CN108461791B

CN108461791B - Composite alkaline polymer electrolyte membrane and preparation and application thereof

Info

Publication number: CN108461791B
Application number: CN201611145388.XA
Authority: CN
Inventors: 王素力; 杨丛荣; 孙公权
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2016-12-13
Filing date: 2016-12-13
Publication date: 2021-03-30
Anticipated expiration: 2036-12-13
Also published as: CN108461791A

Abstract

The invention provides a composite alkaline polymer electrolyte membrane and preparation and application thereof, wherein the composite alkaline polymer electrolyte membrane is formed by interweaving two or three polymers; it is necessary to include one polymer having a positively charged functional group, and the other or both polymers having a negatively charged functional group. The preparation of the composite alkaline polymer electrolyte membrane comprises (1) preparation of a chloromethylation polymer m; (2) preparing a composite alkaline polymer fiber porous membrane by simultaneously spinning chloromethylated polymer m and polymer with negative charge, namely a, by adopting an electrostatic spinning method; (3) the compact composite alkaline polymer electrolyte membrane is prepared by adopting a hot pressing or solvent soaking method. The alkaline polymer electrolyte membrane has good mechanical property, conductivity, liquid absorption capacity and swelling resistance; the preparation method is simple and convenient, and the composite alkaline polymer electrolyte membrane with uniform and controllable thickness and larger area can be prepared.

Description

Composite alkaline polymer electrolyte membrane and preparation and application thereof

Technical Field

The invention belongs to the field of alkaline polymer electrolyte exchange membranes; the invention also relates to a preparation method of the alkaline polymer electrolyte exchange membrane with higher conductivity and good mechanical property.

Background

In recent years, with the shortage of energy and the increasing prominence of environmental issues, new green and environmentally-friendly energy is gradually a hot spot of global research. Electrochemical energy devices (such as alkaline anion exchange membrane fuel cells, water electrolysis cells, flow batteries, metal air batteries and the like) which adopt alkaline polymer electrolyte exchange membranes (APEMs) as solid electrolytes have the advantages of high specific power density, low cost, cleanness, environmental protection and the like, and become the focus of attention of researchers. However, the performance of the APEMs at present can not meet the requirements of the application environment of the electrochemical device. In the working environment, the existence of strong base, high temperature, strong electric field and magnetic field makes the stability, conductivity and mechanical property of the APEMs face a great challenge, how to balance the contradiction between the conductivity and mechanical property of the APEMs, and the improvement of the chemical stability in the high-temperature alkaline environment becomes the research focus in the field of the APEMs.

Much work has been done by researchers to increase the conductivity of APEMs. Guiver et al prepared block copolymer APEMs with polysulfone as the main chain, and the membrane not only has high conductivity, but also keeps lower liquid absorption and swelling, and has certain advantages in performance. The conductivity of APEMs with long side chains prepared by Linanwen et al by click chemistry under water saturation conditions can reach 62mS cm^-1. The research on the improvement of the conductivity is highlighted by the subject group of the Zhulin teacher at Wuhan university, who prepares polysulfone-type APEMs with good micro-phase separation structure through molecular structure design. They form continuous and obvious micro-phase separation structure for APEMs by grafting long hydrophobic side chain onto main chain far away from functional group, and construct structure beneficial to OH^-The channels of transport, thereby effectively increasing the conductivity of APEMs, which exceeds that of commercial products at 80 ℃

The conductivity of the membrane.

