CN112500598A - Polymer anion exchange membrane for fuel cell and preparation method thereof - Google Patents
Polymer anion exchange membrane for fuel cell and preparation method thereof Download PDFInfo
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- CN112500598A CN112500598A CN202011471961.2A CN202011471961A CN112500598A CN 112500598 A CN112500598 A CN 112500598A CN 202011471961 A CN202011471961 A CN 202011471961A CN 112500598 A CN112500598 A CN 112500598A
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- exchange membrane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2287—After-treatment
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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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
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Abstract
A polymer anion exchange membrane for a fuel cell and a preparation method thereof, the membrane is prepared by the following steps: 1) modifying PVA, grafting a side chain group containing carbon-carbon double bonds onto PVA, 2) grafting imidazole mercaptan onto the product obtained in the step 1) through click reaction, 3) quaternizing imidazole in the product obtained in the step 2) by using dihalogenated hydrocarbon and monohalogenated hydrocarbon, crosslinking the imidazole to a certain degree, and putting the product into NaOH aqueous solution for alkalization after film formation to obtain the alkaline anion-exchange membrane. The membrane provided by the invention has the characteristics of simple preparation method, easiness in membrane formation, high conductivity and good electrochemical stability.
Description
Technical Field
The invention belongs to the field of polymer anion exchange electrolyte membranes for fuel cells, and relates to an anion exchange membrane prepared by grafting imidazole functional groups to modified PVA by utilizing click reaction, quaternizing and chemically crosslinking macromolecules and a method.
Background
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.
The cross-linked network anion exchange membrane is a network system formed between polymer macromolecular chains through a cross-linking agent and reaction sites on the macromolecular chains. The advantages are that the cross-linking structure can enhance the binding force between the molecular chains in the anion exchange, and the mechanical property is improved when the anion exchange membrane is in a water saturation state, so the comprehensive performance of the anion exchange can be improved. A great deal of reports about ion exchange membranes, namely that imidazole rings have certain OH after ionization-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 imidazole ring cationic functional group can conduct OH in an auxiliary way- 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 imidazole cation functional group shows excellent alkali-resistant stability.
click chemistry is an emerging synthesis tool box particularly suited for end or side group functionalization, cross-linking of polymer matrices and highly branched materials, the attractiveness of click chemistry is the modular nature of the reaction plus a combination of powerful features such as: regioselectivity, quantitative yield, non-hue purification, use of benign solvents (e.g., water), and mild reaction conditions.
Disclosure of Invention
The invention mainly aims to provide a polymer anion exchange electrolyte membrane and a preparation method thereof, and relates to an anion exchange membrane prepared by grafting imidazole functional groups to modified PVA by means of click reaction, quaternizing and chemically crosslinking macromolecules and a method thereof.
In order to achieve the purpose, the invention adopts the following scheme to realize the purpose:
a polymer anion exchange membrane for a fuel cell and a preparation method thereof can be prepared according to the following processes:
1) in N2Under protection, dissolving a certain amount of polyvinyl alcohol (PVA) in DMSO, adding a certain amount of powdered alkali, magnetically stirring for 2 hours at 70 ℃, then adding a certain amount of DMSO solution of allyl bromide preheated to 70 ℃, violently stirring for reaction for 48-72 hours, pouring the mixture into cold water, precipitating, filtering and collecting, repeatedly washing with water, and drying at low temperature to obtain the modified PVA with the carbon-carbon double bond side chain;
2) adding a certain proportion of the substance prepared in the step 1), imidazole thiol and 2% equivalent of photoinitiator DMPA into methanol at room temperature, stirring and dissolving uniformly in a dark place, then blowing nitrogen to remove oxygen, radiating for 60min under 365nm UV, carrying out rotary evaporation and concentration, washing with NaOH aqueous solution to remove unreacted substance imidazole thiol, washing with deionized water, and drying for later use;
3) dissolving a proper amount of the substance obtained in the step 2) in N, N-dimethylformamide, adding a certain proportion of dihalogenated hydrocarbon, stirring for 10min, pouring the mixed solution on a clean glass plate, putting the glass plate into a 50 ℃ oven for reaction for 8h, adding a certain proportion of halogenated hydrocarbon, continuing to react and fully quaternize for 24h, drying the solvent to obtain a cross-linked membrane, stripping the membrane, and soaking the membrane in a 1M sodium hydroxide solution at room temperature for 24-48h to obtain the hydroxyl cross-linked anion exchange membrane.
