CN112366341A - Cross-linking type solid electrolyte ion exchange membrane for fuel cell and preparation method thereof - Google Patents

Cross-linking type solid electrolyte ion exchange membrane for fuel cell and preparation method thereof Download PDF

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CN112366341A
CN112366341A CN202011348025.2A CN202011348025A CN112366341A CN 112366341 A CN112366341 A CN 112366341A CN 202011348025 A CN202011348025 A CN 202011348025A CN 112366341 A CN112366341 A CN 112366341A
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exchange membrane
polymer
ion exchange
cross
membrane
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张金
蔡超
闫丽丽
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Jiangsu Baolin Business Information Consulting Co ltd
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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
    • 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
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • 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
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H01M8/1088—Chemical modification, e.g. sulfonation
    • 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
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H01M8/1093—After-treatment of the membrane other than by polymerisation mechanical, e.g. pressing, puncturing
    • 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 relates to a cross-linking solid electrolyte ion exchange membrane for a fuel cell and a preparation method thereof, wherein the membrane is prepared by the following steps: 1, polymerizing an N-substituted nitrogen heterocyclic monomer containing double bonds, wherein the nitrogen heterocyclic monomer containing double bonds is dissolved and then polymerized by free radicals; 2. synthesizing polyion liquid, namely quaternizing the N atom of the obtained polymer by using C2-C6 straight-chain alcohol with halogenated terminal; 3. mixing, crosslinking and alkalizing the polyion liquid/polyvinyl alcohol, namely taking the quaternary ammonium polymer to swell and dissolve the quaternary ammonium polymer, adding the polyvinyl alcohol into the quaternary ammonium polymer to dissolve the quaternary ammonium polymer, uniformly stirring and mixing, pouring the mixture into a glass plate, adding glutaraldehyde and trace acid, heating and drying the mixture to prepare a membrane, taking the membrane out, and putting the membrane into alkali liquor to alkalize. The membrane provided by the invention has the characteristics of simple preparation method, easiness in membrane formation, high conductivity and good electrochemical stability.

Description

Cross-linking type solid electrolyte ion exchange membrane for fuel cell and preparation method thereof
Technical Field
The invention belongs to the field of solid electrolyte membranes for fuel cells, relates to a cross-linking type solid electrolyte ion exchange membrane for fuel cells and a preparation method thereof, and particularly relates to a method for quaternizing N heterocyclic rings in a polymer, introducing hydroxyl groups into the polymer and then chemically cross-linking the polymer with polyvinyl alcohol.
Background
As a special device for converting chemical energy into electrical energy, a fuel cell is considered to be one of the most promising new chemical power sources that are environmentally friendly due to incomparable advantages of various other energy generation devices, such as high energy conversion efficiency, low pollution, wide selection range of energy storage substances, low noise, and the like. Among them, the polymer electrolyte membrane fuel cell effectively overcomes the problems of fuel leakage and the like, has the advantages of quick start, quick response to load change and the like, receives more and more attention, and becomes a recent research hotspot.
The polymer electrolyte membrane fuel cell takes the polymer electrolyte membrane as a solid electrolyte, and plays roles in dividing the cathode and the anode and conducting protons (H)+) Or hydroxide ion (OH)-) Is a key component in polymer electrolyte fuel cells. The performance of the polymer electrolyte membrane plays a decisive role in the power generation performance of the polymer electrolyte membrane fuel cell, so that the research and development of the high-performance polymer electrolyte membrane are very important.
Interpenetrating network membranes are (IPNs) blended network systems formed by the entanglement of two or more polymers. The method has the advantages that the cross-linking structure can enhance the compatibility among molecular chains and increase the binding force among phases, thereby improving the comprehensive performance of AEM. The N-heterocyclic compound is an organic compound having a heterocyclic structure in a molecule, and the atoms constituting the ring contain at least one N-heteroatom in addition to a carbon atom. The ionized N heterocyclic compound has certain OH-Conductivity, may act as an "active site" in the membrane with ionic conductivity. Under the strong alkaline working environment of AEMFC, the special meta-ring structure of the N heterocyclic cationic functional group can conduct OH to the auxiliary- The positive charge group plays a certain protection role, and the problem that the positive charge group is easy to degrade in an alkaline solution is solved. Compared with the traditional quaternary ammonium cation functional group and quaternary phosphorus cation functional group, the N heterocyclic cation functional group shows excellent alkali-resistant stability.
