CN108461791A - A kind of compound alkaline polymer electrolyte membrane and its preparation and application - Google Patents

A kind of compound alkaline polymer electrolyte membrane and its preparation and application Download PDF

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CN108461791A
CN108461791A CN201611145388.XA CN201611145388A CN108461791A CN 108461791 A CN108461791 A CN 108461791A CN 201611145388 A CN201611145388 A CN 201611145388A CN 108461791 A CN108461791 A CN 108461791A
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electrolyte membrane
compound alkaline
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CN108461791B (en
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王素力
杨丛荣
孙公权
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

A kind of compound alkaline polymer electrolyte membrane of present invention offer and its preparation and application, the compound alkaline polymer electrolyte membrane, including two or three of polymer are interwoven；Wherein, it is necessary to include a kind of polymer of positively charged functional group, another or two kinds of polymer for negatively charged functional group.The preparation of the compound alkaline polymer electrolyte membrane includes the preparation of (1) chloromethylated polymer m；(2) method of electrostatic spinning is used to claim a spinning simultaneously to prepare compound alkaline polymer fiber multihole film chloromethylated polymer m and negatively charged polymer；(3) hot pressing or solvent soaking method is used to prepare fine and close compound alkaline polymer electrolyte membrane.Alkaline polymer electrolyte membrane of the present invention has good mechanical performance, conductivity, liquid absorption amount and swelling resistance；Preparation method is easy, can prepare the compound alkaline polymer electrolyte membrane of thickness uniformly, controllable, area is larger.

Description

A kind of compound alkaline polymer electrolyte membrane and its preparation and application
Technical field
The invention belongs to alkaline polymer electrolyte exchange membrane fields；The invention further relates to one kind have high conductance, The preparation of good mechanical properties alkaline polymer electrolyte exchange membrane.
Background technology
In recent years, becoming increasingly conspicuous with energy shortage and environmental problem, environmentally protective new energy is increasingly becoming the whole world and grinds The hot spot studied carefully.Due to use alkaline polymer electrolyte exchange membrane (APEMs) for the electrochemical energy device of solid electrolyte (such as Alkaline anion-exchange membrane fuel cell, water electrolytic cell, flow battery, metal-air battery etc.) have specific power density big, at This is low, it is environmental clean the advantages that become researcher's focus of attention.However, the performance of APEMs cannot still meet electrochemistry at present The requirement of device application environment.In its working environment, the presence of highly basic, high temperature, highfield, magnetic field makes the stabilization of APEMs Property, conductivity and mechanical performance face larger challenge, how to balance the contradiction between the conductivity of APEMs and mechanical performance, carry Chemical stability in high high-temperature alkaline environment becomes the research emphasis in the fields APEMs.
In order to improve the conductivity of APEMs, researchers have done many work.Guiver et al. has been prepared is with polysulfones The block copolymer APEMs of main chain, not only conductivity is high for this kind of film, but also maintains lower liquid absorption amount and swelling, performance tool There is some superiority.Li Nanwen et al. utilizes " click chemistry " APEMs with long side chain for preparing under the conditions of water saturation Conductivity can reach 62mS cm-1.Studied in terms of improving conductivity it is more outstanding be Wuhan University's village woods teacher's project Group, the polysulfones type APEMs that they are prepared for having good micron-scale phase separation structure by Molecular Design.They will be by that will grow Hydrophobic side chain is grafted on the main chain far from functional group so that APEMs forms continuous and apparent micron-scale phase separation structure, structure It has built and has been conducive to OH-The channel of transmission has been more than quotient in 80 DEG C of conductivity to be effectively improved the conductivity of APEMs ProductThe conductivity of film.