Preferably, the amount ratio of PVA (repeating unit), allyl bromide and alkali substance in the step 1) is 1 (0.05-1.2): (0.1-2.4).
Preferably, the base in step 1) is one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide and cesium carbonate.
Preferably, the amount ratio of the PVA (repeating unit) and the imidazole thiol substance in the step 2) is 1 (0.05-1.5).
Preferably, the imidazole thiol in step 2) is one or two of N-methylimidazole-2-thiol and N-methylbenzimidazole-2-thiol.
Preferably, the amount ratio of the PVA (repeating unit), the monohalogenated hydrocarbon and the dihalogenated hydrocarbon in the step 3) is 1 (0.05-1.2) (0.05-0.3).
Preferably, the monohalogenated hydrocarbon in the step 3) is R-X, wherein X = Cl, Br, I, R is benzyl or C1-C6 linear alkyl, etc., and the dihalogenated hydrocarbon is p-dibenzyl bromide or
And the like.
The invention has the following beneficial effects:
the invention provides a polymer anion exchange membrane and a preparation method thereof, and relates to an anion exchange membrane and a method for preparing the anion exchange membrane by grafting imidazole functional groups to modified PVA by click reaction, quaternizing and chemically crosslinking among macromolecules.
Drawings
FIG. 1 is a graph showing performance data of electrolyte membranes obtained in examples 1 to 4 of the present invention.
Detailed Description
The present invention is illustrated by the following examples, which are not intended to be limiting.
Example 1
1) In N2Under protection, dissolving a certain amount of 2g of polyvinyl alcohol (PVA) in DMSO, adding a certain amount of powdered alkali KOH of 5.0g, magnetically stirring at 70 ℃ for 2h, then adding a DMSO solution preheated to 70 ℃ and containing 6.6g of allyl bromide, violently stirring for reaction for 48-72h, pouring the mixture into cold water, precipitating, filtering and collecting, repeatedly washing with water, and drying at low temperature to obtain the modified PVA with the carbon-carbon double bond side chain.
2) Adding 2.0g of the substance prepared in the step 1), 3.25g of N-methylimidazole-2-thiol and 2% of equivalent weight of photoinitiator DMPA into methanol at room temperature in a certain proportion, stirring and dissolving uniformly in a dark place, then blowing nitrogen to remove oxygen, radiating for 60min under 365nm UV, carrying out rotary evaporation and concentration, washing with NaOH aqueous solution to remove unreacted imidazole thiol, washing with pure water, and drying for later use.
3) Dissolving 2.0g of a proper amount of the substance obtained in the step 2) in N, N-dimethylformamide, adding 0.38g of 1.2-dibromoethane, stirring for 10min, pouring the mixed solution on a clean glass plate, putting the glass plate into a 50 ℃ oven for reaction for 8h, adding 1.43g of methyl iodide, continuing to react for full quaternization for 24h, drying the solvent to obtain a cross-linked membrane, stripping the membrane, and soaking the membrane in 1M sodium hydroxide solution at room temperature for 24h to obtain the hydroxyl cross-linked anion exchange membrane.
Example 2
1) In N2Under protection, dissolving a certain amount of 2g of polyvinyl alcohol (PVA) in DMSO, adding a certain amount of powdered alkali CsOH 13.0g, magnetically stirring at 70 ℃ for 2h, then adding a DMSO solution preheated to 70 ℃ and 6.6g of allyl bromide, violently stirring for reaction for 48-72h, pouring the mixture into cold water, precipitating, filtering and collecting, repeatedly washing with water, and drying at low temperature to obtain the modified PVA with the carbon-carbon double bond side chain.