Disclosure of Invention
The invention mainly aims to provide a polymer electrolyte ion exchange membrane and a preparation method thereof, the polymer electrolyte ion exchange membrane is prepared by a chemical bond crosslinking mode between synthesized polyion liquid and PVA, the preparation method is simple and easy to implement, the raw materials are easy to obtain, the price is low, the mechanical property, the chemical stability and the thermal stability are better, and the ionic conductivity is higher.
In order to achieve the purpose, the invention adopts the following scheme to realize the purpose:
1) polymerization of an N-substituted double bond-containing azacyclic monomer: dissolving an N-substituted nitrogen heterocyclic monomer containing double bonds in absolute ethyl alcohol, adding a recrystallized initiator azodiisobutyronitrile, introducing nitrogen for 30min, removing oxygen in the system, magnetically stirring uniformly, heating to 65-75 ℃, condensing and refluxing under the protection of nitrogen, reacting for 16-24 hours, pouring a reaction mixed solution into petroleum ether to separate out a polymer, dissolving the polymer, separating out again, and drying in vacuum to obtain a polymer containing nitrogen heterocycles;
2) quaternization of the polymer: ultrasonically dispersing and dissolving the polymer obtained in the step 1) in a solvent, adding a certain amount of monohalogenated straight-chain alcohol, adding trace sodium iodide, introducing nitrogen for 30min, removing oxygen in the system, magnetically stirring uniformly, condensing and refluxing at 50-65 ℃ under the protection of nitrogen, reacting for 36-50 hours to perform quaternization on the polymer N, and evaporating the solvent to obtain a solid substance polyion liquid;
3) preparation of blended cast film solution: adding the polyion liquid solid matter obtained in the step 2) into a mixed solvent (dimethyl sulfoxide, pure water and the like in mass ratio), heating to 60-80 ℃, performing ultrasonic dispersion to swell and dissolve the polyion liquid solid matter, adding a certain proportion of polyvinyl alcohol PVA into the mixed solvent, performing magnetic stirring to swell and dissolve the polyvinyl alcohol PVA, and uniformly mixing;
4) crosslinking to form a film: and (2) putting a proper amount of the mixed solution obtained in the step 3) into a flask, adding 5-10% glutaraldehyde solution and 3-10 drops of diluted hydrochloric acid, magnetically stirring for 10-15min, paving the mixed solution on a glass plate, putting the glass plate into an oven at 30-40 ℃, reacting for 4-8 h, putting the glass plate into a vacuum oven at 60-100 ℃ for 60-80 h to dry the solvent to obtain the cross-linked anion exchange membrane, stripping the cross-linked anion exchange membrane, and soaking the cross-linked anion exchange membrane in 1M sodium hydroxide solution at room temperature for 24-48h to obtain the hydroxyl cross-linked anion exchange membrane.
Preferably, the N-substituted double bond-containing nitrogen heterocyclic monomer in step 1) is one or a mixture of more than two of N-vinylimidazole, N-vinylcarbazole and N-vinylpyrrolidone.
Preferably, the mass ratio of the double-bond-containing nitrogen heterocyclic monomer, the absolute ethyl alcohol and the azobisisobutyronitrile in the step 1) is 1 (4-10) to (0.005-0.01).
Preferably, the solvent in step 2) is one of methanol, ethanol, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide.
Preferably, the monohalogenated straight-chain alcohol in the step 2) has a structure formula of Br- (CH)2) n-OH, wherein n = 2-6.
Preferably, the amount ratio of the polymer (repeating unit), the monohalohydrin and the sodium iodide in the step 2) is 1 (0.1-5) to (0.002-0.01).
Preferably, the mass ratio of the polyion liquid solid, the polyvinyl alcohol and the mixed solvent in the step 3) is 1 (0.2-5) to (10-20).