At present, although the performance of the APEMs can meet the requirements of an electrochemical system, the main chain of the APEMs commonly used contains ether bonds, which causes the stability of the main chain of the APEMs to have certain hidden troubles in the working environment of an electrochemical device. Because of the strong nucleophile OH in the alkaline environment^-Attack the C-O bond in the backbone, which can hydrolyze and break the bond, resulting in the fragmentation of the membrane as a whole (PNAS, February 12,2013, vol.110). Researches show that the polystyrene-based main chain has better chemical stability in a high-temperature alkaline environment. However, polystyrene as a hard material, the mechanical properties of APEMs prepared by functionalizing it are still very challenging (especially for preparing ultrathin films, this problem is more prominent). Therefore, the key point for promoting the development and application of the APEMs is to improve the mechanical property of the polystyrene by utilizing the advantage of the chemical stability of the hydrocarbon main chain. Chemical crosslinking and composite reinforcement are the commonly used methods for enhancing the mechanical property of the membrane at present, although the two methods can improve the mechanical strength of the membrane, reduce the swelling of the membrane and enhance the ruler of the membrane to a certain extentDimensional stability, but both methods still have certain disadvantages. Wherein, the IEC value of the membrane is reduced by adopting a chemical crosslinking method, so that the conductivity of the membrane is reduced; because the ion conducting part and the reinforcing part of the membrane prepared by adopting the composite reinforcing membrane method of the base membrane lack chemical action, the polymer conducting ions can be removed from the base membrane along with the prolonging of the working time, so that the membrane loses the capability of conducting ions; membranes made by blending (especially two or more charged polymers) can suffer from macroscopic phase separation due to poor compatibility of the two polymers, resulting in poor or no ionic conductivity, or even failure to make uniform membranes.

Disclosure of Invention

In view of the above problems, the present invention is directed to preparing an alkaline polymer electrolyte membrane having good mechanical properties, high electrical conductivity, and uniform physical and chemical properties.

The invention adopts an electrostatic spinning technology to prepare a composite alkaline polymer electrolyte membrane with good mechanical property, higher conductivity and uniform physical and chemical properties, and the specific scheme is as follows:

the composite alkaline polymer electrolyte membrane is formed by interweaving two or three polymers. Wherein one polymer having a positively charged functional group must be included, and the other or both polymers are negatively charged polymers. Wherein, electrostatic action can be formed between the polymer with negative charge and the polymer with positive charge functional group, and the structure of the composite type alkaline polymer electrolyte membrane with electrostatic action is shown as follows:

wherein the positive charge functional group is one or more of quaternary ammonium salt, imidazole salt (linear alkane with N1 position of nitrogen of imidazole salt being C1-C10 and/or chain alkane with C2 position being C1-C9, or C3-C6 cyclane, or phenyl, or biphenyl), 1, 4-Diazabicyclooctane (DABCO), and guanidine salt; for anion X^-Is Cl^-Or OH^-(ii) a The main chain connecting positive charges is a polymer containing a styrene structure; the negatively charged functional group is one of carboxylic acid, sulfonic acid and phosphate radical; the main chain of the polymer with the sulfonate group is one of perfluoropolymer, meta-fluoropolymer, polyether ketone, polyether sulfone and polyphenyl ether with a side chain; the main chain of the polymer with carboxylic acid is polypropylene; the polymer main chain with phosphoric acid is polyethylene.

The preparation method of the composite alkaline polymer electrolyte membrane with good mechanical property, high conductivity and uniform physical and chemical properties comprises the following steps:

(1) preparation of chloromethylated main chain polymer containing polystyrene structure

Adding a certain mass of polymer containing a main chain of a polystyrene structure into an organic solvent A with a certain volume, dissolving the polymer at a certain temperature, then sequentially adding a catalyst and a chloromethylation reagent, reacting for a period of time at a certain temperature, then separating out by using a solvent B, washing for more than 2 times by using the solvent B, and drying to obtain a chloromethylation polymer m;

