CN111952649B - Polyvinyl alcohol/polyquaternium anion exchange membrane for anion exchange membrane fuel cell - Google Patents
Polyvinyl alcohol/polyquaternium anion exchange membrane for anion exchange membrane fuel cell Download PDFInfo
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- CN111952649B CN111952649B CN202010752234.7A CN202010752234A CN111952649B CN 111952649 B CN111952649 B CN 111952649B CN 202010752234 A CN202010752234 A CN 202010752234A CN 111952649 B CN111952649 B CN 111952649B
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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
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
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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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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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
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Abstract
The invention provides a polyvinyl alcohol/polyquaternium anion exchange membrane for an anion exchange membrane fuel cell, belonging to the field of fuel cells. The exchange membrane is obtained by soaking a polyvinyl alcohol/polyquaternium cross-linked membrane in an alkaline solution to ionize hydroxide radicals of the polyvinyl alcohol/polyquaternium cross-linked membrane; the polyvinyl alcohol/polyquaternium cross-linked membrane is obtained by cross-linking the polyvinyl alcohol/polyquaternium membrane by glutaraldehyde; the polyvinyl alcohol/polyquaternium film is prepared from the following raw materials in parts by weight: 1 to 5 portions of polyvinyl alcohol and 0.1 to 5 portions of polyquaternium. The exchange membrane has good mechanical property and thermal stability; meanwhile, the water absorption rate and the swelling degree of the water-soluble polyurethane can meet the use requirements; in addition, the exchange membrane has high conductivity which is superior to the prior art; the exchange membrane also has good oxidation resistance and alkali resistance, stable chemical performance and can obviously prolong the service life of the exchange membrane. The exchange membrane can be applied to an anion exchange membrane fuel cell and has good application prospect.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a polyvinyl alcohol/polyquaternium anion exchange membrane for an anion exchange membrane fuel cell.
Background
In recent years, environmental problems have been highly emphasized in various countries of the world, and development and utilization of renewable energy have become one of effective measures for solving the environmental problems. The fuel cell is a chemical device capable of directly converting chemical energy in fuel into electric energy, and among a plurality of renewable energy sources, the fuel cell is unique due to the characteristics of high energy conversion rate, no noise, no pollution and the like, and becomes a novel clean energy source with the most development potential. Fuel cells can be classified into Proton Exchange Membrane Fuel Cells (PEMFCs) and Anion Exchange Membrane Fuel Cells (AEMFCs) according to the operating environment of the ion exchange membrane. PEMFCs are used in many fields due to their advantages of high energy efficiency, high density, low pollution, etc., but the use of a noble metal Pt catalyst and the proton exchange membrane material are very expensive and difficult to form a membrane, which makes PEMFCs costly and greatly limits their commercial development. AEMFCs, which contain non-noble metals (Ag, ni, fe) as catalysts and possess higher electrode reactivity in alkaline media than PEMFCs, are becoming the focus of research in the fuel cell field.
Anion Exchange Membranes (AEMs) are the core components of AEMFCs, and are not only the separator between the anode and cathode, but also the OH - The performance of the conductors of (a) directly determines the actual performance of the AEMFCs. Currently, most studied anion exchange membrane materials mainly comprise polyphenyl ether, polysulfone, polyether ketone, polyether ether ketone, polystyrene, styrene thermoplastic elastomer and the like. However, they generally have to undergo highly complex quaternization processes, including chloromethylation of benzene and quaternization of benzyl chloride. In addition, the reagents used in the chloromethylation step (such as chloromethyl ether) are toxic and carcinogenic. Polyvinyl alcohol (PVA) is a water-soluble high-molecular polymer with wide application, has good film-forming property and good electrochemical stability. Meanwhile, PVA has wide sources, low price, safety and no toxicity, and can be used for preparing anion exchange membranes. Xiong et al prepared a series of cross-linked quaternary ammonium PVA anion exchange membranes, and the test results showed that the ion conductivity of the novel anion exchange membrane can be as high as 7.34X 10 -3 S/cm, higher than other anion exchange membranes. Ye and the like prepare the alkaline nano composite membrane of the completely exfoliated graphene nanosheet and PVA which can be directly used for the methanol fuel cell, when the content of graphene is 0.7wt%, the ionic conductivity of the membrane can be improved by 126%, and the methanol permeability can be reduced by 55%.
In recent years, although the preparation process of anion exchange membranes has been greatly developed, there are problems such as complicated preparation process, high cost, poor alkali-resistant stability of membranes, too large degree of swelling in an alkaline solution, and the like. At the same time, the conductivity of anion exchange membranes is to be further improved for better applications.
Disclosure of Invention
The invention aims to provide a polyvinyl alcohol/polyquaternium anion exchange membrane for an anion exchange membrane fuel cell.
The invention provides a polyvinyl alcohol/polyquaternium anion exchange membrane for an anion exchange membrane fuel cell, which is obtained by soaking a polyvinyl alcohol/polyquaternium cross-linked membrane in an alkaline solution to ionize hydroxide radicals of the polyvinyl alcohol/polyquaternium cross-linked membrane;
the polyvinyl alcohol/polyquaternium cross-linked membrane is obtained by cross-linking the polyvinyl alcohol/polyquaternium membrane by glutaraldehyde;
the polyvinyl alcohol/polyquaternium film is prepared from the following raw materials in parts by weight: 1 to 5 portions of polyvinyl alcohol and 0.1 to 5 portions of polyquaternium.
Further, the alkali solution is N 2 A saturated alkali solution;
preferably, the concentration of the alkali solution is 1M;
more preferably, said N 2 The saturated alkali solution is prepared by the following method: preparing 1M alkali solution by deionized water, and introducing N into the 1M alkali solution 2 Bringing the alkali solution to N 2 Saturation to obtain;
further preferably, the deionized water is used for removing O 2 And CO 2 Deionized water of (4);
still more preferably, the alkali solution is a NaOH solution.
Further, the step of soaking the polyvinyl alcohol/polyquaternium crosslinked film in the alkali solution is to soak the polyvinyl alcohol/polyquaternium crosslinked film in the alkali solution at the temperature of between 20 and 40 ℃ for 24 to 48 hours;
preferably, the step of soaking the polyvinyl alcohol/polyquaternium crosslinked film in the alkali solution is to soak the polyvinyl alcohol/polyquaternium crosslinked film in the alkali solution at the temperature of 30 ℃ for 24 hours;
more preferably, the polyvinyl alcohol/polyquaternium crosslinked film is soaked in the alkaline solution and then is washed;
further preferably, the washing is with N 2 Rinsing with saturated deionized water.
