CN106147197A - A kind of fuel cell many conduction sites polyphenyl ether anion exchange membrane and preparation method thereof - Google Patents

Abstract

The invention discloses a polyphenylene ether-based anion exchange membrane with multiple conductive sites for fuel cells and a preparation method thereof, belonging to the technical field of fuel cell materials. The anion exchange membrane is composed of 99% by weight of nitrogen having the following repeating structural unit II Methylimidazole quaternized polyphenylene ether anion exchange membrane and 1% by weight of polyionic liquid doped therein with structural formula I consist of: Wherein n is an integer not less than 1, and the number of carbon atoms of the straight-chain alkyl group is 5-12; Where x is an integer not less than 0; y is an integer not less than 0, and x and y are not 0 at the same time. The method of the invention has simple process and low cost. The prepared multi-conducting site polyphenylene ether-based anion exchange membrane has the advantages of high proton conductivity, good thermal stability, etc., has wide application prospects, and is especially suitable for anion exchange membrane fuel cells.

Description

A kind of polyphenylene ether-based anion-exchange membrane with multi-conduction sites for fuel cells and its preparation method

technical field

The invention relates to a polyphenylene ether-based anion-exchange membrane with multi-conduction sites for fuel cells and a preparation method thereof, belonging to the technical field of fuel cell materials, in particular to the technical field of anion-exchange membranes.

Background technique

A fuel cell is an efficient and clean energy conversion device. In recent years, polymer membrane fuel cells have been widely used. As a key material, polymer membrane plays a decisive role in the performance and life of fuel cells. The most typical one is DuPont's Nafion membrane, which has excellent conductivity, high mechanical strength and chemical stability, and is the object of reference for researchers. However, polymer membrane fuel cells with proton exchange membranes as electrolytes have a series of disadvantages: (1) under acidic conditions, noble metals such as platinum and gold need to be used as catalysts, which increases the cost of fuel cells; (2) under acidic conditions, The catalyst is prone to CO poisoning, which seriously reduces the performance of the fuel cell; (3) the fuel and protons conduct in the same direction, which easily causes electrode short circuit.

In order to overcome the above disadvantages, anion exchange membranes are considered as alternative materials for proton exchange membranes. Anion exchange membranes have high catalyst stability under alkaline conditions, so non-precious metal materials such as iron, cobalt, and nickel can be used as catalysts, and the oxygen reduction kinetics of catalysts under alkaline conditions is better than that under acidic conditions. However, due to the limitations of the anion exchange membrane itself, it is necessary to greatly improve the ion conductivity, alkali stability and mechanical properties of the anion exchange membrane to reach the commercial level.

The study found that increasing the conduction sites can effectively improve the conductivity of anion exchange membranes. There are two ways to increase the conduction sites: one is to graft ionic groups containing multiple conduction sites onto the polymer backbone through graft polymerization; the other is to graft the ionic groups that can conduct hydroxide Ionic ionic liquids are directly doped into polymers. The second method is simpler and more direct.

Polyphenylene oxide (PPO) is a high-strength engineering plastic developed by General Motors. It has outstanding electrical insulation and water resistance, high heat resistance, and simple structure, which is conducive to quantitative and qualitative research on branched or doped ionic liquids. Effects on the performance of anion exchange membranes.

At present, most of the research objects of ionic liquids are independent conductive groups. One unit of trimidazolium has three conductive groups. In theory, a single unit of trimidazolium can greatly improve the ion conductivity. In addition, trimidazole can also maintain high stability under alkaline conditions.

Therefore, the ion conductivity and stability of the anion exchange membrane can be improved by incorporating the ionic liquid of trimidazolidine into the anion exchange membrane of polyphenylene ether.

Contents of the invention

One of the objectives of the present invention is to provide a polyphenylene ether-based anion exchange membrane with multiple conductive sites for a dye cell, which has high ion conductivity and high stability.