(2) dissolving the chloromethylated polymer m prepared in the step (1) in an organic solvent C to obtain a polymer solution with a certain mass fraction. The negatively charged polymer is referred to as a. Then dissolving the polymer a in a solvent D; respectively filling two polymer solutions into an injector with a needle head, fixing the two polymer solutions on a bracket of an electrospinning machine in parallel, and then spinning the two polymers on a roller with a certain rotating speed and a certain temperature at the same time by adopting an electrospinning technology under a certain voltage and a certain propelling speed to prepare the unfunctionalized compound type alkaline polymer fiber porous membrane;

preparing a functional group composite type alkaline polymer fiber porous membrane: there are two methods for preparing the functional group composite type alkaline polymer fiber porous membrane. One method is that the unfunctionalized compound type fiber porous membrane prepared in the step (2) is placed in a solution of trimethylamine, imidazole compound (the N1 position of the imidazole compound is C1-C10 straight-chain alkane and/or C2 position of C1-C9 chain alkane, or C3-C6 cyclane, or phenyl, or biphenyl), DABCO or guanidine for soaking for a period of time at a certain temperature, and then fully washed by deionized water to obtain the chlorine type functionalized compound type alkaline polymer fiber porous membrane;

or dissolving the chloromethylated polymer m prepared in the step (1) in an organic solvent C, adding trimethylamine, an imidazole compound (the N1 position of the imidazole compound is linear alkane of C1-C10 and/or chain alkane of C2 position of C1-C9, or cycloalkane of C3-C6, or phenyl, or biphenyl), DABCO or guanidine, or reacting to obtain a functionalized polymer solution; negatively charged and/or uncharged polymers are collectively referred to as a; then dissolving the polymer a in a solvent D; respectively filling two polymer solutions into an injector with a needle head, fixing the two polymer solutions on a bracket of an electrospinning machine in parallel, and then simultaneously spinning the two polymers on a roller by adopting an electrospinning technology to prepare a functional group composite type alkaline polymer fiber porous membrane;

(3) preparation of compact composite alkaline polymer electrolyte membrane

And (3) carrying out hot pressing or solvent E soaking treatment on the functional group composite type alkaline polymer fiber porous membrane prepared by adopting the electrospinning technology in the step (2) to obtain the uniform and compact electrolyte diaphragm. And fully washing with deionized water to obtain the chlorine type composite alkaline polymer electrolyte membrane.

Or preparing the hydrogen-oxygen type composite alkaline polymer electrolyte membrane:

and (3) soaking the obtained uniform and compact electrolyte membrane in a potassium hydroxide and/or sodium hydroxide solution at a certain temperature for a period of time to obtain the hydrogen-oxygen type composite alkaline polymer electrolyte membrane.

The preparation of the composite alkaline polymer electrolyte membrane with good mechanical property, higher conductivity and uniform physical and chemical properties comprises the following steps:

the polymer containing the styrene structure in the step (1) is a polystyrene and poly (styrene-ethylene-butylene) block copolymer;

in the step (1), the solvent A is one or more than two of concentrated sulfuric acid, carbon tetrachloride, dichloromethane, chloroform, dichloroethane and tetrachloroethane with the mass fraction of 95-98%; the solvent B is one or more than two of water, methanol, ethanol, isopropanol, ethyl acetate and acetone;

the catalyst in the step (1) is one or more than two of anhydrous stannic chloride, zinc chloride, trifluoroacetic acid and phosphorus trichloride; the chloromethylation reagent is one or more than two of chloromethyl ethyl ether, chloromethyl butyl ether, chloromethyl hexyl ether, chloromethyl octyl ether and 1, 4-dichloromethoxybutane;

the ratio of the mass of the high molecular polymer to the volume of the solvent in the step (1) is 1:15-1:60 g/mL; the mass ratio of the high molecular polymer to the catalyst is 2:1-1: 10; the mass ratio of the high molecular polymer to the chloromethylation reagent is 2:1-1: 10.