Preferably, the mass of the glutaraldehyde solution added in the step 4) is 0.5-2g in a range of 5% -10%.
A method for preparing the ion exchange membrane of polymer electrolyte features that the chemical cross-linking between the hydroxy groups of polyvinyl alcohol and polyionic liquid is performed.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) the preparation method of the polymer anion exchange membrane disclosed by the invention has the advantages of easily available raw materials, simplicity, easiness, low requirements on equipment and reaction conditions and easiness in realizing large-scale production.
(2) The polymer anion exchange membrane disclosed by the invention has the advantages that N heterocyclic rings in polymer molecules are quaternized, conductive functional sites are generated to form polymer ionic liquid, meanwhile, hydroxyl groups are introduced to facilitate cross-linking with PVA, the problem that the ionic liquid and PVA are dissolved in water is solved, the problem that the ionic liquid with large molecules is easy to lose when small molecules are introduced is solved, and therefore, the membrane has stable performance.
Drawings
FIG. 1 is a graph showing performance data of electrolyte membranes obtained in examples 1 to 6 of the present invention.
Detailed Description
Example 1
1) N-vinylimidazole polymerization: dissolving 2.0g of N-vinyl imidazole in 12g of absolute ethyl alcohol, adding 0.02g of recrystallized initiator azobisisobutyronitrile, introducing nitrogen for 30min to remove oxygen in the system, magnetically stirring uniformly, heating to 72 ℃, condensing and refluxing under the protection of nitrogen, reacting for 24 hours, pouring the reaction mixed solution into petroleum ether to separate out a polymer, dissolving the polymer with ethanol again to separate out, and drying in vacuum to obtain the polymer polyvinyl imidazole containing the nitrogen heterocyclic ring.
2) Quaternization of polyvinyl imidazole: dispersing and dissolving 1.0g of the polyvinyl imidazole obtained in the step 1) in ethanol by ultrasonic, adding 3.18g of 3-bromopropanol, adding 0.005g of sodium iodide, introducing nitrogen for 30min to remove oxygen in the system, uniformly stirring by magnetic force, condensing and refluxing at 50 ℃, reacting for 50 hours to quaternize on polymer N, and evaporating the solvent to obtain a solid substance polyion liquid.
3) Preparation of blended cast film solution: adding 0.25g of polyion liquid solid substance obtained in the step 2) into 5.0g of mixed solvent (mass ratio of dimethyl sulfoxide to pure water, and the like), heating to 80 ℃, performing ultrasonic dispersion to swell and dissolve the solid substance, taking 0.125g of polyvinyl alcohol PVA0, adding magnetic stirring to dissolve the polyvinyl alcohol PVA0, and uniformly mixing.
4) Crosslinking to form a film: and (3) putting a proper amount of the mixed solution obtained in the step 3) into a flask, adding 1.0g of 5% glutaraldehyde solution and 5 drops of dilute hydrochloric acid, magnetically stirring for 10min, flatly paving the mixed solution on a glass plate, putting the glass plate into a drying oven at 40 ℃, reacting for 8h, putting the glass plate into a vacuum drying oven at 80 ℃ for 79 h to dry the solvent to obtain a cross-linked anion exchange membrane, stripping the cross-linked anion exchange membrane, and soaking the cross-linked anion exchange membrane in 1M sodium hydroxide solution at room temperature for 47h to obtain the hydroxyl cross-linked anion exchange membrane.
Example 2
1) N-vinylcarbazole polymerization: dissolving 2.0g of N-vinyl carbazole in 14g of absolute ethanol, adding 0.02g of recrystallized initiator azobisisobutyronitrile, introducing nitrogen for 30min to remove oxygen in the system, magnetically stirring uniformly, heating to 72 ℃, condensing and refluxing under the protection of nitrogen, reacting for 24 hours, pouring the reaction mixed solution into petroleum ether to separate out a polymer, dissolving the polymer with ethanol again to separate out, and drying in vacuum to obtain the polymer polyvinyl carbazole containing the nitrogen heterocycle.