Above-mentioned purpose of the present invention is achieved through the following technical solutions:

A polyphenylene ether-based anion-exchange membrane with multiple conductive sites for a fuel cell, characterized in that: the anion-exchange membrane is made of 98-99% by weight polyphenylene quaternized with nitrogen-methylimidazole having the following repeating structural unit II Composition of ether anion exchange membrane and 1-2% by weight of polyionic liquid with structural formula I doped therein:

Where n is an integer not less than 1, and the number of carbon atoms in the straight-chain alkyl group is 5-12;

Where x is an integer not less than 0; y is an integer not less than 0, and x and y are not 0 at the same time.

Preferably, in the structural unit II, x:y=7:3.

Preferably, the structural formula I is poly 1,3,5-tris(3-pentyl-1-imidazole), poly 1,3,5-tris(3-octyl-1-imidazole) or poly 1,3 , 5-tris(3-dodecyl-1-imidazole) benzene ionic liquid.

Another object of the present invention is to provide a method for preparing the above-mentioned multi-conducting site polyphenylene ether-based anion exchange membrane.

Above-mentioned purpose of the present invention is achieved through the following technical solutions:

A method for preparing a polyphenylene ether-based anion exchange membrane with multiple conductive sites for a fuel cell, comprising the steps of:

(1) Synthesis of polyphenylene ether (PPO) nitrogen methyl imidazole skeleton

Add polyphenylene ether into the reaction device, heat to 40-60°C under nitrogen atmosphere, after the polyphenylene ether is completely dissolved, add benzoyl peroxide (PPO) and N-bromosuccinimide (NBS) , raise the temperature to 70-90°C, react for 3-5 hours, then lower the temperature to room temperature, rotate the reactant solution at 40-80°C until the color turns brownish yellow, and then precipitate in methanol to obtain light Yellow solid, dissolve the light yellow solid with dichloromethane, spin evaporate, and precipitate, repeat this operation to obtain pure light yellow brominated polyphenylene ether (BPPO), dry it, dissolve it in DMF solution, and wait until it is completely dissolved , add N-methylimidazole, react, and completely quaternize the brominated site to obtain polyphenylene ether quaternized with nitrogen methylimidazole;

(2) Preparation of polytrimidazolium benzene ionic liquid

(i) Preparation of 1,3,5-three (1-imidazole) benzene:

Add 1,3,5-tribromobenzene, imidazole, potassium carbonate and copper sulfate into the container, blow in nitrogen, raise the temperature to 170-190°C, and react for 8-16 hours, then the temperature of the product drops to room temperature, and use Washing with ionic water, filtering, collecting the upper layer solid, extracting the crude product with dichloromethane, collecting the organic layer, and rotary evaporating to obtain 1,3,5-tris(1-imidazole)benzene;

(ii) preparation of polytrimidazolium benzene ionic liquid:

Dissolve 1,3,5-tris(1-imidazole)benzene in N,N-dimethylformamide (DMF) solution at 80-120°C, add halogenated alkanes, and react for 6-18 hours to obtain a yellow solid. After filtering, it is dried in an oven to obtain the polytrimidazolium benzene ionic liquid;

(3) Preparation of polyphenylene ether-based anion exchange membranes with multi-conducting sites

Weigh the product obtained in step 2, add the same amount of product obtained in step (1), sonicate for 0.5 hours and stir for 0.5 hours, pour the final product into an ultra-flat surface dish, and dry it in an oven at 60°C to obtain light yellow transparent membrane, and then soak the membrane in 1mol/L NaOH solution for two days to obtain the final anion exchange membrane.

Preferably, the repeated operation in the step (1) is 3 times.

Preferably, the halogenated alkane in the step (2) is dibromopentane, dibromooctane or dibromododecane.

Preferably, the polytrimidazole benzene ionic liquid in the step (2) is poly 1,3,5-tris(3-pentyl-1-imidazole), poly 1,3,5-tris(3-octyl base-1-imidazole) or poly-1,3,5-tris(3-dodecyl-1-imidazole) benzene ionic liquid.