The dissolving temperature in the step (1) is between room temperature and 80 ℃; the reaction in the step (1) is carried out at room temperature of-80 ℃; the reaction time in the step (1) is more than 4 h;

the solvent C in the step (2) is one or more than two of tetrahydrofuran, trichloromethane, monochloroethane, toluene, xylene, dimethylacetamide, dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; the solvent D in the step (2) is one or more than two of water, methanol, ethanol, isopropanol, dimethylacetamide, dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone;

the volume ratio of the mass of the chloromethylated polymer m in the step (2) to the solvent C is 1:20-1: 3; the volume ratio of the mass of the polymer a to the volume of the solvent D in the step (2) is 1:10-1: 2; the mass ratio of the polymer with the positive charge functional group to the other or two polymers with the negative charge is 10:1-1: 1;

the spinning voltage in the step (2) is 12-24 kV; the propelling speed in the step (2) is 0.1-0.5 mm/min; in the step (2), the rotating speed of the roller is 0-180 r/min; the spinning temperature in the step (2) is room temperature to 60 ℃;

the soaking temperature in the step (2) is room temperature to 40 ℃; the soaking time in the step (3) is more than 24 hours; the reaction temperature in the step (3) is room temperature to 60 ℃; the reaction time in the step (3) is more than 12 h;

the volume ratio of the mass of the polymer to the trimethylamine, the imidazole compound, the DABCO or the guanidine in the reaction in the step (2) is 1:10-1:1

The hot pressing temperature in the step (3) is 90-140 ℃; the pressure of the hot pressing in the step (4) is 1000-; the hot pressing time in the step (4) is 0.5 to 6 hours;

the solvent in the step (3) is one or more than two of tetrahydrofuran, toluene, xylene, dimethylacetamide, dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; the soaking time in the step (4) is less than 20 min;

the total concentration of the potassium hydroxide and/or the sodium hydroxide in the step (3) is 0.1-4 mol/L; the temperature of the solution is between room temperature and 65 ℃; the treatment time is >6 h.

The preparation method of the composite alkaline polymer electrolyte membrane has the following advantages:

(1) the electrostatic interaction between the negatively charged polymer and the positively charged polymer enables the alkaline polymer electrolyte membrane to have good mechanical properties;

(2) the conductivity, the liquid absorption amount, the swelling and the mechanical properties of the alkaline polymer electrolyte membrane can be optimized by adjusting the proportion of the positively charged polymer to the negatively charged polymer; the conductivity of the membrane reaches 30mS/cm in deionized water at 60 ℃;

(3) the hot pressing and solution soaking method is simple and convenient, and the composite alkaline polymer electrolyte membrane with uniform and controllable thickness and larger area can be prepared.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of chloromethylated polystyrene in example 1.

Fig. 2 is a graph showing the change of the electrical conductivity with temperature of the composite type alkaline polymer electrolyte membrane in example 1. Test conditions for conductivity: the test device is immersed in deionized water, and the test temperature is controlled by adopting a water bath heating mode.

Detailed Description

Example 1

2g of polystyrene were dissolved in 30mLCCl at 40 ℃₄In (1). Then, 4g of anhydrous tin tetrachloride and 10g of 1, 4-dichlorotoluene were sequentially added under the ice-water bath condition (-5 ℃ C.)Oxybutane, stirred for 0.5h under ice-water bath conditions, and then reacted for 10h at 20 ℃. And pouring the reaction solution to ethanol after the reaction solution is returned to the room temperature to separate out a white solid, fully washing the white solid with ethanol, and performing vacuum drying for 48 hours at the room temperature to obtain the chloromethylated polystyrene.

1g of chloromethylated polystyrene prepared above was dissolved in 10mL of dimethylacetamide. To 20mL of 5% Nafion/alcohol-water mixed solution, 10mL of dimethylacetamide was added, and rotary evaporation was carried out at 60 ℃ to obtain a Nafion/dimethylacetamide solution. The two solutions were injected into 20mL disposable syringes, respectively, and fixed in the holders of the electrospinning machine. Then the voltage of the electric spinning is set to be 18kV, the speed of the propeller is set to be 0.3mm/min, the rotating speed of the roller is set to be 140 r/min, and the temperature on the roller is set to be 40 ℃. And after setting is finished, carrying out electrospinning for 8 hours to obtain the white unfunctionalized composite type alkaline polymer fiber porous membrane with the thickness of about 100 mu m. Soaking the porous membrane in trimethylamine solution at room temperature for 48h, and then hot-pressing the porous membrane at 12000psi and 100 ℃ for 2h to obtain the compact and transparent light yellow composite alkaline polymer electrolyte membrane with the thickness of-15 mu m. The test was carried out after soaking the mixture in 4M KOH solution at room temperature for 8 hours and then washing the soaked mixture sufficiently with deionized water.

