CN110760038B - Imidazole side chain type anion exchange membrane for fuel cell and preparation method thereof - Google Patents
Imidazole side chain type anion exchange membrane for fuel cell and preparation method thereof Download PDFInfo
- Publication number
- CN110760038B CN110760038B CN201911127496.8A CN201911127496A CN110760038B CN 110760038 B CN110760038 B CN 110760038B CN 201911127496 A CN201911127496 A CN 201911127496A CN 110760038 B CN110760038 B CN 110760038B
- Authority
- CN
- China
- Prior art keywords
- exchange membrane
- anion exchange
- monomer
- imidazole
- chain type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- 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
-
- 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
-
- 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
-
- 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
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- 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 an imidazole side chain type anion exchange membrane for a fuel cell and a preparation method thereof, belonging to the fields of polymer chemistry and anion exchange membrane fuel cells. The anion exchange membrane is different in monomer molar ratio: the molar ratio of the methyl hydroquinone monomer to the allyl bisphenol S monomer is as follows: a: b (a and b are both integers of 1-9, and a + b = 10); the invention also provides a preparation method of the imidazole side chain type anion exchange membrane, which comprises the step of polymerizing by utilizing nucleophilic polycondensation reaction according to different monomer molar ratios to form polyaryletherketone sulfones containing the methyl hydroquinone monomer and the allyl bisphenol S monomer in different proportions to prepare the imidazole side chain type anion exchange membrane. The imidazole side chain type anion exchange membrane has the ion conductivity of 0.157S/cm at the temperature of 80 ℃.
Description
Technical Field
The invention belongs to the field of polymer chemistry and anion exchange membrane fuel cells, and particularly relates to an imidazole side chain type anion exchange membrane for a fuel cell and a preparation method thereof.
Background
In recent years, in order to pursue rapid economic development, fossil energy has been excessively used, and problems such as energy depletion and environmental pollution have been caused. At present, most of research focuses on the field of proton exchange membrane fuel cells, but because the catalysts of the proton exchange membrane fuel cells need to adopt expensive metals, the popularization and the development of the proton exchange membrane fuel cells are greatly limited. In contrast, the anion exchange membrane fuel cell has the advantages of fast fuel oxidation rate, low liquid alcohol fuel permeability, capability of using non-noble metal catalysts and the like, and has a wide application prospect, so that research on the anion exchange membrane fuel cell is widely concerned by researchers.
The performance of an anion exchange membrane as a core component of an anion exchange membrane fuel cell directly determines the performance of the anion exchange membrane fuel cell. The types of anion exchange membrane materials researched at present are quite various, and polyether sulfone, polyether ketone, polyvinyl alcohol, polyphenyl ether and the like can be used as the anion exchange membrane matrix materials. The anion exchange membrane also has a plurality of advantages, the catalyst with low price can be selected to replace the noble metal catalyst, the use cost of the fuel cell is greatly reduced, the application in a large range can not depend on the existing resource reserves, the popularization and the application in a large area are facilitated, and the anion exchange membrane is undoubtedly a great breakthrough for promoting the rapid development of the fuel cell.
Disclosure of Invention
The invention aims to provide an imidazole side chain type anion exchange membrane for a fuel cell and a preparation method thereof.
The invention firstly provides an imidazole side chain type anion exchange membrane for a fuel cell, the anion exchange membrane is polymerized according to different molar ratios of monomers, the larger the proportion of the double bond-containing monomer is, the higher the double bond content in the polymer is, and the number of imidazole is increased:
wherein the molar ratio of the methyl hydroquinone monomer to the allyl bisphenol S monomer is as follows: a: b (a and b are both integers of 1-9, and a + b = 10);
the structural formula of the imidazole functionalized polyaryletherketone sulfone is respectively shown as formula I:
formula I
Wherein m and n are the number of repeating units, and m and n are integers more than or equal to 1.