Preferably, the amount of the product obtained in the step (1) in the step (3) is reduced by half.

Compared with the prior art, the present invention has obvious advantages:

1. The preparation process of the membrane is simple. The polyionic liquid is directly doped into the polyphenylene oxide (PPO) anion exchange membrane skeleton, which simplifies the synthesis steps of the membrane.

2. The ion conductivity of the membrane is high. In addition to the conductivity of the membrane itself, the invention introduces a ternary polyionic liquid, and each unit can conduct three hydroxide ions, which greatly enhances the ion conductivity of the membrane.

3. The dimensional stability of the membrane is good. Pure polyphenylene oxide (PPO) skeleton anion exchange membrane has high water absorption and expansion rate, and it is easy to break during the test. After adding the ternary polyionic liquid, the membrane can still maintain relative integrity after the test is completed.

The present invention will be described in detail below with reference to the drawings and specific embodiments. It should be understood that the examples described only refer to the preferred embodiments of the present invention, and various changes and improvements are possible without departing from the spirit and scope of the present invention.

Description of drawings

Fig. 1 is the NMR spectrum of 1,3,5-three (1-imidazole) benzene synthesized by the present invention, H ² corresponds to the hydrogen on the benzene ring, H ¹ , H ³ , H ⁴ correspond to the hydrogen on the imidazole ring respectively three hydrogens.

Fig. 2 is the NMR spectrum of poly 1,3,5-tris(3-pentyl-1-imidazole) phenyl ionic liquid (PTPIB) synthesized in the present invention, wherein H ¹ is the hydrogen on the benzene ring, H ² , H ³ , H ⁴ are three hydrogens on the imidazole ring, H ⁵ , H ⁶ are hydrogens on two carbons connected to nitrogen on the imidazole ring, and H ⁷ is other hydrogens on the dodecyl chain.

Fig. 3 is the NMR spectrum of poly 1,3,5-tris(3-octyl-1-imidazole) benzene ionic liquid (PTOIB) synthesized in the present invention, wherein H ¹ is the hydrogen on the benzene ring, H ² , H ³ , H ⁴ are three hydrogens on the imidazole ring, H ⁵ , H ⁶ are hydrogens on two carbons connected to nitrogen on the imidazole ring, and H ⁷ is other hydrogens on the dodecyl chain.

Fig. 4 is the NMR image of poly 1,3,5-tris(3-dodecyl-1-imidazole) benzene ionic liquid (PTDIB) synthesized in the present invention, wherein H ¹ is the hydrogen on the benzene ring, H ² , H ³ and H ⁴ are three hydrogens on the imidazole ring respectively, H ⁵ and H ⁶ are hydrogens on two carbons connected with nitrogen on the imidazole ring respectively, and H ⁷ is other hydrogens on the dodecyl chain.

Fig. 5 is the synthetic polyphenylene ether nitrogen methyl imidazole anion exchange membrane of the present invention: the nuclear magnetic resonance spectrum of the polyphenylene ether of nitrogen methyl imidazole quaternization, wherein H ¹ is the hydrogen on the methyl group that connects on the benzene ring, H ² is the hydrogen on the methyl group attached to the quaternary ammonium salt, H ³ is the hydrogen on the methylene group attached to the benzene ring, H ⁴ and H ⁵ are the hydrogen on the benzene ring.

Fig. 6 is a graph showing the relationship between the ion conductivity and the temperature change of the polyphenylene ether nitrogen methylimidazole anion exchange membrane 1-4 synthesized in the present invention.