2) Quaternization of polyvinylcarbazole: dispersing and dissolving 1.0g of the polyvinylcarbazole obtained in the step 1) in ethanol by ultrasonic, adding 2.99g of 2-bromoethanol, adding 0.005g of sodium iodide, introducing nitrogen for 30min to remove oxygen in the system, uniformly stirring by magnetic force, condensing and refluxing at 50 ℃, carrying out reaction for 50 hours to quaternize the polymer N, and evaporating the solvent to obtain a solid substance polyion liquid.
3) Preparation of blended cast film solution: adding 0.25g of polyion liquid solid substance obtained in the step 2) into 5.0g of mixed solvent (mass ratio of dimethyl sulfoxide to pure water, and the like), heating to 80 ℃, performing ultrasonic dispersion to swell and dissolve the solid substance, taking 0.25g of polyvinyl alcohol PVA0, adding magnetic stirring to dissolve the polyvinyl alcohol PVA0, and uniformly mixing.
4) Crosslinking to form a film: and (3) putting a proper amount of the mixed solution obtained in the step 3) into a flask, adding 1.0g of 5% glutaraldehyde solution and 5 drops of dilute hydrochloric acid, magnetically stirring for 10min, flatly paving the mixed solution on a glass plate, putting the glass plate into a drying oven at 40 ℃, reacting for 8h, putting the glass plate into a vacuum drying oven at 80 ℃ for 79 h to dry the solvent to obtain a cross-linked anion exchange membrane, stripping the cross-linked anion exchange membrane, and soaking the cross-linked anion exchange membrane in 1M sodium hydroxide solution at room temperature for 47h to obtain the hydroxyl cross-linked anion exchange membrane.
Example 3
1) N-vinylpyrrolidone polymerization: dissolving 2.0g of N-vinyl pyrrolidone in 12g of absolute ethyl alcohol, adding 0.02g of recrystallized initiator azodiisobutyronitrile, introducing nitrogen for 30min to remove oxygen in the system, uniformly stirring by magnetic force, heating to 72 ℃, condensing and refluxing under the protection of nitrogen, reacting for 24 hours, pouring the reaction mixed solution into petroleum ether to separate out a polymer, dissolving the polymer by using ethyl alcohol to separate out again, and drying in vacuum to obtain the polymer polyvinylpyrrolidone containing the nitrogen heterocycle.
2) Quaternization of polyvinylpyrrolidone: dispersing and dissolving 1.0g of polyvinylpyrrolidone obtained in the step 1) in ethanol by ultrasonic, adding 2.95g of 2-bromoethanol, adding 0.005g of sodium iodide, introducing nitrogen for 30min to remove oxygen in the system, uniformly stirring by magnetic force, condensing and refluxing at 50 ℃, reacting for 50 hours to quaternize on the polymer N, and evaporating the solvent to obtain a solid substance polyion liquid.
3) Preparation of blended cast film solution: adding 0.25g of polyion liquid solid substance obtained in the step 2) into 5.0g of mixed solvent (mass ratio of dimethyl sulfoxide to pure water, and the like), heating to 80 ℃, performing ultrasonic dispersion to swell and dissolve the solid substance, taking 0.75g of polyvinyl alcohol PVA, adding magnetic stirring to dissolve the polyvinyl alcohol PVA, and uniformly mixing.
4) Crosslinking to form a film: and (3) putting a proper amount of the mixed solution obtained in the step 3) into a flask, adding 1.0g of 5% glutaraldehyde solution and 5 drops of dilute hydrochloric acid, magnetically stirring for 10min, flatly paving the mixed solution on a glass plate, putting the glass plate into a drying oven at 40 ℃, reacting for 8h, putting the glass plate into a vacuum drying oven at 78 ℃ for 79 h to dry the solvent to obtain a cross-linked anion exchange membrane, stripping the cross-linked anion exchange membrane, and soaking the cross-linked anion exchange membrane in 1M sodium hydroxide solution at room temperature for 47h to obtain the hydroxyl cross-linked anion exchange membrane.