Currently, although the performance of APEMs disclosure satisfy that the requirement of electrochemical system, the common main chains of APEMs contain Ehter bond, this allows for the stability of APEMs main chains, and there are certain hidden danger in the working environment of electrochemical device.Because in alkalinity In environment, strong nucleopilic reagent OH-The C-O keys in main chain can be attacked, make its hydrolyze scission of link, cause film Integral-crushing (PNAS, February 12,2013, vol.110).Studies have shown that polystyrene-based main chain has preferableization in high-temperature alkaline environment Learn stability.However, polystyrene is carried out the mechanical performance of the APEMs of function dough preparation and face as hard material Face huge challenge (especially preparing ultrathin membrane, this problem is more prominent).So steady using this kind of hydrocarbon backbone chemistry of polystyrene Qualitative advantage, it is the key that promote such APEMs development, application to improve its mechanical performance.Chemical crosslinking and composite strengthening are The method of currently used enhancing film mechanical performance, although the machinery that both methods can improve film to a certain extent is strong Degree, the swelling for reducing film, enhance the dimensional stability of film, but there are still certain deficiencies for both methods.Wherein use chemistry Cross-linking method can be such that the IEC values of film reduce, and membrane conductivity is caused to reduce；Using the diversion of film prepared by the composite strengthening embrane method of basement membrane Subdivision is with strengthening part due to lacking chemical action, and with the extension of working time, the polymer for conducting ion can be from basement membrane Middle removing so that film loses the ability of conduction ion；Using blending (two or more especially electrically charged polymer are blended) Film prepared by method can exist since the poor compatibility of two kinds of polymer the two occurs in phase separation macroscopically, lead to its biography The ability of diversion is poor or does not have conduction ion energy, or even cannot prepare uniform films.
Invention content
In view of the above-mentioned problems, a kind of with good mechanical properties, high conductance and object it is an object of the invention to prepare Reason, the uniform alkaline polymer electrolyte membrane of chemical property.
The present invention prepares one kind using electrostatic spinning technique and has both good mechanical properties, high conductance and physics, chemistry Uniformly compound alkaline polymer electrolyte membrane, concrete scheme are as follows for performance：
Compound alkaline polymer electrolyte membrane includes that two or three of polymer is interwoven.Wherein, it is necessary to include A kind of polymer of positively charged functional group, another or two kinds of polymer are negatively charged polymer.Wherein, negatively charged Polymer and the polymer of positively charged functional group between can form electrostatic interaction, with electrostatic interaction compound alkalinity The structural representation of polymer dielectric film is as follows：
Wherein, the functional group of positive charge is quaternary ammonium salt, the imidazole salts (linear paraffin that the positions nitrogen N1 of imidazole salts are C1-C10 And/or the chain alkane that the positions carbon C2 are C1-C9, or be the cycloalkane of C3-C6, or be phenyl or be xenyl), Isosorbide-5-Nitrae-two One or more of azabicyclooctane (DABCO), guanidine salt；To anion X-For Cl-Or OH-；Connect the master of positive charge Chain is the polymer containing styryl structures；Negatively charged functional group is one kind in carboxylic acid, sulfonic acid, phosphate radical；Band sulfonate radical Main polymer chain be the (per) fluoropolymer with side chain, inclined fluoropolymer, polyether-ketone, polyether sulfone, one kind in polyphenylene oxide；Band carboxylic The main polymer chain of acid is polypropylene；Main polymer chain with phosphoric acid is polyethylene.