Further, the glutaraldehyde is a glutaraldehyde methanol solution;
preferably, the concentration of the glutaraldehyde in the glutaraldehyde methanol solution is 1-7 wt%;
more preferably, the concentration of the glutaraldehyde in the glutaraldehyde methanol solution is 3 to 5wt%;
further preferably, the glutaraldehyde concentration in the glutaraldehyde methanol solution is 3wt%.
Further, the temperature of the crosslinking is 30-40 ℃, and the time is 3-6 h;
preferably, the temperature of the crosslinking is 30 ℃ and the time is 4h.
Further, the polyvinyl alcohol/polyquaternary ammonium salt membrane is prepared from the following raw materials in parts by weight: 1 part of polyvinyl alcohol and 0.25-1.5 parts of polyquaternium;
preferably, the polyvinyl alcohol/polyquaternium membrane is prepared from the following raw materials in parts by weight: 1 part of polyvinyl alcohol and 0.75-1.25 parts of polyquaternium;
more preferably, the polyvinyl alcohol/polyquaternary ammonium salt membrane is prepared from the following raw materials in parts by weight: 1 part of polyvinyl alcohol and 1 part of polyquaternium.
Further, the preparation method of the polyvinyl alcohol/polyquaternary ammonium salt membrane comprises the following steps: respectively preparing polyvinyl alcohol solution and polyquaternary ammonium salt solution by using deionized water, uniformly mixing, removing bubbles, and then removing the solvent to obtain the polyvinyl alcohol and polyquaternary ammonium salt solution;
preferably, the concentration of the polyvinyl alcohol solution is 10wt%; the concentration of the polyquaternium solution is 4wt%;
and/or, the condition of uniform mixing is that the mixture is stirred for 1 to 3 hours at the temperature of between 20 and 40 ℃;
and/or, the bubble removal is carried out for 5 to 10 hours under the vacuum condition with the temperature of 20 to 40 ℃ and the pressure of-100 kPa, and then the mixture is kept stand overnight;
and/or, the solvent is removed, and the mixture is placed for 24 to 72 hours at the temperature of between 20 and 30 ℃;
more preferably, the condition of uniform mixing is stirring for 1h at 30 ℃;
and/or, the bubble removal is carried out for 6 hours under the vacuum condition with the temperature of 30 ℃ and the pressure of-100 kPa, and then the standing is carried out overnight;
and/or, the solvent is removed by standing for 24-48 h at the temperature of 30 ℃.
Further, the polymerization degree of the polyvinyl alcohol is 1700, and the alcoholysis degree is 99%;
and/or the polyquaternium is polyquaternium-10.
The invention also provides the application of the polyvinyl alcohol/polyquaternium anion exchange membrane as an anion exchange membrane of a fuel cell; preferably, the fuel cell is an anion exchange membrane fuel cell.
The invention also provides the application of the polyvinyl alcohol/polyquaternium anion exchange membrane in preparing an anion exchange membrane for a fuel cell; preferably, the fuel cell is an anion exchange membrane fuel cell.
In the present invention, the hydroxyl group ionization means anion in the polyvinyl alcohol/polyquaternium anion exchange membrane (e.g., cl in polyquaternium-10) - ) Is fully converted into hydroxyl ions (OH) - )。
In the invention, the room temperature is 25 +/-5 ℃; overnight means 12. + -.2 h.
The invention takes PVA as a matrix material, polyquaternium (PQ-10) as an anion carrier and GA as a cross-linking agent, and prepares the polyvinyl alcohol/polyquaternium anion exchange membrane by a simple solution casting membrane-forming method. The prepared anion exchange membrane is uniform and flat, and has good mechanical property and thermal stability; within a proper range of PVA and polyquaternium ratio and GA dosage, the water absorption rate and the swelling capacity of the anion exchange membrane can meet the use requirement of the anion exchange membrane as a fuel cell, and the ion exchange capacity is high and can reach 1.73 meq/g at most; the mass ratio of PVA to polyquaternium is 1:1. at the dosage of 3wt% of GA, the conductivity of the cross-linked membrane can reach 79.37mS/cm at the maximum at 80 ℃, and can exceed that of a plurality of current anion-exchange membranes; in addition, the polyvinyl alcohol/polyquaternium anion exchange membrane has good oxidation resistance and alkali resistance, the GA dosage is 3wt%, and the mass ratio of the PVA to the polyquaternium is 1: the mass residual rate of the anion exchange membrane 1 after being oxidized for 2 hours in a Fenton reagent at 80 ℃ is 93.29 percent, and the residual rate of the conductivity of the anion exchange membrane still remains 56.68 percent after the anion exchange membrane is soaked in a 1M NaOH solution at 60 ℃ for 10 days.
In a word, the prepared polyvinyl alcohol/polyquaternium anion exchange membrane is uniform and flat, and has good mechanical property and thermal stability; meanwhile, the water absorption rate and the swelling degree of the anion exchange membrane can meet the use requirement of the anion exchange membrane, and the ion exchange capacity is high; in addition, the polyvinyl alcohol/polyquaternium anion exchange membrane has high conductivity, which is superior to the prior art; the anion exchange membrane also has good oxidation resistance and alkali resistance, stable chemical performance and can obviously prolong the service life of the anion exchange membrane. The polyvinyl alcohol/polyquaternium anion exchange membrane can be applied to an anion exchange membrane fuel cell and has good application prospect.
It will be apparent that various other modifications, substitutions and alterations can be made in the present invention without departing from the basic technical concept of the invention as described above, according to the common technical knowledge and common practice in the field.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 is a schematic diagram of an interpenetrating network simulation of a PVA/PQ-10 cross-linked membrane.