Example 4
1) N-vinylimidazole, N-vinylcarbazole polymerization: dissolving 1.0g of N-vinyl imidazole and 1.0g of 1. 1.0g N-vinyl carbazole in 15g of absolute ethanol, adding 0.02g of recrystallized initiator azobisisobutyronitrile, introducing nitrogen for 30min to remove oxygen in the system, magnetically stirring uniformly, heating to 72 ℃, condensing and refluxing under the protection of nitrogen, reacting for 24 hours, pouring the reaction mixed solution into petroleum ether to separate out a polymer, dissolving the polymer with ethanol, separating out the polymer again, and drying in vacuum to obtain the copolymer containing the nitrogen heterocycle.
2) Quaternization of the copolymer: dispersing and dissolving 1.0g of the copolymer obtained in the step 1) in ethanol by ultrasonic, adding 3.26g of 2-bromoethanol, adding 0.005g of sodium iodide, introducing nitrogen for 30min to remove oxygen in the system, uniformly stirring by magnetic force, condensing and refluxing at 50 ℃, reacting for 50 hours to perform quaternization on the polymer N, and evaporating the solvent to obtain a solid substance polyion liquid.
3) Preparation of blended cast film solution: adding 0.25g of polyion liquid solid substance obtained in the step 2) into 5.0g of mixed solvent (mass ratio of dimethyl sulfoxide to pure water, and the like), heating to 80 ℃, performing ultrasonic dispersion to swell and dissolve the solid substance, taking 0.25g of polyvinyl alcohol PVA0, adding magnetic stirring to dissolve the polyvinyl alcohol PVA0, and uniformly mixing.
4) Crosslinking to form a film: and (3) putting a proper amount of the mixed solution obtained in the step 3) into a flask, adding 1.0g of 5% glutaraldehyde solution and 5 drops of dilute hydrochloric acid, magnetically stirring for 10min, flatly paving the mixed solution on a glass plate, putting the glass plate into a drying oven at 40 ℃, reacting for 8h, putting the glass plate into a vacuum drying oven at 78 ℃ for 79 h to dry the solvent to obtain a cross-linked anion exchange membrane, stripping the cross-linked anion exchange membrane, and soaking the cross-linked anion exchange membrane in 1M sodium hydroxide solution at room temperature for 47h to obtain the hydroxyl cross-linked anion exchange membrane.
Example 5
1) N-vinylimidazole, N-vinylpyrrolidone polymerization: dissolving 1.0g of N-vinyl imidazole and 1.0g of N-vinyl pyrrolidone in 15g of absolute ethanol, adding 0.02g of recrystallized initiator azobisisobutyronitrile, introducing nitrogen for 30min to remove oxygen in the system, uniformly stirring by magnetic force, heating to 72 ℃, condensing and refluxing under the protection of nitrogen, reacting for 24 hours, pouring the reaction mixed solution into petroleum ether to separate out a polymer, dissolving the polymer by using the ethanol, separating out the polymer again, and drying in vacuum to obtain the copolymer containing the nitrogen heterocycle.
2) Quaternization of the copolymer: dispersing and dissolving 1.0g of the copolymer obtained in the step 1) in ethanol by ultrasonic, adding 2.96g of 2-bromoethanol, adding 0.005g of sodium iodide, introducing nitrogen for 30min to remove oxygen in the system, uniformly stirring by magnetic force, condensing and refluxing at 50 ℃, reacting for 50 hours to perform quaternization on the polymer N, and evaporating the solvent to obtain a solid substance polyion liquid.
3) Preparation of blended cast film solution: adding 0.25g of polyion liquid solid substance obtained in the step 2) into 5.0g of mixed solvent (mass ratio of dimethyl sulfoxide to pure water, and the like), heating to 80 ℃, performing ultrasonic dispersion to swell and dissolve the solid substance, taking 0.25g of polyvinyl alcohol PVA0, adding magnetic stirring to dissolve the polyvinyl alcohol PVA0, and uniformly mixing.