detailed description

Comparative Example 1

1. Preparation of polyphenylene ether (PPO) nitrogen methyl imidazole skeleton:

Add 0.3g of commercially available polyphenylene ether into a 100mL three-necked flask equipped with a stirrer, condenser and gas guide tube, and heat it to 50°C under nitrogen atmosphere. After the polyphenylene ether is completely dissolved, add 4.64g of commercially available peroxide Benzoyl (PPO) and 0.232g commercially available N-bromosuccinimide (NBS), the temperature of the oil bath was raised to 80°C, after 4 hours of reaction, the temperature was lowered to room temperature, and the reactant solution was transferred to In a rotary evaporator, at 60°C, rotary evaporate until the color of the solution turns brownish-yellow, then precipitate in methanol to obtain a light yellow solid, dissolve the light yellow solid with commercially available dichloromethane, rotary evaporate, and precipitate, repeat the process Operate 3 times to obtain pure light yellow brominated polyphenylene ether (BPPO), dry it in an oven at 60°C, dissolve 0.25g of dried BPPO in 15mL of commercially available DMF solution, and add 207μL of commercially available DMF solution after it is completely dissolved. Sell N-methylimidazole and react for 12 hours to completely quaternize the brominated sites to obtain polyphenylene ether quaternized with nitrogen-methylimidazole.

As shown in Figure 5, it is the nuclear magnetic resonance spectrum of polyphenylene ether trimethylamine film, wherein, H ¹ is the hydrogen on the methyl group connected on the benzene ring, H ² is the hydrogen on the methyl group connected on the quaternary ammonium salt, H ³ is the hydrogen of the methylene connected on the benzene ring, H ⁴ and H ⁵ are the hydrogen on the benzene ring.

2. Preparation of polyphenylene ether-based anion exchange membrane:

Pour the product obtained in step 1 into an ultra-flat surface dish, place it in an oven and dry it at 60°C to obtain a light yellow transparent film, and then soak the film in 1mol/L NaOH solution for two days to obtain the final polystyrene for fuel cell Ether-based anion exchange membrane 1, the thickness of the membrane was measured with a screw micrometer. The polyphenylene ether-based anion exchange membrane was used as a control sample, and no polyionic liquid was added.

Example 1

1. Preparation of polyphenylene ether (PPO) nitrogen methyl imidazole skeleton:

Add 0.3g of commercially available polyphenylene ether into a 100mL three-necked flask equipped with a stirrer, condenser and gas guide tube, and heat it to 50°C under nitrogen atmosphere. After the polyphenylene ether is completely dissolved, add 4.64g of commercially available peroxide Benzoyl (PPO) and 0.232g commercially available N-bromosuccinimide (NBS), the temperature of the oil bath was raised to 80°C, after 4 hours of reaction, the temperature was lowered to room temperature, and the reactant solution was transferred to In a rotary evaporator, at 60°C, rotary evaporate until the color of the solution turns brownish-yellow, then precipitate in methanol to obtain a light yellow solid, dissolve the light yellow solid with commercially available dichloromethane, rotary evaporate, and precipitate, repeat the process Operate 3 times to obtain pure light yellow brominated polyphenylene ether (BPPO), dry it in an oven at 60°C, dissolve 0.25g of dried BPPO in 15mL of commercially available DMF solution, and add 207μL of commercially available DMF solution after it is completely dissolved. N-methylimidazole was sold and reacted for 12 hours to completely quaternize the brominated sites to obtain polyphenylene ether quaternized with nitrogen-methylimidazole, the NMR spectrum of which is shown in Figure 5.

2. Preparation of poly-1,3,5-tris(3-pentyl-1-imidazole) phenyl ionic liquid (PTPIB):

(1), the preparation of 1,3,5-three (1-imidazole) benzene:

Add 2.52g of commercially available 1,3,5-tribromobenzene, 5.44g of commercially available imidazole, 4.42g of commercially available potassium carbonate, and 0.05g of commercially available copper sulfate into a 100mL three-necked flask, blow in nitrogen, and raise the temperature to 180 ℃, reacted for 12 hours, then the temperature of the product was lowered to room temperature, washed five times with 30mL deionized water, filtered, and collected the upper layer solid, the crude product was extracted 5 times with 30mL commercially available dichloromethane, and the organic layer was collected and then rotary evaporated to obtain 1 ,3,5-tris(1-imidazole)benzene.