FIG. 2 is an infrared spectrum of different PVA/PQ-10 anion exchange membranes: in the figure, line a represents a PVA/PQ-10 membrane (PVA/PQ-10 mass ratio of 1; the line b is an anion exchange membrane prepared by crosslinking a glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 of 1.75,3 wt%; the line c is an anion exchange membrane prepared by crosslinking a glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 of 1,1wt%; the line d is an anion exchange membrane prepared by crosslinking 1,3wt% of glutaraldehyde methanol solution of PVA and PQ-10; and the line e is an anion exchange membrane prepared by crosslinking 1,5wt% of glutaraldehyde methanol solution of PVA and PQ-10.
FIG. 3 is an SEM photograph of various groups of PVA/PQ-10 anion exchange membranes, PVA/PQ-10 crosslinked membrane Cl not ionized by hydroxyl - EDS map of distribution and macro photo of PVA/PQ-10 anion exchange membrane: a is an exchange membrane prepared by cross-linking 1,1wt% of glutaraldehyde methanol solution of PVA and PQ-10; b is an exchange membrane prepared by crosslinking 1,3wt% of glutaraldehyde methanol solution of PVA and PQ-10; c is an exchange membrane prepared by crosslinking a glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 of 1,5 wt%; d is an exchange membrane prepared by crosslinking a glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 of 1.25, 3wt%; e is an exchange membrane prepared by crosslinking a glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 of 1.75 and 3wt%; f is an exchange membrane prepared by crosslinking a glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 of 1,3 wt%; g is an exchange membrane prepared by crosslinking a glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 of 1.25, 3wt%; h is an exchange membrane prepared by crosslinking 1.5,3wt% of glutaraldehyde methanol solution of PVA and PQ-10; i is Cl in a PVA/PQ-10 cross-linked membrane (not hydroxyl ionized) prepared by cross-linking a glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 being 1,3wt percent and prepared by cross-linking - An EDS map of the distribution; j is a macroscopic photograph of the PVA/PQ-10 anion exchange membrane.
FIG. 4 is a TGA and DTG plot for each group of PVA/PQ-10 anion exchange membranes: a is an anion exchange membrane prepared by different mass ratios of PVA and PQ-10 when the concentration of glutaraldehyde in the cross-linking agent solution is 3wt%; b is an anion exchange membrane prepared by different glutaraldehyde concentrations in the cross-linking agent solution when the mass ratio of PVA to PQ-10 is 1.
FIG. 5 shows the mechanical properties of various groups of PVA/PQ-10 anion exchange membranes: a is the tensile strength and elongation at break of anion exchange membranes prepared by different mass ratios of PVA to PQ-10 when the concentration of glutaraldehyde in the cross-linking agent solution is 3wt%; b is the tensile strength of anion exchange membranes prepared from PVA and PQ-10 with different mass ratios under different glutaraldehyde concentrations; and c is the elongation at break of the anion exchange membranes prepared by PVA and PQ-10 with different mass ratios under different glutaraldehyde concentrations.
FIG. 6 shows the water absorption and swelling results for various groups of PVA/PQ-10 anion exchange membranes: a is a water absorption swelling diagram of anion exchange membranes with different mass ratios of PVA to PQ-10 when the concentration of glutaraldehyde is 3wt%; b and c are PVA and PQ-10 with different mass ratios, and the water absorption rate and the swelling degree of the anion exchange membrane are prepared under different glutaraldehyde dosages; d and e are the changes of the water absorption rate and the swelling degree of the anion exchange membrane with different mass ratios of PVA to PQ-10 along with the temperature when the concentration of the glutaraldehyde is 3wt%; f and g are the mass ratio of PVA to PQ-10 of 1:1, the water absorption and swelling degree of the anion exchange membrane prepared by different glutaraldehyde dosage change with temperature.
FIG. 7 shows the conductivity results for each group of PVA/PQ-10 anion exchange membranes: a is the conductivity of anion exchange membranes with different mass ratios of PVA to PQ-10 at different temperatures when the concentration of glutaraldehyde is 3wt%; b is an Arrhenius curve graph of ln sigma to 1000/T corresponding to the conductivity of the anion-exchange membrane with different mass ratios of PVA to PQ-10 at different temperatures when the concentration of glutaraldehyde is 3wt%; c is the mass ratio of PVA to PQ-10 of 1: at 0.75 moment, the anion exchange membrane prepared by different glutaraldehyde dosages has electric conductivity at different temperatures; d is the mass ratio of PVA to PQ-10 is 1: at 0.75 moment, the Arrhenius curve graph of ln sigma to 1000/T corresponding to the conductivity of the anion-exchange membrane prepared by different glutaraldehyde dosages at different temperatures; e is the mass ratio of PVA to PQ-10 is 1:1, preparing the anion exchange membrane with different glutaraldehyde dosages to obtain the anion exchange membrane with the conductivity at different temperatures; f is the mass ratio of PVA to PQ-10 of 1:1, preparing Arrhenius graphs of corresponding ln sigma to 1000/T of the conductivity of the anion-exchange membrane at different temperatures by using different amounts of glutaraldehyde; g is the mass ratio of PVA to PQ-10 of 1:1.25 hours, the anion exchange membrane prepared by different glutaraldehyde dosages has conductivity at different temperatures; h is the mass ratio of PVA to PQ-10 of 1:1.25, arrhenius curve graphs of ln sigma corresponding to the conductivity at different temperatures of the anion exchange membrane prepared by different glutaraldehyde dosages to 1000/T.
FIG. 8 shows the oxidation resistance test results for various groups of PVA/PQ-10 anion exchange membranes: a is the oxidation mass residual rate of the anion exchange membrane with different mass ratios of PVA to PQ-10 when the concentration of glutaraldehyde is 3wt%; b is the oxidation mass residual rate of the anion exchange membrane prepared under different dosage of glutaraldehyde and different mass ratio of PVA to PQ-10.
FIG. 9 shows the results of alkali resistance tests for various groups of PVA/PQ-10 anion exchange membranes: a is the conductivity residual rate in the alkali resistance test of the anion-exchange membrane with different mass ratios of PVA to PQ-10 when the concentration of glutaraldehyde is 3wt%; b is the mass ratio of PVA to PQ-10 is 1: and 1, the conductivity residue rate in the alkali resistance test of the anion exchange membrane prepared by different glutaraldehyde dosage.