4) Crosslinking to form a film: and (3) putting a proper amount of the mixed solution obtained in the step 3) into a flask, adding 1.0g of 5% glutaraldehyde solution and 5 drops of dilute hydrochloric acid, magnetically stirring for 10min, flatly paving the mixed solution on a glass plate, putting the glass plate into a drying oven at 40 ℃, reacting for 8h, putting the glass plate into a vacuum drying oven at 78 ℃ for 79 h to dry the solvent to obtain a cross-linked anion exchange membrane, stripping the cross-linked anion exchange membrane, and soaking the cross-linked anion exchange membrane in 1M sodium hydroxide solution at room temperature for 47h to obtain the hydroxyl cross-linked anion exchange membrane.
Example 6
1) N-vinylcarbazole, N-vinylpyrrolidone polymerization: dissolving 1.0g of N-vinyl carbazole and 1.0g of N-vinyl pyrrolidone in 15g of absolute ethanol, adding 0.02g of recrystallized initiator azobisisobutyronitrile, introducing nitrogen for 30min to remove oxygen in the system, uniformly stirring by magnetic force, heating to 72 ℃, condensing and refluxing under the protection of nitrogen, reacting for 24 hours, pouring the reaction mixed solution into petroleum ether to separate out a polymer, dissolving the polymer by using ethanol, separating out the polymer again, and drying in vacuum to obtain the copolymer containing the nitrogen heterocycle.
2) Quaternization of the copolymer: dispersing and dissolving 1.0g of the copolymer obtained in the step 1) in ethanol by ultrasonic, adding 3.2g of 2-bromoethanol, adding 0.005g of sodium iodide, introducing nitrogen for 30min to remove oxygen in the system, uniformly stirring by magnetic force, condensing and refluxing at 50 ℃, reacting for 50 hours to perform quaternization on the polymer N, and evaporating the solvent to obtain a solid substance polyion liquid.
3) Preparation of blended cast film solution: adding 0.25g of the polyion liquid solid substance obtained in the step 2) into 5.0g of a mixed solvent (mass ratio of dimethyl sulfoxide to pure water), heating to 80 ℃, performing ultrasonic dispersion to swell and dissolve the solid substance, adding 0.5g of polyvinyl alcohol PVA0, and stirring by magnetic force to dissolve the polyvinyl alcohol PVA0 until the mixture is uniformly mixed.
4) Crosslinking to form a film: and (3) putting a proper amount of the mixed solution obtained in the step 3) into a flask, adding 1.0g of 5% glutaraldehyde solution and 5 drops of dilute hydrochloric acid, magnetically stirring for 10min, flatly paving the mixed solution on a glass plate, putting the glass plate into a drying oven at 40 ℃, reacting for 8h, putting the glass plate into a vacuum drying oven at 82 ℃ for 79 h to dry the solvent to obtain a cross-linked anion exchange membrane, stripping the cross-linked anion exchange membrane, and soaking the cross-linked anion exchange membrane in 1M sodium hydroxide solution at room temperature for 47h to obtain the hydroxyl cross-linked anion exchange membrane.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.

Claims (9)

1. A cross-linked solid electrolyte ion exchange membrane for a fuel cell, characterized by being prepared by the following process:
1) polymerization of an N-substituted double bond-containing azacyclic monomer: dissolving an N-substituted nitrogen heterocyclic monomer containing double bonds in absolute ethyl alcohol, adding a recrystallized initiator azodiisobutyronitrile, introducing nitrogen for 30min, removing oxygen in the system, magnetically stirring uniformly, heating to 65-75 ℃, condensing and refluxing under the protection of nitrogen, reacting for 16-24 hours, pouring a reaction mixed solution into petroleum ether to separate out a polymer, dissolving the polymer, separating out again, and drying in vacuum to obtain a polymer containing nitrogen heterocycles;
2) quaternization of the polymer: ultrasonically dispersing and dissolving the polymer obtained in the step 1) in a solvent, adding a certain amount of monohalogenated straight-chain alcohol, adding trace sodium iodide, introducing nitrogen for 30min, removing oxygen in the system, magnetically stirring uniformly, condensing and refluxing at 50-65 ℃ under the protection of nitrogen, reacting for 36-50 hours to perform quaternization on the polymer N, and evaporating the solvent to obtain a solid substance polyion liquid;
3) preparation of blended cast film solution: adding the polyion liquid solid matter obtained in the step 2) into a mixed solvent (dimethyl sulfoxide, pure water and the like in mass ratio), heating to 60-80 ℃, performing ultrasonic dispersion to swell and dissolve the polyion liquid solid matter, adding a certain proportion of polyvinyl alcohol PVA into the mixed solvent, performing magnetic stirring to swell and dissolve the polyvinyl alcohol PVA, and uniformly mixing;
4) crosslinking to form a film: and (2) putting a proper amount of the mixed solution obtained in the step 3) into a flask, adding 5-10% glutaraldehyde solution and 3-10 drops of diluted hydrochloric acid, magnetically stirring for 10-15min, paving the mixed solution on a glass plate, putting the glass plate into an oven at 30-40 ℃, reacting for 4-8 h, putting the glass plate into a vacuum oven at 60-100 ℃ for 60-80 h to dry the solvent to obtain the cross-linked anion exchange membrane, stripping the cross-linked anion exchange membrane, and soaking the cross-linked anion exchange membrane in 1M sodium hydroxide solution at room temperature for 24-48h to obtain the hydroxyl cross-linked anion exchange membrane.