As shown in Figure 1, it is the NMR spectrum of 1,3,5-tris(1-imidazole)benzene, where H ¹ corresponds to the hydrogen on the benzene ring, and H ² , H ³ , and H ⁴ correspond to the imidazole ring respectively on the three hydrogens.

(2), preparation of poly 1,3,5-tris(3-pentyl-1-imidazole) phenyl ionic liquid (PTPIB):

Dissolve 0.15g of commercially available 1,3,5-tris(1-imidazole)benzene in 15mL of commercially available N,N-dimethylformamide (DMF) solution at 100°C, add 0.375g of commercially available dibromopentane , and reacted for 12 hours to obtain a yellow solid, which was filtered and dried in an oven at 60° C. to obtain poly-1,3,5-tris(3-pentyl-1-imidazole)phenylene ionic liquid (PTPIB).

As shown in Figure 2, it is the nuclear magnetic resonance spectrum of poly 1,3,5-tris(3-pentyl-1-imidazole) phenyl ionic liquid (PTPIB), wherein, H ¹ is the hydrogen on the benzene ring, H ² , H ³ , H ⁴ are the three hydrogens on the imidazole ring, H ⁵ , H ⁶ are the hydrogens on the two carbons connected to the nitrogen on the imidazole ring, and H ⁷ is the other hydrogens on the dodecyl chain.

3. Preparation of polyphenylene ether-based anion exchange membrane with multi-conducting sites:

Weigh 0.003g of the product obtained in step 2, add the same amount of the product obtained in step 1, sonicate for 0.5 hours and stir for 0.5 hours, pour the final product into an ultra-flat surface dish, and dry it in an oven at 60°C to obtain light yellow transparent membrane, and then soak the membrane in 1mol/L NaOH solution for two days to obtain the final polyphenylene ether-based anion exchange membrane 2 with multiple conductive sites for fuel cells, and measure the thickness of the membrane with a screw micrometer.

Example 2

1. Preparation of polyphenylene ether (PPO) nitrogen methyl imidazole skeleton:

Add 0.3g of commercially available polyphenylene ether into a 100mL three-necked flask equipped with a stirrer, condenser and gas guide tube, and heat it to 50°C under nitrogen atmosphere. After the polyphenylene ether is completely dissolved, add 4.64g of commercially available peroxide Benzoyl (PPO) and 0.232g commercially available N-bromosuccinimide (NBS), the temperature of the oil bath was raised to 80° C. after 4 hours of reaction, the temperature was lowered to room temperature, and the reactant solution was transferred to In a rotary evaporator, 60°C rotary steam until the solution turns brownish yellow, and then precipitate in methanol to obtain a light yellow solid, dissolve the light yellow solid with commercially available dichloromethane, rotary steam, and precipitate, repeat this operation 3 times, Obtain pure light yellow brominated polyphenylene ether (BPPO), dry it in an oven at 60°C, dissolve 0.25g of dried BPPO in 15mL of commercially available DMF solution, and after it is completely dissolved, add 207μL of commercially available N-formazan imidazole, reacted for 12 hours, completely quaternized the brominated site, and obtained polyphenylene ether quaternized with nitrogen methyl imidazole;

2. Preparation of poly-1,3,5-tris(3-octyl-1-imidazole)benzene ionic liquid (PTOIB):

(1), the preparation of 1,3,5-three (1-imidazole) benzene:

Add 2.52g of commercially available 1,3,5-tribromobenzene, 5.44g of commercially available imidazole, 4.42g of commercially available potassium carbonate, and 0.05g of commercially available copper sulfate into a 100mL three-necked flask, blow in nitrogen, and raise the temperature to 180 ℃, reacted for 12 hours, then the temperature of the product was lowered to room temperature, washed five times with 30mL deionized water, filtered, and collected the upper layer solid, the crude product was extracted 5 times with 30mL commercially available dichloromethane, and the organic layer was collected and then rotary evaporated to obtain 1 ,3,5-tris(1-imidazole)benzene.