Detailed Description
The raw materials and equipment used in the embodiment of the present invention are known products and commercially available products. The main materials are as follows:
polyquaternium-10 (PQ-10), purchased from Allantin; polyvinyl alcohol 1799 (PVA, degree of polymerization DP =1700, degree of alcoholysis 99%), glutaraldehyde (GA, 50wt.% aqueous solution), anhydrous methanol, and other reagents were all from the chengdong chemical reagent plant. All reagents were analytical grade and were not further purified during use.
EXAMPLE 1 preparation of the inventive PVA/PQ-10 anion exchange Membrane
1. Preparation of PVA/PQ-10 film
Preparation of PVA aqueous solution and PQ-10 aqueous solution: PVA is added into deionized water and stirred for 6h at 95 ℃ to be completely dissolved, and 10wt% PVA water solution is prepared. PQ-10 is added into deionized water at room temperature and stirred for 4h, and PQ-10 is completely dissolved to prepare 4wt% PQ-10 aqueous solution.
Preparing PVA/PQ-10 film-forming solution: the PVA aqueous solution and the PQ-10 aqueous solution were weighed and mixed in a mass ratio of 1. Stirring the PVA/PQ-10 mixed solution at 30 ℃ for 1h to uniformly mix the mixed solution to obtain a film forming solution, then placing the film forming solution in a vacuum oven at 30 ℃ and under the pressure of-100 kPa for 6h to carry out vacuum defoaming, taking out the film forming solution and standing overnight to further remove bubbles in the film forming solution.
Film forming process: the debubbled deposition solution was slowly poured into a tetrafluoro dish (13 cm. Times.13 cm) and spread uniformly on the bottom of the dish. And (3) placing the tetrafluoro disc in an oven at 30 ℃ for 24h to remove the solvent, then stripping the PVA/PQ-10 film from the tetrafluoro disc, and placing the tetrafluoro disc in an oven at 30 ℃ for 24h to further remove residual moisture in the film, thus obtaining the PVA/PQ-10 film.
2. Cross-linking of PVA/PQ-10 membranes
And (2) taking a 3wt% glutaraldehyde methanol solution (a preparation method is that 6g of 50wt% glutaraldehyde water solution is dissolved in 94g of anhydrous methanol) as a cross-linking agent solution, immersing the PVA/PQ-10 membrane prepared in the step (1) in the 3wt% glutaraldehyde methanol solution, placing the membrane in an oven at 30 ℃ for 4h for cross-linking reaction, taking the PVA/PQ-10 membrane out of the glutaraldehyde methanol solution after the cross-linking process is finished, and placing the membrane in the oven at 30 ℃ for 24h to remove the residual glutaraldehyde methanol solution in the membrane, thereby obtaining the PVA/PQ-10 cross-linked membrane.
3. Hydroxide ionization of PVA/PQ-10 crosslinked membranes
Boiling deionized water to remove O 2 And CO 2 Cooling, preparing 1M NaOH solution, and continuously introducing N into 1M NaOH solution 2 The NaOH solution is brought to N for 5h 2 And (4) saturation. Soaking the PVA/PQ-10 cross-linked membrane prepared in the step 2 in N at the temperature of 30 DEG C 2 Adding into saturated NaOH solution for 24h, and adding AgNO 3 And HNO 3 Detection was performed to ensure chloride ion (Cl) in the membrane - ) Fully convert into OH - . After the conversion was complete, the membrane was removed from the NaOH solution and replaced with N 2 Rinsing with saturated deionized water to neutral to remove excess OH - And obtaining the hydroxyl ionized PVA/PQ-10 cross-linked membrane (PVA/PQ-10 anion exchange membrane). And putting the prepared hydroxyl ionized PVA/PQ-10 cross-linked membrane (PVA/PQ-10 anion exchange membrane) into a dryer for storage for later use. The simulation diagram of the interpenetrating network of the PVA/PQ-10 cross-linked membrane is shown in figure 1.
Examples 2 to 6 preparation of PVA/PQ-10 anion exchange membranes of the invention
By the preparation method of example 1, only in the step 1 "preparation of PVA/PQ-10 film-forming solution", the mass ratio of PVA to PQ-10 was changed to 1. Thus obtaining the PVA/PQ-10 anion exchange membrane with different PQ-10 concentrations.
Example 2: a glutaraldehyde methanol solution of PVA and PQ-10 with the mass ratio of 1.25,3wt% is used as a cross-linking agent solution;
example 3: a glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 of 1:0.5,3wt% is used as a cross-linking agent solution;
example 4: a glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 being 1.75,3 wt% is used as a cross-linking agent solution;
example 5: a glutaraldehyde methanol solution of PVA and PQ-10 with the mass ratio of 1.25,3wt% is used as a cross-linking agent solution;
example 6: a glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 being 1.5,3wt% was used as a crosslinking agent solution.
Examples 7 to 9 preparation of PVA/PQ-10 anion exchange membranes of the invention
Using the preparation method of example 1, only the "concentration of glutaraldehyde methanol solution" of step 2 was changed to 1wt%, 5wt%, or 7wt%. Thus obtaining the glutaraldehyde methanol solution cross-linked PVA/PQ-10 anion exchange membrane with different concentrations.
Example 7: 1,1,1wt% of glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 as a cross-linking agent solution;
example 8: a glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 being 1,5wt% is used as a cross-linking agent solution.
Example 9: a glutaraldehyde methanol solution of PVA and PQ-10 at a mass ratio of 1,7wt% was used as a cross-linking agent solution.
Examples 10 to 15 preparation of PVA/PQ-10 anion exchange membranes of the invention
The preparation method of example 1 was adopted, and the PVA/PQ-10 anion exchange membrane of the invention was prepared by changing only the mass ratio of PVA to PQ-10 in the step 1 "preparation of PVA/PQ-10 film-forming solution" and the concentration of glutaraldehyde methanol solution in the step 2.
Example 10: 1, taking a glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 of 1;
example 11: 1.25 mass percent of PVA and PQ-10, and 1wt percent of glutaraldehyde methanol solution as a cross-linking agent solution;
example 12: a glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 being 1.75,5 wt% is used as a cross-linking agent solution;
example 13: a glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 of 1.25,5wt% is used as a cross-linking agent solution;
example 14: a glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 being 1.75,7 wt% is used as a cross-linking agent solution;
example 15: glutaraldehyde methanol solution with the mass ratio of PVA to PQ-10 being 1.25,7wt% was used as the cross-linking agent solution.