A kind of satisfactory mechanical property, conductivity be higher and the uniform compound alkaline polymer of physics, chemical property The preparation of dielectric film includes the following steps：
(1) preparation of chloromethylation structural backbone containing polystyrene polymer
The polymer of the structural backbone containing polystyrene of certain mass is added in the organic solvent A of certain volume, by it It dissolves at a certain temperature, then sequentially adds catalyst and chloromethylation reagents, after reacting a period of time at a certain temperature It is precipitated with solvent B, is washed 2 times or more with solvent B, be dried to obtain chloromethylated polymer m；
(2) the chloromethylated polymer m prepared in step (1) is dissolved in organic solvent C, obtains certain mass score Polymer solution.Negatively charged polymer is known as a.Then polymer a is dissolved in solvent D；By two kinds of polymer solution point It is not filling in the syringe with syringe needle, it is parallel to be fixed on the holder of Electrospun machine, then in certain voltage, certain propulsion Electrospinning is used under speed, and two kinds of polymer is spun on the idler wheel with certain rotating speed, certain temperature simultaneously, is prepared Go out the compound alkaline polymer fiber multihole film of non-function dough；
The preparation of the compound alkaline polymer fiber multihole film of function dough：The compound alkaline polymerization fibres of function dough There are two types of methods for the preparation of perforated membrane.A kind of method is to set non-function dough composite fibre perforated membrane prepared by step (2) In trimethylamine, glyoxaline compound, (linear paraffin and/or the positions carbon C2 that the positions nitrogen N1 of glyoxaline compound are C1-C10 be The chain alkane of C1-C9, or be the cycloalkane of C3-C6, or be phenyl or be xenyl), in the solution of DABCO or guanidine one Determine to be soaked for a period of time at temperature, then fully be washed with deionized water, obtains the compound alkaline polymer of chlorine type function dough Fiber multihole film；
Or the chloromethylated polymer m prepared in step (1) is dissolved in organic solvent C, trimethylamine, imidazoles are added Conjunction object (the chain alkane that the linear paraffin and/or the positions carbon C2 that the positions nitrogen N1 of glyoxaline compound are C1-C10 are C1-C9, Or the cycloalkane for C3-C6, or be phenyl or be xenyl), DABCO or one kind in guanidine or two kinds or more, be obtained by the reaction Functional group's fluidized polymer solution；Negatively charged and/or uncharged polymer is referred to as a；Then polymer a is dissolved in solvent In D；Two kinds of polymer solution is filling in the syringe with syringe needle respectively, it is parallel to be fixed on the holder of Electrospun machine, Then Electrospinning is used, two kinds of polymer is spun on having an idler wheel simultaneously, it is poly- to prepare the compound alkalinity of function dough Close fibres perforated membrane；
(3) preparation of fine and close compound alkaline polymer electrolyte membrane
The compound alkaline polymer fiber multihole film of function dough prepared using Electrospinning in step (2) is carried out Solvent E processing is impregnated in hot pressing, obtains even compact electrolyte membrance.It is compound that chlorine type is obtained after fully being washed with deionized water Alkaline polymer electrolyte membrane.
Or the preparation of the compound alkaline polymer electrolyte membrane of hydrogen-oxygen type：
The electrolyte membrance of the even compact of above-mentioned gained will be placed in potassium hydroxide and/or sodium hydroxide solution one Determine to be soaked for a period of time at temperature, obtains the compound alkaline polymer electrolyte membrane of hydrogen-oxygen type.
Above-mentioned satisfactory mechanical property, conductivity be higher and the uniformly compound alkaline polymer electrolysis of physics, chemical property The preparation of plasma membrane：
Polymer containing styryl structures described in step (1) is polystyrene, poly- (styrene-ethylene-butadiene) block Copolymer；
It is the 95-98% concentrated sulfuric acids, carbon tetrachloride, dichloromethane, chloroform, two that solvent A described in step (1), which is mass fraction, One or more of chloroethanes, tetrachloroethanes；The solvent B is water, methanol, ethyl alcohol, isopropanol, ethyl acetate, third One or more of ketone；
Step (1) described catalyst is anhydrous stannic chloride, zinc chloride, trifluoroacetic acid, one kind in phosphorus trichloride or two Kind or more；The chloromethylation reagents are chloromethyl ether, chloromethyl butyl ether, chloromethyl hexyl ether, chloromethyl octyl ether, 1,4- dichloros One or more of methyl butyl ether；
The ratio of the volume of the quality and solvent of high molecular polymer described in step (1) is 1:15-1:60g/mL；The height The mass ratio of Molecularly Imprinted Polymer and catalyst is 2:1-1:10；The mass ratio of the high molecular polymer and chloromethylation reagents is 2:1-1:10。
