); wherein the vinyl imidazole sulfonate comprises vinyl imidazole sulfonate monomers, a vinyl imidazole sulfonate aqueous phase crosslinking agent and a vinyl imidazole sulfonate oil phase crosslinking agent at a mass ratio of 1: (0.01-0.3): (0.01-0.3); The mixture slurry after degassing is uniformly coated on a support substrate to form a thin film and to perform a polymerization reaction, so as to obtain a micellar polyionic liquid ion exchange membrane.

3. The method for preparing a micelle-type polyionic liquid ion exchange membrane according to claim 2, characterized in that, The additive is a thermal initiator, a photo initiator, a radiation initiator or a microwave initiator.

4. The method for preparing a micelle-type polyionic liquid ion exchange membrane according to claim 2, characterized in that, The polymerization reaction condition is that the reaction temperature is 0-75 DEG C, the reaction irradiation condition is ultraviolet light, visible light or microwave irradiation, and the reaction time is 1 minute-12 hours; The irradiation wavelength of the ultraviolet light and the visible light is selected from 250-800 nm.

5. The method for preparing a micelle-type polyionic liquid ion exchange membrane according to claim 2, characterized in that, The mixture slurry after degassing is uniformly coated on a support substrate by using a method of blade coating, pressure coating or roller coating.

6. The method for preparing a micelle-type polyionic liquid ion exchange membrane according to claim 2, characterized in that, The polar solvent is selected from one of water, glycerol, methanol, ethanol, butanol, propanol, ethylene glycol, acetic acid, dichloromethane, trichloromethane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, ethylene carbonate, propylene carbonate, diethyl carbonate and methyl ethyl carbonate.

7. The preparation method of the micellar polyionic liquid ion exchange membrane according to claim 2, wherein the vinyl imidazole sulfonate monomer is selected from any one of the following: 1-vinyl-3-n-hexylimidazole 1-methyl sulfonate, 1-vinyl-3-n-hexylimidazole 1-vinyl sulfonate, 1-vinyl-3-n-hexylimidazole 1-cyclopropyl sulfonate, 1-vinyl-3-n-hexylimidazole 1-phenyl sulfonate, 1-vinyl-3-n-hexylimidazole 1-bromomethyl sulfonate, 1-vinyl-3-n-hexylimidazole 4-methyl benzene sulfonate and 1-vinyl-3-n-hexylimidazole 4-bromobenzene sulfonate. ​ The vinyl imidazole sulfonate aqueous phase crosslinking agent is selected from any one of the following: 3-vinyl-1-({26-[(3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24- octaoxa hexacosyl}oxy)imidazole bis(1-methyl sulfonate); 3-vinyl-1-({26-[(3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24-octaoxa hexacosyl}oxy)imidazole bis(1-vinyl sulfonate); 3-vinyl-1-({26-[(3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24-octaoxa hexacosyl}oxy)imidazole bis(1-phenyl sulfonate); 3-vinyl-1-({26-[(3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24-octaoxa hexacosyl}oxy)imidazole bis(4-methyl phenyl sulfonate); 3-vinyl-1-({26-[(3-vinylimidazolyl)oxy]-3,6,9,12,15,18,21,24-octaoxa hexacosyl}oxy)imidazole bis(4-bromophenyl sulfonate). The vinyl imidazole sulfonate oil phase crosslinking agent is selected from any one of the following: 3-vinyl-1-[11-(3-vinylimidazolyl)undecyl]imidazole bis(1-methyl sulfonate); 3-vinyl-1-[11-(3-vinylimidazolyl)undecyl]imidazole bis(1-vinyl sulfonate); 3-vinyl-1-[11-(3-vinylimidazolyl)undecyl]imidazole bis(1-phenyl sulfonate); 3-vinyl-1-[11-(3-vinylimidazolyl)undecyl]imidazole bis(4-methyl phenyl sulfonate); 3-vinyl-1-[11-(3-vinylimidazolyl)undecyl]imidazole bis(4-bromophenyl sulfonate).

8. The method of claim 2, wherein the support substrate is selected from the group consisting of polyethylene terephthalate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer, polycarbonate, polyurethane, phenol formaldehyde resin, polytetrafluoroethylene, polyvinylidene fluoride, and polyether sulfone.

9. The method of claim 2, wherein the pressure of the support substrate is in the range of 5 N / m to 30 N / m.

10. The fuel cell comprising the fuel cell anion exchange membrane of claim 1. ​ ​ ​

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