The advantageous effects of the present invention are demonstrated by specific test examples below.
Test example 1 structural characterization of the PVA/PQ-10 anion exchange Membrane of the invention
1. Test method
The chemical structures of the PVA/PQ-10 anion-exchange membranes and PVA/PQ-10 membranes of the invention were characterized by Fourier Infrared Spectroscopy (Bruker Tensor 27, bruker, germany): the measuring range is 1000-4000cm -1 Resolution of 4cm -1 。
The surfaces of the PVA/PQ-10 anion exchange membrane and the PVA/PQ-10 membrane were subjected to vacuum gold spraying, and the surface micro-topography of the membranes was subjected to scanning test using a scanning electron microscope (JSM-5900 LV, japan K.K.) at an acceleration voltage of 5kV.
2. Test results
The infrared spectra of different PVA/PQ-10 anion exchange membranes and PVA/PQ-10 membranes are shown in FIG. 2. 3312cm in the figure -1 The nearby broad peak is the stretching vibration absorption peak of hydroxyl O-H in PVA and PQ-10 molecules; 2925cm -1 And 2860cm -1 The absorption peak at (A) is due to the stretching vibration absorption peak of saturated C-H; 1644cm -1 The absorption peak is caused by water molecules in the membrane, 1434cm -1 And 1341cm -1 The absorption peak at (A) is due to the C-CH within the molecule of PQ-10 3 Is bentVibrating; 1231cm -1 The weak peak is the stretching vibration absorption peak of C-N in the molecule of PQ-10; 1065cm -1 The nearby peak is the C-O-C stretching vibration absorption peak in the film. Each of the crosslinked membranes (i.e., PVA/PQ-10 anion exchange membranes) was found to be 1065cm as compared to the PVA/PQ-10 uncrosslinked membrane (line a in FIG. 2, i.e., PVA/PQ-10 membrane) -1 The absorption peaks in (A) are significantly enhanced, indicating that GA does undergo a crosslinking reaction with PVA and PQ-10 to form an ether bond.
FIG. 3 is a surface SEM picture of PVA/PQ-10 anion exchange membranes prepared with different PVA to PQ-10 mass ratios and different GA dosages (crosslinking concentrations). FIG. 3j is a macroscopic photograph of a PVA/PQ-10 anion-exchange membrane sample, and it can be seen that the anion-exchange membrane prepared by the invention is a white transparent membrane, the surface is smooth and flat, and the crosslinked membrane has good flexibility, can be arbitrarily curled and folded, and can be cut into any shape.
As shown in FIGS. 3a-c, when the amount of the cross-linking agent GA is 1wt% and 3wt%, the surface of the exchange membrane is uniform and dense, and no obvious micropores and phase separation phenomenon exist; when the GA dosage is 5wt%, the surface of the exchange membrane is not flat and compact any more, and a large number of micropores are formed. The reason is that the cross-linking degree of the membrane is increased along with the increase of the amount of GA, the compatibility between two components of the blend membrane is reduced, a certain degree of phase separation is generated, the PQ-10 molecules which are not cross-linked migrate out of the membrane and dissolve into a cross-linking agent solution (methanol), the membrane material is cleaned, the PQ-10 in the membrane is further lost, a large number of micropores are generated in the membrane, and the disadvantage of the performance of the anion exchange membrane is seen due to the excessive amount of GA.
As can be seen from FIGS. 3d-h, when the amount of GA is 3wt%, the surfaces of the anion exchange membranes prepared according to different mass ratios of PVA to PQ-10 are flat and compact, and the compatibility between the two components of the blend membrane is good.
FIG. 3i shows the mass ratio of PVA to PQ-10 is 1:1. cl in crosslinked film not ionized by hydroxyl at the amount of GA 3wt% - EDS picture of distribution, the distribution of green point in the picture is Cl - Distribution of (2) can be seen, cl in the film - Is uniformly and densely distributed and can be OH - Provide sufficient transmission channels, and thus PVA/PQ-10 crosslinked membranes are suitable for use asIs an anion exchange membrane applied to a fuel cell.
Test example 2 thermogravimetric analysis and mechanical property test of PVA/PQ-10 anion exchange membrane of the invention
1. Test method
The test samples were dried in a vacuum oven at 60 ℃ for 24h and subjected to thermogravimetric analysis (TA 2950, duPont, usa) under the following conditions: the temperature range is 30-600 ℃, the heating rate is 10 ℃/min, and the test atmosphere is N 2 。
The test specimens were prepared as 40X 10mm specimens and subjected to tensile testing in a universal materials testing machine (Instron 5567, instron Inc., USA) at a tensile rate of 50mm/min and a grip interval of 20mm in a room temperature environment.
2. Test results
The anion exchange membrane for the fuel cell has higher requirements on the use temperature and needs to ensure the stable use at 0-80 ℃, so the PVA/PQ-10 anion exchange membrane is used in N 2 Thermogravimetric analysis tests were performed to characterize the thermal stability of the membrane material. As can be seen from FIG. 4, the thermal weight loss process of the PVA/PQ-10 anion exchange membrane is divided into three stages: the weight loss in the first stage (0-150 ℃) is mainly the thermal evaporation of a small amount of water adsorbed in the membrane material; the weight loss in the second stage (150-330 ℃) is mainly the thermal decomposition of quaternary ammonium groups on PQ-10 in the membrane; the weight loss in the third stage (330-450 ℃) is mainly due to the degradation of the PVA and PQ-10 molecular backbones within the membrane. As shown in FIGS. 4a and 4b, the thermal stability of the PVA/PQ-10 anion exchange membrane tends to be improved as the amount of PQ-10 and the amount of GA are increased. The thermogravimetric characterization of the membrane material can show that the PVA/PQ-10 anion exchange membrane has good thermal stability.
As shown in fig. 5a, when the glutaraldehyde concentration in the cross-linking agent solution is 3wt%, the tensile strength of the membrane gradually decreases with the increase of the amount of PQ-10 in the PVA/PQ-10 anion exchange membrane, while the elongation at break of the membrane increases and then decreases, and when the mass ratio of PVA to PQ-10 is 1. However, when the ratio of PVA to PQ-10 exceeds 1. As can be seen from fig. 5b and 5c, the tensile strength of the film increased and then decreased with the increase of the amount of GA, and when the amount of GA was 3wt% and the ratio of PVA to PQ-10 was 1; while the elongation at break of the film tended to decrease with increasing GA usage. Comprehensively considering, when the GA dosage is 3wt%, and the mass ratio of PVA to PQ-10 is 1.