- 80 DEG C of solution temperature room temperature described in step (1)；- 80 DEG C of room temperature is reacted described in step (1)；Step (1) is described Reaction time>4h；
Step (2) described solvent C is tetrahydrofuran, chloroform, monochlorethane, toluene, dimethylbenzene, dimethylacetamide One or more of amine, dimethylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone；Step (2) the solvent D For in water, methanol, ethyl alcohol, isopropanol, dimethylacetylamide, dimethylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone It is one or more kinds of；
The quality of step (2) the chloromethylated polymer m and the volume ratio of solvent C are 1:20-1:3；Step (2) is described The quality of polymer a is 1 with the volume ratio of solvent D:10-1:2；The polymer of the positively charged functional group and another kind or two The mass ratio of the negatively charged polymer of kind is 10:1-1:1；
Spinning voltage described in step (2) is 12-24kV；Fltting speed described in step (2) is 0.1-0.5mm/min； Idler wheel rotating speed described in step (2) is that 0-180 turns/min；Spinning temperature described in step (2) is -60 DEG C of room temperature；
Soaking temperature described in step (2) is -40 DEG C of room temperature；Soaking time described in step (3)>24h；Step (3) institute The reaction temperature stated is -60 DEG C of room temperature；Reaction time described in step (3)>12h；
The volume ratio of polymer quality and trimethylamine, glyoxaline compound, DABCO or guanidine in reaction described in step (2) It is 1:10-1:1
Hot pressing temperature described in step (3) is 90-140 DEG C；The pressure of step (4) described hot pressing is 1000-24000 pounds； Hot pressing time described in step (4) is 0.5-6h；
Solvent described in step (3) is tetrahydrofuran, toluene, dimethylbenzene, dimethylacetylamide, dimethylformamide, two One or more of methyl sulfoxide, N-Methyl pyrrolidone；Soaking time described in step (4)<20min；
The total concentration of potassium hydroxide and/or sodium hydroxide described in step (3) is 0.1-4mol/L；The solution temperature is - 65 DEG C of room temperature；The processing time>6h.
The preparation of compound alkaline polymer electrolyte membrane of the present invention has the following advantages that：
(1) electrostatic interaction between negatively charged polymer and positively charged polymer makes alkaline polymer be electrolysed Plasma membrane has good mechanical performance；
(2) by the ratio of modulation positively charged polymer and negatively charged polymer, alkaline polymer electrolysis can be optimized Conductivity, liquid absorption amount, swelling and the mechanical performance of plasma membrane；At 60 DEG C, in deionized water, the conductivity of film reaches 30mS/cm；
(3) method of hot pressing and soaking solution is easier, can prepare thickness uniformly, larger compound of controllable, area Type alkaline polymer electrolyte membrane.
Description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum of chloromethylated polystyrene in embodiment 1.
Fig. 2 is that the conductivity of compound alkaline polymer electrolyte membrane in embodiment 1 varies with temperature curve.Conductivity Test condition：Test device is immersed in deionized water, and test temperature is controlled using heating water bath mode.
Specific implementation mode
Embodiment 1
Under the conditions of 40 DEG C, 2g polystyrene is dissolved in 30mLCCl4In.Then under conditions of ice-water bath (- 5 DEG C) according to Secondary addition 4g anhydrous stannic chlorides, 10g1,4- dichloro methyl butyl ethers stir 0.5h, then at 20 DEG C under the conditions of ice-water bath Under the conditions of react 10h.It is poured into after reaction solution restores to room temperature and white solid is precipitated in ethyl alcohol, rear chamber is fully washed with ethyl alcohol Temperature is lower to be dried in vacuo 48h, obtains chloromethylated polystyrene.
The chloromethylated polystyrene of the above-mentioned preparations of 1g is dissolved in 10mL dimethylacetylamides.To 20mL5%'s 10mL dimethylacetylamides are added in Nafion/ alcohol water mixed solutions, it is molten that 60 DEG C of revolvings obtain Nafion/ dimethylacetylamides Liquid.Two kinds of solution are injected separately into 20mL disposable syringes, are fixed in the fixed seat of Electrospun machine.Then setting electricity The voltage of spinning is 18kV, and the speed of propeller is 0.3mm/min, and the rotating speed of idler wheel is 140 turns/min, and temperature is 40 on idler wheel ℃.Electrospun is proceeded by after setting, it is about the non-compound alkali of function dough of 100 μm of whites that duration 8h, which obtains thickness, Property polymer fiber perforated membrane.By perforated membrane in trimethylamine solution after soaking at room temperature 48h under the conditions of 12000psi, 100 DEG C Hot pressing 2h obtains -15 μm of compound alkaline polymer electrolyte membranes of fine and close clear, yellowish.Place it in 4M KOH solutions in It is tested after fully being washed with deionized water after immersion 8h at room temperature.