The structure and degree of chloromethylation of polystyrene were quantitatively characterized by Bruker ACII 400, which has a resonance frequency of 400.13 MHz. During experiment, a small amount of sample to be tested is dissolved in deuterated chloroform, and the sample is obtained on a nuclear magnetic resonance apparatus¹H NMR spectrum with Tetramethylsilane (TMS) as internal standard. FIG. 1 is a drawing of polystyrene¹H NMR. From FIG. 1¹The successful preparation of chloromethylated polystyrene and the corresponding degree of chloromethylation can be seen from the characteristic peak positions of 2 and 1 and the hydrogen peak area ratio in H NMR. The degree of chloromethylation of polystyrene in this example was 0.3.

And (3) characterizing the micro-morphology of the composite type alkaline polymer fiber porous membrane by adopting a Scanning Electron Microscope (SEM). The applied voltage was 15kV for the experiment.

The liquid absorption and swelling ratio of the alkaline polymer electrolyte membrane can be calculated from the changes in the membrane mass and size before and after vacuum drying at 80 ℃. Firstly, wiping water on the surface of a wet film by using filter paper, weighing the mass or measuring the length and the thickness of the wet film, then fully drying the wet film in a vacuum drying oven at 80 ℃, weighing the mass of a dry film, and measuring the length and the thickness of the dry film.

The calculation formula of the liquid absorption amount is as follows:

wherein M is_WetFor wet film quality, M_{Dry matter}The quality of the dry film is shown.

The swelling ratio is calculated by the formula:

wherein L is_WetIs the wet film length, L_{Dry matter}Is the dry film length.

The Ion Exchange Capacity (IEC) of the membrane was determined by back titration. The specific process is as follows: after vacuum drying a membrane sample at 80 ℃, weighing a certain mass of the membrane, soaking the membrane in a certain volume of 0.01M HCl solution for 48 hours at room temperature, and then titrating with 0.01M KOH solution, thereby calculating the amount of residual hydrochloric acid in the soaking solution. In addition, the same volume of 0.01M HCl solution was titrated with 0.01M KOH solution to calculate the amount of species of HCl solution that soaked the membrane. And (4) judging the titration end point by adopting a pH meter. The calculation formula of IEC is:

in the formula N_0HCl、N_iHClRespectively the amount of HCl solution used for soaking the membrane and the amount of HCl solution remained for soaking the membrane; m_{Dry matter}The quality of the oxyhydrogen dry film.

The calculation formula of the hydration number of the alkaline anion-exchange membrane is as follows:

table 1 below is a table of values for the liquid uptake, swelling, IEC and hydration number parameters of the membranes. It can be seen from table 1 that such films have a better liquid absorption capacity.

The conductivity of the prepared poly (styrene-ethylene-butylene) block copolymer type alkaline anion exchange membrane with the hydrophobic long side chain is tested by adopting an alternating current impedance method. The conductivity is calculated as:

where σ is the conductivity (S/cm) of the film, L is the distance (cm) between the SensorI and SensorII electrodes, W is the width (cm) of the film, T is the thickness (cm) of the film, and R is the impedance (Ω) of the measured film.