Test example 3 ion exchange Capacity and Water swelling of the PVA/PQ-10 anion exchange Membrane of the present invention
1. Test method
(1) Water absorption and swelling degree test
Preparing sample to be tested into 40 × 10mm sample band, drying in vacuum oven at 60 deg.C to constant weight, and placing sample band at 30 deg.C N 2 Soaking in saturated deionized water for 24h, taking out the completely swollen anion exchange membrane, absorbing excessive water on the membrane surface with filter paper, quickly weighing the mass of the sample, measuring the length of the sample, and respectively marking as W w And L w (ii) a Finally, the fully swollen sample film is dried in a vacuum oven at 60 ℃ to constant weight, the mass of the sample is again weighed and its length is measured, respectively marked as W d And L d 。
The water absorption (WU) and swelling capacity (SR) of the anion exchange membrane were calculated using the following formulas, respectively:
wherein, W w And W d The mass of the fully swollen and fully dried anion exchange membrane, respectively; l is w And L d The length of the fully swollen and fully dried anion exchange membrane, respectively.
(2) Ion Exchange Capacity (IEC)
A certain amount ofDrying the PVA/PQ-10 anion exchange membrane in a vacuum oven at 60 ℃ to constant weight, weighing the weight, and recording the weight as m d Soaking the weighed anion exchange membrane in 30mL of HCl solution with the concentration of 0.01M, and stirring for 24h at 30 ℃ to ensure OH in the membrane - Is totally covered with H + And (4) neutralizing. Then using phenolphthalein as an indicator, titrating the solution for soaking the anion exchange membrane by using a calibrated 0.01M NaOH solution, and calculating the ion exchange capacity by using the following formula:
wherein, V 0,NaOH The volume of NaOH solution used for titration of a 0.01M HCl solution; v NaOH The volume of NaOH solution used to titrate the HCl solution that has soaked the anion exchange membrane; c NaOH The concentration of the NaOH solution is calibrated by potassium hydrogen phthalate; m is d The weight of the completely dry anion exchange membrane.
2. Test results
The ion exchange capacity refers to the amount of ions that can be exchanged per unit volume or mass of the ion exchange material, and the size of the ion exchange capacity of an anion exchange membrane directly determines its electrical conductivity. The IEC values for anion exchange membranes for different PVA to PQ-10 mass ratios and different GA dosages are given in tables 1 and 2, respectively.
As can be seen from tables 1 and 2, as the amount of PQ-10 component in the membrane increased, the IEC value of the membrane material gradually increased; with the increase of the amount of GA, the IEC value of the membrane material is increased and then decreased, because proper crosslinking can improve the compatibility of PVA and PQ-10, so that the PQ-10 in the membrane is relatively more, the IEC value of the membrane material is higher, but the compatibility between two components in the membrane is reduced due to excessive crosslinking degree, a certain degree of phase separation is generated, and a great amount of PQ-10 loss is caused in the crosslinking process and the subsequent experiment cleaning process of the membrane material, so the IEC of the membrane material is reduced.
According to the IEC value and the WU value corresponding to the anion exchange membrane, the number of water molecules absorbed by a single quaternary ammonium group can be calculated and is expressed as lambda (the smaller the lambda value is, the less the number of water molecules absorbed by the single quaternary ammonium group in the membrane is), and the calculation formula is as follows:
wherein WU is the water absorption of the anion exchange membrane, and the unit is; IEC is the ion exchange capacity of the same anion exchange membrane in meq.
The more the number of water molecules adsorbed by a single quaternary ammonium group in the membrane is, the more the OH can be transmitted in the membrane - The conductivity of the anion-exchange membrane can be effectively improved by selecting a proper mass ratio of PVA to PQ-10 and the amount of GA.
As can be seen from the lambda values in tables 1 and 2, the lambda value of the membrane material decreased as the amount of PQ-10 and the amount of GA increased.
TABLE 1. Different PVA to PQ-10 mass ratios at 20 ℃ for anion exchange membranes prepared with a glutaraldehyde concentration of 3 wt.% IEC, WU and lambda
TABLE 2 anion exchange membranes prepared at different glutaraldehyde concentrations IEC, WU and lambda at 20 deg.C
The water absorption and swelling degree of the anion exchange membrane for the fuel cell influence the use performance of the anion exchange membrane, the water in the membrane is beneficial to the conduction of anions, the conductivity of the membrane is improved, however, the mechanical strength of the anion exchange membrane is reduced when the water absorption is too high, and the deformation of the membrane is too large, so that the anion exchange membrane has proper water absorption and swelling degree.
FIG. 6 shows the effect of PVA to PQ-10 mass ratio, GA usage and temperature on the water absorption and swelling of a cross-linked PVA/PQ-10 anion exchange membrane. As can be seen from FIGS. 6a-c, as the amount of PQ-10 and the amount of GA increase, both the water absorption and the swelling degree of the membrane material decrease; along with the increase of the GA dosage, the crosslinking degree of the PVA/PQ-10 crosslinking membrane is increased, the interaction between molecules in the membrane is enhanced, the arrangement of molecular chains becomes orderly and compact, so that the water molecules enter the membrane difficultly, and the water absorption rate and the swelling degree of the membrane are reduced. As shown in FIGS. 6d-g, the water absorption and swelling degree of the membrane materials with different PVA-PQ-10 mass ratios and different GA dosages increased with increasing temperature; and as the dosage of PQ-10 and GA is increased, the water absorption rate and the swelling degree of the membrane material are reduced under the influence of temperature. Through tests on the water absorption rate and the swelling degree of the cross-linked PVA/PQ-10 anion exchange membrane, the water absorption rate and the swelling degree of the membrane material are too high to meet the use requirement of the membrane material as the anion exchange membrane when the PQ-10 component in the membrane is less than 0.75 and the GA dosage is less than 3 percent.