Quantitatively characterizing is carried out to the structure and degree of the chloromethylation of polystyrene using Bruker ACIII 400, is total to Vibration frequency is 400.13MHz.When experiment, a small amount of sample to be tested is taken to be dissolved in deuterochloroform, in obtaining sample in Nuclear Magnetic Resonance Product1H NMR spectras, using tetramethylsilane (TMS) as internal standard.Fig. 1 is polystyrene1H NMR.By in Fig. 11In H NMR 2 can be seen that the successful preparation of chloromethylated polystyrene and corresponding chloromethyl with 1 characteristic peak positions and hydrogen peak area ratio Change degree.The chloromethylation degree of polystyrene is 0.3 in the present embodiment.
The microscopic appearance of compound alkaline polymer fiber multihole film is characterized using scanning electron microscope (SEM).Experiment When applied voltage be 15kV.
By the variation of 80 DEG C of vacuum drying front and back film quality and size, alkaline polymer electrolyte membrane can be calculated Liquid absorption amount and swelling ratio.The water of moisture membrane surface is dried with filter paper first, weigh quality or measures its length, thickness, then will It is fully dry in 80 DEG C of vacuum drying chamber, weighs the quality of dry film, measures length, the thickness of dry film.
The calculation formula of liquid absorption amount is：
Wherein MIt is wetFor wet film quality, MIt is dryFor dry film quality.
The calculation formula of swelling ratio is：
Wherein LIt is wetFor wet film length, LIt is dryFor dry film length.
The ion exchange capacity (IEC) of film is measured using back titration.Detailed process is：By membrane sample at 80 DEG C After lower vacuum drying, the film of certain mass is weighed, impregnates 48h in the 0.01M HCl solutions of certain volume under room temperature, so It is titrated afterwards with 0.01M KOH solutions, the amount of the substance of remaining hydrochloric acid in soak is calculated with this.In addition, using 0.01M The 0.01M HCl solutions of KOH solution titration same volume are to calculate the amount of the substance for the HCl solution for impregnating film.Sentenced using pH meter Disconnected titration end-point.The calculation formula of IEC is：
N in formula0HCl、NiHClRespectively impregnate the amount of HCl solution used in film, the substance for impregnating film residue HCl solution；MIt is dryFor The quality of hydrogen-oxygen type dry film.
The calculation formula of the hydration number of alkaline anion-exchange membrane is：
The following table 1 is the numerical value of the liquid absorption amount of film, swelling, IEC and hydration number parameter.Such film has as can be seen from Table 1 Preferable imbibition ability.
Using AC impedence method long poly- (styrene-ethylene-butadiene) block copolymer of side chain hydrophobic to the band of above-mentioned preparation The conductivity of type alkaline anion-exchange membrane is tested.The calculation formula of conductivity is：
σ is the conductivity (S/cm) of film in formula, and L is the distance between SensorI and SensorII electrodes (cm), and W is film Width (cm), T be film thickness (cm), R by survey film impedance (Ω).
Alkaline polymer electrolyte membrane is cut into 0.5*4cm before test2Rectangle, be fixed in Teflon mould Between, wire (filamentary silver, copper wire or platinum filament) is put into the slot of mold and exports each of three electrodes, mold is then put into deionized water In, the impedance that Based on AC Impedance Measurements film is used after at least 30min is balanced at a temperature of setting.Laboratory apparatus is Solartron AC1260 impedance analyzers and 1287 electrochemical workstations, range of scanned frequencies 1-106Hz.The conductivity of film is repeatedly to measure The average value of impedance computation result.
Fig. 2 is that the conductivity of the compound alkaline polymer electrolyte membrane prepared by embodiment 1 varies with temperature curve. In Fig. 2, abscissa is temperature (DEG C), and ordinate is conductivity (mS cm-1)；As shown in Figure 2, the conductance of such film at room temperature Rate>30mS cm-1, in 80 DEG C of conductivity>80mS cm-1, disclosure satisfy that fuel cell to alkaline alkaline polymer electrolyte membrane The basic demand of conductivity.