2) Adding 2.0g of the substance prepared in the step 1), 3.25g of N-methylimidazole-2-thiol and 2% of equivalent weight of photoinitiator DMPA into methanol at room temperature in a certain proportion, stirring and dissolving uniformly in a dark place, then blowing nitrogen to remove oxygen, radiating for 60min under 365nm UV, carrying out rotary evaporation and concentration, washing with NaOH aqueous solution to remove unreacted imidazole thiol, washing with pure water, and drying for later use.
3) Dissolving 2.0g of a proper amount of the substance obtained in the step 2) in N, N-dimethylformamide, adding 0.44g of 1.4-dibromobutane, stirring for 10min, pouring the mixed solution on a clean glass plate, putting the glass plate into a 50 ℃ oven for reaction for 8h, adding 1.43g of methyl iodide, continuing to react for full quaternization for 24h, drying the solvent to obtain a cross-linked membrane, stripping the membrane, and soaking the membrane in 1M sodium hydroxide solution at room temperature for 24h to obtain the hydroxyl cross-linked anion exchange membrane.
Example 3
1) In N2Under protection, a certain amount of 2g of polyvinyl alcohol (PVA) is dissolved in DMSO, a certain amount of powdered alkali CsOH 13.0g is added, magnetic stirring is carried out for 2 hours at 70 ℃, then a DMSO solution preheated to 70 ℃ and containing 6.6g of allyl bromide is added, reaction is carried out for 48 to 72 hours under vigorous stirring, the mixture is poured into cold water, precipitation and filtration collection are carried out, and washing is carried out repeatedlyWashing and drying at low temperature to obtain the modified PVA with the carbon-carbon double bond side chain.
2) Adding 2.0g of the substance prepared in the step 1), 4.63g of N-methylbenzimidazole-2-mercaptan and 2% of photoinitiator DMPA into methanol at room temperature in a certain proportion, stirring and dissolving uniformly in a dark place, then blowing nitrogen to remove oxygen, radiating for 60min under 365nm UV, carrying out rotary evaporation and concentration, washing with NaOH aqueous solution to remove unreacted imidazole mercaptan, washing with water, and drying for later use.
3) Dissolving 2.0g of a proper amount of the substance obtained in the step 2) in N, N-dimethylformamide, adding 0.35g of 1.4-dibromobutane, stirring for 10min, pouring the mixed solution on a clean glass plate, putting the glass plate into a 50 ℃ oven for reaction for 8h, adding 0.85g of bromoethane, continuing to react and fully quaternize for 24h, drying the solvent to obtain a cross-linked membrane, stripping the membrane, and soaking the membrane in 1M sodium hydroxide solution at room temperature for 24h to obtain the hydroxyl cross-linked anion exchange membrane.
Example 4
1) In N2Under protection, dissolving a certain amount of 2g of polyvinyl alcohol (PVA) in DMSO, adding a certain amount of powdered alkali CsOH 13.0g, magnetically stirring at 70 ℃ for 2h, then adding a DMSO solution preheated to 70 ℃ and 6.6g of allyl bromide, violently stirring for reaction for 48-72h, pouring the mixture into cold water, precipitating, filtering and collecting, repeatedly washing with water, and drying at low temperature to obtain the modified PVA with the carbon-carbon double bond side chain.
2) Adding 2.0g of the substance prepared in the step 1), 4.63g of N-methylbenzimidazole-2-mercaptan and 2% of photoinitiator DMPA into methanol at room temperature in a certain proportion, stirring and dissolving uniformly in a dark place, then blowing nitrogen to remove oxygen, radiating for 60min under 365nm UV, carrying out rotary evaporation and concentration, washing with NaOH aqueous solution to remove unreacted imidazole mercaptan, washing with water, and drying for later use.