Test example 4 ion conductivity of the PVA/PQ-10 anion exchange Membrane of the present invention
1. Test method
Preparing a sample film to be tested into a sample strip of 40 multiplied by 5mm and placing the sample strip in N 2 Soaking in saturated deionized water for 24 hr, taking out the membrane, fixing on a conductivity test mold to ensure good contact between the membrane and the electrode, and placing the mold in N 2 Completely immersing the membrane in a constant-temperature water bath in saturated constant-temperature deionized water; the conductivity test was carried out by an electrochemical workstation (CHI 650E, shanghai Chenghua instruments Co., ltd.) at an isothermal interval of 20 ℃ in the temperature range of 40-80 ℃ by means of an alternating current impedance method at a test frequency of 10kHz-0.1Hz and a test voltage of 5mV.
Conductivity σ (mS. Cm) -1 ) Calculated by the following formula:
wherein l (cm) is the distance between two electrodes of the test fixture; r (k Ω) is the resistance of the crosslinked film measured by the electrochemical workstation; d (cm) and w (cm) are the width and thickness of the crosslinked film, respectively.
2. Test results
The anion exchange membrane applied to the fuel cell is required to have high ionic conductivity, and the conductivity of the PVA/PQ-10 anion exchange membrane of the invention is tested at 40-80 ℃, and the result is shown in FIG. 7.
As can be seen from FIG. 7a, the conductivity of the PVA/PQ-10 anion-exchange membrane is in positive correlation with the temperature, the temperature is increased, the movement capacity of molecular chains in the membrane is enhanced, and meanwhile, the water absorption swelling of the membrane is increased to a certain extent, which is beneficial to the transmission of ions in the membrane and the conductivity of the membrane is increased; at a specific temperature, with the increase of the dosage of PQ-10 in the film, the quaternary ammonium groups in the film are increased, and OH - The electric conductivity of the chemical crosslinking membrane is increased, and the mass ratio of PVA to PQ-10 is 1:1, the conductivity of the membrane can be as high as 79.37mS/cm, whereas when the mass ratio of PVA to PQ-10 exceeds 1:1, a certain degree of phase separation occurs due to poor compatibility between PVA and PQ-10 in the membrane, causing partial release of PQ-10 from the membrane during membrane treatment, resulting in a decrease in the conductivity of the crosslinked membrane.
FIG. 7c,7e,7g discloses that glutaraldehyde in the cross-linking agent at 1wt% is used to achieve a low degree of cross-linking and a high degree of water swelling of the membrane, resulting in too low a density of quaternised groups in the membrane and a low conductivity of the membrane; the conductivity of the membrane is increased along with the increase of the dosage of glutaraldehyde in the cross-linking agent, however, when the cross-linking agent is excessively cross-linked, the molecular weights of cross-linked PVA and cross-linked PQ-10 in the membrane are increased, the compatibility between two components of the blend membrane is reduced, a certain degree of phase separation is generated, and in the membrane treatment process, the non-cross-linked PQ-10 molecules migrate out of the membrane, so that a large amount of PQ-10 in the membrane is lost, and the conductivity of the membrane is rapidly reduced.
The dependence of the conductivity of the anion exchange membrane on temperature at low temperatures is generally considered to be of the Arrhenuis type:
σ＝σ 0 exp(-Ea/RT) (6)
in the formula, σ 0 Is a pre-exponential factor, ea is offThe apparent activation energy of the daughter migration, R is the molar gas constant, and T is the thermodynamic temperature (K). By further processing the electrical conductivity of 7a,7c,7e,7g and plotting corresponding ln σ vs 1000/T curves, it can be found that the law of electrical conductivity as a function of temperature follows the Arrhenuis equation.
Test example 5 chemical stability of the PVA/PQ-10 anion exchange Membrane of the present invention
1. Test method
(1) And (3) oxidation resistance test: the sample film to be tested was dried to constant weight and its weight was recorded, then immersed in Fenton's reagent (containing 2ppm of FeSO) at 80 deg.C 4 3% of 2 O 2 Aqueous solution), taking out the membrane, washing with deionized water, drying to constant weight, recording the residual weight, and calculating the weight residual rate after oxidation.
(2) Alkali resistance test: a sample membrane to be tested is prepared into a sample strip with the size of 40 multiplied by 5mm, the sample membrane is soaked in 1M NaOH solution at the temperature of 60 ℃, the membrane is taken out every 2 days, the conductivity of the membrane at the temperature of 60 ℃ is tested according to the method of the test example 4, the continuous test is carried out for 10 days, and the conductivity residual rate of the membrane is calculated.
2. Test results
Since the conduction mechanism of the anion exchange membrane generates oxygen free radicals in the cell, the oxygen free radicals are accompanied by oxidative degradation of the anion exchange membrane during the operation of the fuel cell, which requires the anion exchange membrane to have good oxidation resistance. As shown in FIG. 8, by performing an oxidation test of the cross-linked PVA/PQ-10 anion exchange membrane with a Fenton reagent at 80 ℃, it was found that as the amount of PQ-10 component in the membrane increases, the mass residual rate of the membrane material after oxidation decreases, and the oxidation resistance thereof decreases; the mass residue rate of the cross-linked anion-exchange membranes with different ratios of PVA to PQ-10 after oxidation increases with the amount of GA. The result of an oxidation experiment shows that the minimum mass residual rate of the anion exchange membrane material after oxidation can still reach about 70 percent, so that the PVA/PQ-10 anion exchange membrane has better oxidation resistance.
In the use process of the alkaline anion exchange membrane, quaternary ammonium groups in the membrane are subjected to OH in solution - Influence will generate Hofmann degradation to generate tertiary amine and alcohol, quaternary ammoniumThe reduction of the radicals lowers the conductivity of the anion exchange membrane, and therefore the alkali resistance of the membrane is an important factor in determining the service life of the anion exchange membrane. All PVA/PQ-10 crosslinked membranes were intact during the alkali resistance test, and the residual condition of the conductivity was as shown in FIG. 9. As can be seen from the graph, the conductivity of the crosslinked film gradually decreased with the lapse of time, and the decrease tendency tended to be gentle. All the cross-linked membranes can still keep about 50% of the original conductivity after being soaked in 1M NaOH solution for 10 days, wherein the GA dosage is 3%, and the ratio of PVA to PQ-10 is 1: the conductivity residual rate of the crosslinked film of 1 is 56.68%, and better alkali resistance is shown.