The mechanical strength of compound alkaline polymer electrolyte membrane is tested using the Q800 of TA companies.Utilize stretching Pattern, rate of extension 10%.The tensile strength of the film of preparation is 87MPa, but its elongation at break is 30%, shows this kind of film With good mechanical performance, have the potentiality applied in a fuel cell.
Comparative example
Intend preparing by the way of by quaternary poly styrene polymer solution and Nafion solution physical mixed compound Alkaline polymer electrolyte membrane is precipitated as a result, it has been found that the moment that the two mixes is had solid matter, cannot complete the preparation of film.

Claims (7)

1. a kind of compound alkaline polymer electrolyte membrane, it is characterised in that:Compound alkaline polymer electrolyte membrane includes Two or three of polymer is interwoven；Wherein, it is necessary to include a kind of polymer of positively charged functional group, it is another or two kinds Polymer is negatively charged；Electrostatic work can be formed between negatively charged polymer and the polymer of positively charged functional group With the structural representation of the compound alkaline polymer electrolyte membrane with electrostatic interaction is as follows：
Wherein, the functional group of positive charge is one kind in quaternary ammonium salt, imidazole salts, Isosorbide-5-Nitrae-diazabicyclooctane (DABCO), guanidine salt Or two kinds or more；It is Cl or OH to anion；The main polymer chain for connecting positive charge is the polymer containing styryl structures；
Negatively charged functional group is one kind in carboxylic acid, sulfonic acid, phosphate radical；Main polymer chain with sulfonate radical is with side chain One kind in (per) fluoropolymer, inclined fluoropolymer, polyether-ketone, polyether sulfone, polyphenylene oxide；Main polymer chain with carboxylic acid is poly- third Alkene；Main polymer chain with phosphoric acid is polyethylene.
2. according to compound alkaline polymer electrolyte membrane described in claim 1, it is characterised in that:Positively charged functional group gathers It is 10 that object, which is closed, with another or two kinds of negatively charged polymer mass ratio:1-1:1.
3. the preparation method of compound alkaline polymer electrolyte membrane described in a kind of claims 1 or 2, it is characterised in that：Including Following steps,
(1) preparation of chloromethylation structural backbone containing polystyrene polymer
In organic solvent A be added the structural backbone containing polystyrene polymer, dissolved, then sequentially add catalyst and Chloromethylation reagents are precipitated with solvent B after reaction, are washed 2 times or more with solvent B, be dried to obtain chloromethylated polymer m；
(2) the chloromethylated polymer m prepared in step (1) is dissolved in organic solvent C, obtains polymer solution；It is negatively charged The polymer of lotus is known as a；Then polymer a is dissolved in solvent D；Two kinds of polymer solution is filling in the note with syringe needle respectively It is parallel to be fixed on the holder of Electrospun machine in emitter, Electrospinning is then used, two kinds of polymer is spun one simultaneously On idler wheel, the compound alkaline polymer fiber multihole film of non-function dough is prepared；
The preparation of the compound alkaline polymer fiber multihole film of function dough：It is that the non-function dough for preparing step (2) is compound Fiber type perforated membrane, which is placed in a kind of in trimethylamine, glyoxaline compound, DABCO or guanidine or two kinds or more of solution, to be soaked Bubble, is then fully washed with deionized water, obtains the compound alkaline polymer fiber multihole film of chlorine type function dough；
Or, the chloromethylated polymer m prepared in step (1) is dissolved in organic solvent C, trimethylamine, imidazoles chemical combination is added One kind in object, DABCO or guanidine or two kinds or more, are obtained by the reaction functional group's fluidized polymer solution；Negatively charged polymer Referred to as a；Then polymer a is dissolved in solvent D；Two kinds of polymer solution is filling in the syringe with syringe needle respectively, it puts down Row is fixed on the holder of Electrospun machine, then uses Electrospinning, and two kinds of polymer is spun on having an idler wheel simultaneously, Prepare the compound alkaline polymer fiber multihole film of function dough；
(3) preparation of fine and close compound alkaline polymer electrolyte membrane
The compound alkaline polymer fiber multihole film of function dough prepared using Electrospinning in step (2) is subjected to hot pressing Or solvent E processing is impregnated, obtain even compact electrolyte membrance；The compound alkalinity of chlorine type is obtained after fully being washed with deionized water Polymer dielectric film；
Or, the preparation of the compound alkaline polymer electrolyte membrane of hydrogen-oxygen type：
The electrolyte membrance of the even compact of above-mentioned gained is placed in potassium hydroxide and/or sodium hydroxide solution and is impregnated, is obtained The compound alkaline polymer electrolyte membrane of hydrogen-oxygen type.