(2), preparation of poly 1,3,5-tris(3-octyl-1-imidazole) benzene ionic liquid (PTOIB):

Dissolve 0.15g of commercially available 1,3,5-tris(1-imidazole)benzene in 15mL of commercially available N,N-dimethylformamide (DMF) solution at 100°C, add 0.443g of commercially available dibromooctane , and reacted for 12 hours to obtain a yellow solid, which was filtered and dried in an oven at 60°C to obtain poly-1,3,5-tris(3-octyl-1-imidazole)benzene ionic liquid (PTOIB).

As shown in Figure 3, it is poly 1,3,5-three (3-octyl-1-imidazole) benzene ionic liquid (PTOIB) nuclear magnetic resonance spectrum (PTOIB) synthesized by the present invention, wherein H For the hydrogen ^on the benzene ring , H ² , H ³ , H ⁴ are the three hydrogens on the imidazole ring, H ⁵ , H ⁶ are the hydrogens on the two carbons connected to the nitrogen on the imidazole ring, and H ⁷ is the other hydrogen on the dodecyl chain of hydrogen.

3. Preparation of polyphenylene ether-based anion exchange membrane with multi-conducting sites:

Weigh 0.0038g of the product obtained in step 2, add the same amount of the product obtained in step 1, sonicate for 0.5 hours and stir for 0.5 hours, pour the final product into an ultra-flat surface dish, and dry it in an oven at 60°C to obtain light yellow transparent membrane, and then soak the membrane in 1mol/L NaOH solution for two days to obtain the final polyphenylene ether-based anion exchange membrane 3 with multiple conductive sites for fuel cells, and measure the thickness of the membrane with a screw micrometer.

Example 3

1. Preparation of polyphenylene ether (PPO) nitrogen methyl imidazole skeleton:

Add 0.3g of commercially available polyphenylene ether into a 100mL three-necked flask equipped with a stirrer, condenser and gas guide tube, and heat it to 50°C under nitrogen atmosphere. After the polyphenylene ether is completely dissolved, add 4.64g of commercially available peroxide Benzoyl (PPO) and 0.232g commercially available N-bromosuccinimide (NBS), the temperature of the oil bath was raised to 80° C. after 4 hours of reaction, the temperature was lowered to room temperature, and the reactant solution was transferred to In a rotary evaporator bottle, 60 ° C rotary evaporation until the solution is brownish yellow, and then precipitate in methanol to obtain a light yellow solid, use commercially available dichloromethane to dissolve the light yellow solid, rotary evaporation, and precipitation, repeat this operation 3 times to obtain Pure light yellow brominated polyphenylene ether (BPPO), dried in an oven at 60°C, dissolved 0.25g of dry BPPO in 15mL of commercially available DMF solution, after complete dissolution, added 207μL of commercially available N-methyl Imidazole was reacted for 12 hours to completely quaternize the brominated site to obtain polyphenylene ether quaternized with nitrogen methyl imidazole;

2. Preparation of poly-1,3,5-tris(3-octyl-1-imidazole)benzene ionic liquid (PTOIB):

(1), the preparation of 1,3,5-three (1-imidazole) benzene:

Add 2.52g of commercially available 1,3,5-tribromobenzene, 5.44g of commercially available imidazole, 4.42g of commercially available potassium carbonate, and 0.05g of commercially available copper sulfate into a 100mL three-necked flask, blow in nitrogen, and raise the temperature to 180 ℃, reacted for 12 hours, then the temperature of the product was lowered to room temperature, washed five times with 30mL deionized water, filtered, collected the upper layer solid, extracted the crude product 5 times with 30mL commercially available dichloromethane, collected the organic layer and then rotary evaporated to obtain the final product.

(2), preparation of poly 1,3,5-tris(3-dodecyl-1-imidazole) benzene ionic liquid (PTDIB):

Dissolve 0.15g of commercially available 1,3,5-tris(1-imidazole)benzene in 15mL of commercially available N,N-dimethylformamide (DMF) solution at 100°C, add 0.535g of commercially available dibromideca alkane, and reacted for 12 hours to obtain a yellow solid, which was filtered and dried in an oven at 60°C to obtain poly-1,3,5-tris(3-dodecyl-1-imidazole)benzene ionic liquid (PTDIB).