In conclusion, the prepared polyvinyl alcohol/polyquaternium anion exchange membrane is uniform and flat, and has good mechanical property and thermal stability; meanwhile, the water absorption rate and the swelling degree of the anion exchange membrane can meet the use requirement of the anion exchange membrane, and the ion exchange capacity is high and can reach 1.73 meq/g at most; in addition, the polyvinyl alcohol/polyquaternary ammonium salt anion exchange membrane has high conductivity which can reach 79.37mS/cm at most and is superior to the prior art; the anion exchange membrane also has good oxidation resistance and alkali resistance, stable chemical performance and can obviously prolong the service life. The polyvinyl alcohol/polyquaternium anion exchange membrane can be applied to an anion exchange membrane fuel cell and has good application prospect.
Claims (20)
1. A polyvinyl alcohol/polyquaternium anion exchange membrane for use in an anion exchange membrane fuel cell, characterized by: the method is characterized in that a polyvinyl alcohol/polyquaternium crosslinked film is immersed in an alkaline solution, so that hydroxide radicals of the polyvinyl alcohol/polyquaternium crosslinked film are ionized to obtain the polyvinyl alcohol/polyquaternium crosslinked film;
the polyvinyl alcohol/polyquaternium cross-linked membrane is obtained by cross-linking the polyvinyl alcohol/polyquaternium membrane by glutaraldehyde; the glutaraldehyde is a glutaraldehyde methanol solution; the concentration of glutaraldehyde in the glutaraldehyde methanol solution is 3wt%;
the polyvinyl alcohol/polyquaternium film is prepared from the following raw materials in parts by weight: 1 part of polyvinyl alcohol and 1 part of polyquaternium;
the polyquaternium is polyquaternium-10.
2. The polyvinyl alcohol/polyquaternium anion exchange membrane of claim 1, wherein: the alkali solution is N 2 A saturated alkali solution.
3. The polyvinyl alcohol/polyquaternium anion exchange membrane of claim 2, wherein: the concentration of the alkali solution is 1M.
4. The polyvinyl alcohol/polyquaternium anion exchange membrane of claim 3, wherein: said N is 2 The saturated alkali solution is prepared by the following method: preparing 1M alkaline solution by deionized water, and introducing N into the 1M alkaline solution 2 Bringing the alkali solution to N 2 And (5) saturation to obtain the product.
5. The polyvinyl alcohol/polyquaternium anion exchange membrane according to claim 4, wherein: the deionized water is used for removing O 2 And CO 2 Deionized water.
6. The polyvinylalcohol/polyquaternium anion exchange membrane of claim 5 wherein: the alkali solution is NaOH solution.
7. The polyvinyl alcohol/polyquaternium anion exchange membrane of claim 1, wherein: the step of soaking the polyvinyl alcohol/polyquaternium crosslinked film in the aqueous alkali is to soak the polyvinyl alcohol/polyquaternium crosslinked film in the aqueous alkali at the temperature of 20-40 ℃ for 24-48 h.
8. The polyvinylalcohol/polyquaternium anion exchange membrane of claim 7 wherein: the step of soaking the polyvinyl alcohol/polyquaternium crosslinked film in the alkali solution is to soak the polyvinyl alcohol/polyquaternium crosslinked film in the alkali solution at the temperature of 30 ℃ for 24 hours.
9. The polyvinylalcohol/polyquaternium anion exchange membrane of claim 8 wherein: the polyvinyl alcohol/polyquaternium crosslinked film is soaked in an alkali solution and then is washed.
10. The polyvinyl alcohol/polyquaternium anion exchange membrane of claim 9, wherein: the washing is with N 2 Rinsing with saturated deionized water.
11. The polyvinyl alcohol/polyquaternium anion exchange membrane of claim 1, wherein: the temperature of the cross-linking is 30-40 ℃, and the time is 3-6 h.
12. The polyvinyl alcohol/polyquaternium anion exchange membrane according to claim 11, wherein: the temperature of the crosslinking is 30 ℃ and the time is 4h.
13. The polyvinyl alcohol/polyquaternium anion exchange membrane according to claim 1, wherein: the preparation method of the polyvinyl alcohol/polyquaternium membrane comprises the following steps: respectively preparing polyvinyl alcohol solution and polyquaternium solution from polyvinyl alcohol and polyquaternium by using deionized water, uniformly mixing, removing bubbles, and then removing the solvent to obtain the product.
14. The polyvinyl alcohol/polyquaternium anion exchange membrane of claim 13, wherein: the concentration of the polyvinyl alcohol solution is 10wt%; the concentration of the polyquaternium solution is 4wt%;
and/or, the condition of uniform mixing is that the mixture is stirred for 1 to 3 hours at the temperature of between 20 and 40 ℃;
and/or, the bubble removal is carried out for 5 to 10 hours under the vacuum condition with the temperature of 20 to 40 ℃ and the pressure of-100 kPa, and then the mixture is kept stand overnight;
and/or, the solvent is removed under the condition of 20-30 ℃ for 24-72 h.
15. The polyvinyl alcohol/polyquaternium anion exchange membrane of claim 14, wherein: the condition of uniform mixing is that the mixture is stirred for 1 hour at the temperature of 30 ℃;
and/or, the bubble removal is carried out for 6 hours under the vacuum condition of 30 ℃ and the pressure of-100 kPa, and then the mixture is kept stand overnight;
and/or, the solvent is removed by standing for 24-48 h at the temperature of 30 ℃.
16. The polyvinyl alcohol/polyquaternium anion exchange membrane of claim 1, wherein: the polymerization degree of the polyvinyl alcohol is 1700, and the alcoholysis degree of the polyvinyl alcohol is 99%.
17. Use of a polyvinyl alcohol/polyquaternium anion exchange membrane as defined in any of claims 1 to 16 as an anion exchange membrane for a fuel cell.
18. Use according to claim 17, characterized in that: the fuel cell is an anion exchange membrane fuel cell.
19. Use of a polyvinyl alcohol/polyquaternium anion exchange membrane as claimed in any of claims 1 to 16 in the preparation of an anion exchange membrane for a fuel cell.
20. Use according to claim 19, characterized in that: the fuel cell is an anion exchange membrane fuel cell.
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