4. according to the preparation method of compound alkaline polymer electrolyte membrane described in claim 3, it is characterised in that：
Polymer containing styryl structures described in step (1) is polystyrene or poly- (styrene-ethylene-butadiene) block copolymerization Object；
Solvent A described in step (1) be mass fraction be 95-98% the concentrated sulfuric acid, carbon tetrachloride, dichloromethane, chloroform, dichloro One or more of ethane, tetrachloroethanes；The solvent B is water, methanol, ethyl alcohol, isopropanol, ethyl acetate, acetone One or more of；
Step (1) described catalyst be anhydrous stannic chloride, zinc chloride, trifluoroacetic acid, one or both of phosphorus trichloride with On；The chloromethylation reagents are chloromethyl ether, chloromethyl butyl ether, chloromethyl hexyl ether, chloromethyl octyl ether, 1,4- dichloro methoxies One or more of base butane；
The ratio of the volume of the quality and solvent A of high molecular polymer described in step (1) is 1:15-1:60g/mL；The high score The mass ratio of sub- polymer and catalyst is 2:1-1:10；The mass ratio of the high molecular polymer and chloromethylation reagents is 2: 1-1:10；
20-80 DEG C of solution temperature described in step (1)；20-80 DEG C of reaction temperature described in step (1)；Step (1) described reaction Time>4h.
5. according to the preparation method of compound alkaline polymer electrolyte membrane described in claim 3, it is characterised in that：
Step (2) described solvent C is tetrahydrofuran, chloroform, monochlorethane, toluene, dimethylbenzene, dimethylacetylamide, two One or more of methylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone；Step (2) the solvent D be water, One kind in methanol, ethyl alcohol, isopropanol, dimethylacetylamide, dimethylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone Or it is two or more；
The quality of step (2) the chloromethylated polymer m and the volume ratio of solvent C are 1:20-1:3；Step (2) described polymerization The quality of object a is 1 with the volume ratio of solvent D:10-1:2；
Spinning voltage described in step (2) is 12-24kV；Fltting speed described in step (2) is 0.1-0.5mm/min；Step (2) idler wheel rotating speed described in is that 0-180 turns/min；Spinning temperature described in step (2) is -60 DEG C of room temperature；
Soaking temperature described in step (2) is -40 DEG C of room temperature；Soaking time described in step (2)>24h；Described in step (2) Reaction temperature is -60 DEG C of room temperature；Reaction time described in step (2)>12h；
Polymer quality and one kind or two in trimethylamine, glyoxaline compound, DABCO or guanidine in reaction described in step (2) Kind or more volume ratio be 1:10-1:1.
6. according to the preparation method of compound alkaline polymer electrolyte membrane described in claim 3, it is characterised in that：
Hot pressing temperature described in step (3) is 90-140 DEG C；The pressure of step (3) described hot pressing is 1000-24000 pounds；Step (3) hot pressing time described in is 0.5-6h；
Solvent described in step (3) is tetrahydrofuran, toluene, dimethylbenzene, dimethylacetylamide, dimethylformamide, dimethyl One or more of sulfoxide, N-Methyl pyrrolidone；Soaking time described in step (3)<20min；
The total concentration of potassium hydroxide and/or sodium hydroxide described in step (3) is 0.1-4mol/L；The solution temperature is room - 65 DEG C of temperature；The processing time>6h.
7. the application of compound alkaline polymer electrolyte membrane in a fuel cell described in a kind of claims 1 or 2.
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