As shown in Figure 4, it is the NMR figure of poly 1,3,5-three (3-dodecyl-1-imidazole) benzene ionic liquid (PTDIB) synthesized by the present invention, wherein H is the hydrogen ^on the benzene ring , H ² , H ³ , H ⁴ are the three hydrogens on the imidazole ring, H ⁵ , H ⁶ are the hydrogens on the two carbons connected to the nitrogen on the imidazole ring, and H ⁷ is the other hydrogen on the dodecyl chain of hydrogen.

3. Preparation of polyphenylene ether-based anion exchange membrane with multi-conducting sites:

Weigh 0.0049g of the product obtained in step 2, add the same amount of the product obtained in step 1, sonicate for 0.5 hours and stir for 0.5 hours, pour the final product into an ultra-flat surface dish, and dry it in an oven at 60°C to obtain light yellow transparent membrane, and then soak the membrane in 1mol/L NaOH solution for two days to obtain the final polyphenylene ether-based anion exchange membrane 4 with multiple conductive sites for fuel cells, and measure the thickness of the membrane with a screw micrometer.

The amount of the product obtained in step 1 added in step 3 can be reduced by half.

In the invention, the film is doped with polyionic liquid by casting method to obtain polyphenylene ether-based anion exchange membrane with multiple conduction sites, and the preparation process is simple and the cost is low. The prepared multi-conducting site polyphenylene ether-based anion exchange membrane has the advantages of high proton conductivity and good thermal stability, uniform thickness (120-150 μm), and an ionic liquid doping amount of 1%, which has broad application prospects and is especially suitable for Suitable for anion exchange membrane fuel cells.

Performance Testing:

Using the electrochemical AC impedance method, in a saturated water environment, from 30 ℃ to 80 ℃, test the ion exchange membrane 1-4 of the multi-conduction site polyphenylene ether-based anion exchange membrane 1-4 for the fuel cell obtained in the comparison example 1 and embodiment 1-3. Conductivity, the results are shown in Figure 6.

As shown in Figure 6, it is the polyphenylene ether-based anion exchange membrane 1-4 with multi-conduction sites synthesized by the present invention for the fuel cell (that is, the polyphenylene ether nitrogen methylimidazole anion exchange membrane synthesized by the present invention and adding poly 1, 3,5-tris(3-pentyl-1-imidazole) phenyl ionic liquid (PTPIB), poly 1,3,5-tris (3-octyl-1-imidazole) phenyl ionic liquid (PTOIB), poly 1,3,5-tris(3-dodecyl-1-imidazolium)benzene ionic liquid (PTDIB) ion exchange membrane (PTDIB) ion conductivity versus temperature.

The embodiments of the present invention have been described in detail above. All embodiments are implemented on the premise of the technical solutions of the present invention, and detailed implementation methods and specific operating procedures are provided, but the protection scope of the present invention is not limited to the above-mentioned implementation. example.

Claims (9)