3) Dissolving 2.0g of a proper amount of the substance obtained in the step 2) in N, N-dimethylformamide, adding 0.44g of p-dibenzyl bromide, stirring for 10min, pouring the mixed solution on a clean glass plate, putting the glass plate into an oven at 50 ℃ for reaction for 8h, adding 0.85g of bromoethane, continuing to react for full quaternization for 24h, drying the solvent to obtain a cross-linked membrane, stripping the membrane, and soaking the membrane in 1M sodium hydroxide solution at room temperature for 24h to obtain the hydroxide cross-linked anion exchange membrane.
Claims (7)
1. A polymer anion exchange membrane for a fuel cell and a preparation method thereof are characterized by comprising the following steps:
in N2Under protection, dissolving a certain amount of polyvinyl alcohol (PVA) in DMSO, adding a certain amount of powdered alkali, magnetically stirring for 2 hours at 70 ℃, then adding a certain amount of DMSO solution of allyl bromide preheated to 70 ℃, violently stirring for reaction for 48-72 hours, pouring the mixture into cold water, precipitating, filtering and collecting, repeatedly washing with water, and drying at low temperature to obtain the modified PVA with the carbon-carbon double bond side chain;
adding a certain proportion of the substance prepared in the step 1), imidazole thiol and 2% equivalent of photoinitiator DMPA into methanol at room temperature, stirring and dissolving uniformly in a dark place, then blowing nitrogen to remove oxygen, radiating for 60min under 365nm UV, carrying out rotary evaporation and concentration, washing with NaOH aqueous solution to remove unreacted substance imidazole thiol, washing with deionized water, and drying for later use;
dissolving a proper amount of the substance obtained in the step 2) in N, N-dimethylformamide, adding a certain proportion of dihalogenated hydrocarbon, stirring for 10min, pouring the mixed solution on a clean glass plate, putting the glass plate into a 50 ℃ oven for reaction for 8h, adding a certain proportion of halogenated hydrocarbon, continuing to react and fully quaternize for 24h, drying the solvent to obtain a cross-linked membrane, stripping the membrane, and soaking the membrane in a 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 anion-exchange membrane according to claim 1, wherein the amount ratio of the PVA (repeating unit), the allyl bromide and the alkali substance in the step 1) is 1 (0.05-1.2): (0.1-2.4).
3. The method for preparing the polymeric anion exchange membrane according to claim 1, wherein the base in the step 1) is one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide and cesium carbonate.
4. The method for preparing the polymer anion exchange membrane according to claim 1, wherein the amount ratio of the PVA (repeating unit) to the imidazole thiol substance in the step 2) is 1 (0.05-1.5).
5. The method for preparing the polymeric anion exchange membrane according to claim 1, wherein the imidazole thiol in the step 2) is one or two of N-methylimidazole-2-thiol and N-methylbenzimidazole-2-thiol.
6. The method for preparing a polymer anion exchange membrane according to claim 1, wherein the amount ratio of the PVA (repeating unit), the monohalogenated hydrocarbon and the dihalogenated hydrocarbon in the step 3) is 1 (0.05-1.2) (0.05-0.3).
7. The method for preparing the polymeric anion exchange membrane according to claim 1, wherein the monohalogenated hydrocarbon in the step 3) is R-X, wherein X = Cl, Br, I, R is benzyl or C1-C6 linear alkyl, etc., and the dihalogenated hydrocarbon is p-dibenzyl bromide or
And the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202011471961.2A CN112500598A (en) | 2020-12-15 | 2020-12-15 | Polymer anion exchange membrane for fuel cell and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011471961.2A CN112500598A (en) | 2020-12-15 | 2020-12-15 | Polymer anion exchange membrane for fuel cell and preparation method thereof |
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| CN202011471961.2A Withdrawn CN112500598A (en) | 2020-12-15 | 2020-12-15 | Polymer anion exchange membrane for fuel cell and preparation method thereof |
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