2. The method for preparing the polymer electrolyte ion exchange membrane according to claim 1, wherein the N-substituted double bond-containing nitrogen heterocyclic monomer in the step 1) is one or a mixture of two or more of N-vinylimidazole, N-vinylcarbazole and N-vinylpyrrolidone.
3. The method for preparing the polymer electrolyte ion exchange membrane according to claim 1, wherein the mass ratio of the double bond-containing nitrogen heterocyclic monomer, the absolute ethyl alcohol and the azobisisobutyronitrile in the step 1) is 1 (4-10) to (0.005-0.01).
4. The method for preparing the polymer electrolyte ion exchange membrane according to claim 1, wherein the solvent in step 2) is one of methanol, ethanol, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide.
5. The method for preparing the polymer electrolyte ion exchange membrane according to claim 1, wherein the monohalogenated linear alcohol in the step 2) has a structure formula of Br- (CH)2) n-OH, wherein n = 2-6.
6. The method for preparing a polymer electrolyte ion exchange membrane according to claim 1, wherein the amount ratio of the polymer (repeating unit), the monohalohydrin and the sodium iodide in the step 2) is 1 (0.1-5) to (0.002-0.01).
7. The method for preparing the polymer electrolyte ion exchange membrane according to claim 1, wherein the mass ratio of the polyion liquid solid, the polyvinyl alcohol and the mixed solvent in the step 3) is 1 (0.2-5) to (10-20).
8. The method for preparing the polymer electrolyte ion exchange membrane according to claim 1, wherein the mass of the glutaraldehyde solution added in the step 4) is 0.5-2g to 5-10%.
9. The method for preparing the ion exchange membrane with the polymer electrolyte according to the claims 1 to 8, wherein the crosslinking method is chemical crosslinking between the hydroxyl groups of the polyvinyl alcohol and the polyionic liquid.
CN202011348025.2A 2020-11-26 2020-11-26 Cross-linking type solid electrolyte ion exchange membrane for fuel cell and preparation method thereof Withdrawn CN112366341A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114006017A (en) * 2021-10-29 2022-02-01 中汽创智科技有限公司 Proton exchange membrane and preparation method and application thereof
CN115838495A (en) * 2022-11-29 2023-03-24 南开大学 Self-supporting covalent cross-linking functional polyelectrolyte porous membrane and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114006017A (en) * 2021-10-29 2022-02-01 中汽创智科技有限公司 Proton exchange membrane and preparation method and application thereof
CN114006017B (en) * 2021-10-29 2023-05-26 中汽创智科技有限公司 Proton exchange membrane and preparation method and application thereof
CN115838495A (en) * 2022-11-29 2023-03-24 南开大学 Self-supporting covalent cross-linking functional polyelectrolyte porous membrane and preparation method and application thereof
CN115838495B (en) * 2022-11-29 2023-09-19 南开大学 Self-supporting covalent cross-linking functional polyelectrolyte porous membrane and preparation method and application thereof

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Application publication date: 20210212