The alkaline polymer electrolyte membranes were cut to 0.5 x 4cm before testing²The method comprises the following steps of fixing the rectangular membrane in the middle of a polytetrafluoroethylene mould, putting metal wires (silver wires, copper wires or platinum wires) into a groove of the mould to lead out three electrodes, then putting the mould into deionized water, balancing at a set temperature for at least 30min, and then measuring the impedance of the membrane by adopting alternating current impedance. The experimental apparatus is a Solartron AC1260 impedance analyzer and a 1287 electrochemical workstation, and the scanning frequency range is 1-10⁶Hz. The conductivity of the membrane is the average of the results of the impedance calculations measured a number of times.

Fig. 2 is a graph showing the change of conductivity with temperature of the composite type alkaline polymer electrolyte membrane prepared in example 1. In FIG. 2, the abscissa is temperature (. degree. C.) and the ordinate is conductivity (mS cm)^-1) (ii) a Conductivity of such membranes at room temperature>30mS cm^-1Electrical conductivity at 80 ℃>80mS cm^-1Can meet the basic requirement of the fuel cell on the conductivity of the alkaline polymer electrolyte membrane.

The mechanical strength of the composite alkaline polymer electrolyte membrane was tested using Q800 of TA corporation. With the stretching mode, the stretching rate was 10%. The tensile strength of the prepared membrane is 87MPa, but the elongation at break of the prepared membrane is 30%, which indicates that the membrane has good mechanical properties and has potential application in fuel cells.

Comparative example

The method is to prepare the composite alkaline polymer electrolyte membrane by physically mixing the quaternary ammonium salt type polystyrene polymer solution and the Nafion solution, and as a result, the solid substances are separated out at the moment of mixing the quaternary ammonium salt type polystyrene polymer solution and the Nafion solution, and the preparation of the membrane cannot be finished.

Claims

1. A preparation method of a composite alkaline polymer electrolyte membrane is characterized by comprising the following steps: the composite alkaline polymer electrolyte membrane is formed by interweaving two or three polymers; wherein, one polymer with a positive charge functional group is necessary, and the other polymer or two polymers are negative charge polymers; an electrostatic action can be formed between the polymer with negative charges and the polymer with positive charge functional groups, and the structure of the composite type alkaline polymer electrolyte membrane with the electrostatic action is shown as follows:

wherein the positive charge functional group is one or more of quaternary ammonium salt, imidazole salt, 1, 4-Diazabicyclooctane (DABCO) and guanidine salt of trimethylamine; for anions being Cl^-Or OH^-(ii) a The main chain of the polymer connected with positive charges is a polymer containing a styrene structure;

the negatively charged functional group is one of carboxylic acid, sulfonic acid and phosphate radical; the main chain of the polymer with the sulfonate group is one of perfluoropolymer, meta-fluoropolymer, polyether ketone, polyether sulfone and polyphenyl ether with a side chain; the main chain of the polymer with carboxylic acid is polypropylene; the main chain of the polymer with phosphoric acid is polyethylene;

the preparation method of the composite alkaline polymer electrolyte membrane comprises the following steps,

Adding a polymer containing a polystyrene structure main chain into an organic solvent A, dissolving the polymer, then sequentially adding a catalyst and a chloromethylation reagent, separating out the reaction product by using a solvent B, washing the reaction product for more than 2 times by using the solvent B, and drying the reaction product to obtain a chloromethylation polymer m;

(2) dissolving the chloromethylated polymer m prepared in the step (1) in an organic solvent C to obtain a polymer solution 1; the negatively charged polymer is referred to as a; then dissolving the polymer a in a solvent D to obtain a polymer solution 2;

respectively filling the polymer solution 1 and the polymer solution 2 into an injector with a needle head, fixing the polymer solution 1 and the polymer solution 2 on a bracket of an electrospinning machine in parallel, and then spinning the polymer solution 1 and the polymer solution 2 on a roller simultaneously by adopting an electrospinning technology to prepare the unfunctionalized compound type alkaline polymer fiber porous membrane; preparing a functional group composite type alkaline polymer fiber porous membrane: soaking the unfunctionalized composite type alkaline polymer fiber porous membrane prepared in the step (2) in one or more than two solutions of trimethylamine, imidazole compound, DABCO or guanidine, and then fully washing with deionized water to obtain a chlorine type functionalized composite type alkaline polymer fiber porous membrane;