1. A polyphenylene ether-based anion-exchange membrane with multiple conduction sites for a fuel cell, characterized in that: the anion-exchange membrane is quaternized by 98-99% by weight of nitrogen-methylimidazole with the following repeating structural unit II Composition of polyphenylene ether anion exchange membrane and 1-2% by weight of polyionic liquid with structural formula I doped therein: Where n is an integer not less than 1, and the number of carbon atoms in the straight-chain alkyl group is 5-12; Where x is an integer not less than 0; y is an integer not less than 0, and x and y are not 0 at the same time. 2. The polyphenylene ether-based anion exchange membrane with multiple conductive sites for fuel cells according to claim 1, characterized in that: in the repeating structural unit II, x:y=7:3. 3. The polyphenylene ether-based anion exchange membrane with multiple conduction sites for fuel cells according to claim 2, characterized in that: said structural formula I is poly 1,3,5-three (3-pentyl-1-imidazole ), poly-1,3,5-tris(3-octyl-1-imidazole) or poly-1,3,5-tris(3-dodecyl-1-imidazole) benzene ionic liquid. 4. A method for preparing a polyphenylene ether-based anion-exchange membrane with multiple conduction sites for a fuel cell, comprising the steps of: (1) Synthesis of polyphenylene ether nitrogen methyl imidazole skeleton Add polyphenylene ether into the reaction device, heat to 40-60°C under nitrogen atmosphere, after the polyphenylene ether is completely dissolved, add benzoyl peroxide and N-bromosuccinimide, and raise the temperature to 70 -90°C, after reacting for 3-5 hours, lower the temperature to room temperature, rotate the reactant solution at 40-80°C until the color of the solution turns brownish yellow, then precipitate in methanol to obtain a light yellow solid, use di Dissolve the light yellow solid with methyl chloride, spin evaporate, and precipitate. Repeat this operation to obtain pure light yellow brominated polyphenylene ether. Dry it and dissolve it in DMF solution. After it is completely dissolved, add N-methylimidazole, Reaction, complete quaternization of brominated sites to obtain polyphenylene ether quaternized with nitrogen methyl imidazole; (2) Preparation of polytrimidazolium benzene ionic liquid (i) Preparation of 1,3,5-three (1-imidazole) benzene: Add 1,3,5-tribromobenzene, imidazole, potassium carbonate and copper sulfate into the container, blow in nitrogen, raise the temperature to 170-190°C, and react for 8-16 hours, then the temperature of the product drops to room temperature, and use Washing with ionic water, filtering, collecting the upper layer solid, extracting the crude product with dichloromethane, collecting the organic layer, and rotary evaporating to obtain 1,3,5-tris(1-imidazole)benzene; (ii) preparation of polytrimidazolium benzene ionic liquid: Dissolve 1,3,5-tris(1-imidazole)benzene in N,N-dimethylformamide solution at 80-120°C, add halogenated alkanes, and react for 6-18 hours to obtain a yellow solid, which is filtered and placed drying in an oven to obtain the polytrimidazole benzene ionic liquid; (3) Preparation of polyphenylene ether-based anion exchange membranes with multi-conducting sites Weigh the product obtained in step (2), add an equivalent amount of the product obtained in step (1), stir ultrasonically, pour the final product into an ultra-flat surface dish, place it in an oven and dry it to obtain a light yellow transparent film, and then put The membrane is soaked in NaOH solution to obtain the final anion exchange membrane. 5. the preparation method of multi-conduction site polyphenylene ether-based anion exchange membrane for fuel cell according to claim 4, is characterized in that: the time of ultrasonic stirring described in the described step (3) is 0.5 hour, described The drying temperature is 60° C., the concentration of the NaOH solution is 1 mol/L, and the soaking time is two days. 6 . The method for preparing a polyphenylene ether-based anion exchange membrane with multiple conduction sites for fuel cells according to claim 4 , wherein the repeat operation in the step (1) is 3 times. 6 . 7. the preparation method of polyphenylene ether-based anion exchange membrane with multi-conduction site for fuel cell according to claim 4, is characterized in that: described in described step (2) halogenated alkane dibromopentane, dibromooctyl alkane or dibromododecane. 8. the preparation method of polyphenylene ether-based anion exchange membrane with multi-conduction sites for fuel cell according to claim 4, is characterized in that: the polytriimidazole benzene ionic liquid described in the described step (2) is poly-1, 3,5-tris(3-pentyl-1-imidazole), poly-1,3,5-tris(3-octyl-1-imidazole) or poly-1,3,5-tris(3-dodecyl -1-imidazole) benzene ionic liquid. 9. the preparation method of multi-conduction site polyphenylene ether-based anion exchange membrane for fuel cell according to claim 4, is characterized in that: the add-on of described step (1) gained product in described step (3) reduces half.