or, dissolving the chloromethylated polymer m prepared in the step (1) in an organic solvent C, adding one or more of trimethylamine, imidazole compounds, DABCO or guanidine, and reacting to obtain a functionalized polymer solution 3; the negatively charged polymer is referred to as a; then dissolving the polymer a in a solvent D to obtain a polymer solution 2; respectively filling the functionalized polymer solution 3 and the polymer solution 2 into an injector with a needle head, fixing the functionalized polymer solution 3 and the polymer solution 2 on a bracket of an electrospinning machine in parallel, and then spinning the functionalized polymer solution 3 and the polymer solution 2 on a roller simultaneously by adopting an electrospinning technology to prepare the chlorine type functionalized composite alkaline polymer fiber porous membrane;

(3) preparation of compact composite alkaline polymer electrolyte membrane

Carrying out hot pressing or solvent E soaking treatment on the chlorine type functionalized composite alkaline polymer fiber porous membrane prepared by adopting the electrospinning technology in the step (2) to obtain a uniform and compact electrolyte diaphragm; fully washing with deionized water to obtain a chlorine type composite alkaline polymer electrolyte membrane;

and (3) soaking the obtained uniform and compact electrolyte membrane in a potassium hydroxide and/or sodium hydroxide solution to obtain the oxyhydrogen type composite alkaline polymer electrolyte membrane.

2. The method of claim 1, wherein: the mass ratio of the polymer having a positively charged functional group to the other or two polymers having a negative charge is (10: 1) to (1: 1).

3. The method of claim 1, wherein:

the polymer containing the polystyrene structure main chain in the step (1) is polystyrene or a poly (styrene-ethylene-butylene) block copolymer;

the ratio of the mass of the polymer containing the polystyrene structure main chain to the volume of the solvent A in the step (1) is (1: 15) - (1: 60) g/mL; the mass ratio of the polymer containing the main chain of the polystyrene structure to the catalyst is (2: 1) - (1: 10); the mass ratio of the polymer containing the styrene structure to the chloromethylation reagent is (2: 1) - (1: 10);

the dissolving temperature in the step (1) is 20-80 ℃; the reaction temperature in the step (1) is 20-80 ℃; the reaction time of the step (1) is more than 4 h.

4. The method of claim 1, wherein:

the volume ratio of the mass of the chloromethylated polymer m in the step (2) to the solvent C is (1: 20) - (1: 3) g/mL; the voltage of the electric spinning in the step (2) is 12-24 kV; the rotating speed of the roller in the step (2) is 0-180 r/min; the temperature of the electrospinning in the step (2) is between room temperature and 60 ℃;

the soaking temperature in the step (2) is between room temperature and 40 ℃; the soaking time in the step (2) is more than 24 hours; the reaction temperature in the step (2) is between room temperature and 60 ℃; the reaction time of the step (2) is more than 12 h.

5. The method of claim 1, wherein:

the temperature of the hot pressing in the step (3) is 90-140 ℃; the pressure of the hot pressing in the step (3) is 1000-; the hot pressing time in the step (3) is 0.5-6 h;

the solvent E in the step (3) is one or more than two of tetrahydrofuran, toluene, xylene, dimethylacetamide, dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; the soaking time in the step (3) is less than 20 min;

the total concentration of the potassium hydroxide and/or the sodium hydroxide in the step (3) is 0.1-4 mol/L; the temperature of the solution is between room temperature and 65 ℃; the time of the treatment was >6 h.

6. A composite alkaline polymer electrolyte membrane produced by the production method according to any one of claims 1 to 5.

7. Use of the composite alkaline polymer electrolyte membrane according to claim 6 in a fuel cell.