The invention also provides a preparation method of the imidazole side chain type anion exchange membrane for the fuel cell, which comprises the following steps:
the method comprises the following steps: dissolving imidazole functionalized polyaryletherketone sulfone in a solvent to obtain a clear orange solution, adding 1-allyl-3-methylimidazole chloride, stirring for 8 hours, adding benzoyl peroxide, stirring for 3 hours at 80 ℃, and discharging in distilled water to obtain a gray solid;
step two: dissolving the gray solid obtained in the first step in tetrachloroethane, adding benzoyl peroxide and N-bromosuccinamide into an 80-DEG oil bath, stirring for 5 hours, and discharging in alcohol to obtain light yellow floccule;
step three: dissolving the light yellow floccule obtained in the second step into a solvent to obtain a clear orange solution;
step four: adding benzoyl peroxide and 1-vinyl imidazole into the solution obtained in the third step, stirring for 12-24 hours to obtain a deep yellow film forming solution, polymerizing an anion exchange membrane according to different molar ratios of a methyl hydroquinone monomer to an allyl bisphenol S monomer, wherein the molar ratio of the methyl hydroquinone monomer to the allyl bisphenol S monomer is as follows: a: b (a and b are each an integer of 1 to 9, and a + b = 10)
Step five: and D, performing casting film forming on the film forming solution obtained in the step four by adopting a tape casting method to obtain the imidazole side chain type anion exchange membrane for the fuel cell.
Preferably, the preparation method of the imidazole functionalized polyaryletherketone sulfone comprises the following steps (taking the molar ratio of methyl hydroquinone monomer to allyl bisphenol S monomer as an example of 5: 5): under the protection of nitrogen, 0.02mol of 4, 4' -difluorobenzophenone, 0.01mol of allyl bisphenol S and 0.01mol of methylhydroquinone are added into a three-necked bottle, uniformly mixed, added with a salt forming agent, a water carrying agent and a solvent, refluxed with water at 125-145 ℃ for 3-5 hours, then discharged with the water carrying agent, heated to 185-190 ℃, and continuously reacted for 2-3 hours to obtain the imidazole functionalized polyaryletherketone sulfone.
Preferably, the imidazole is 1-allyl-3-methylimidazole and 1-vinylimidazole.
Preferably, the bisphenol monomer is allyl bisphenol S.
Preferably, the solvent is one of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), or Dimethylsulfoxide (DMSO).
Preferably, the water-carrying agent is toluene.
The invention has the advantages of
The invention firstly provides an imidazole side chain type anion exchange membrane for a fuel cell, the anion exchange membrane is polymerized according to different molar ratios of monomers, the larger the proportion of the double bond-containing monomer is, the higher the double bond content in the polymer is, and the number of imidazole is increased: in the anion exchange membrane, the imidazole nitrogen heterocycle on the branched chain can be used as a donor of ions and a receptor of the ions, so that the anion exchange membrane can receive the ions and give the ions, the ions are transferred between the imidazoles in a jumping manner to form an ion transmission channel, and then the problem of reduction of ionic conductivity caused by dehydration of the membrane at high temperature is solved, meanwhile, the imidazole branched chain between allyl bisphenol S in the anion exchange membrane forms double bonds, so that the crosslinking effect is generated, the compactness of the membrane is increased, the membrane material is favorably ensured to have certain ionic conductivity at high temperature, the compact membrane structure effectively inhibits excessive swelling of the membrane, and the dimensional stability of the membrane is improved, and experimental results show that: the imidazole side chain type anion exchange membrane has the ionic conductivity of 0.123-0.157S/cm at 80 ℃, and the thickness of the imidazole side chain type anion exchange membrane is 20-25 mu m.
The invention also provides a preparation method of the imidazole side chain type anion exchange membrane for the fuel cell, which is used for preparing imidazole functionalized polyaryletherketone sulfone by utilizing nucleophilic polycondensation. The imidazole side chain type anion exchange membrane has the advantages of simple preparation process, short production period, low cost and wide commercial prospect, and can be applied to the field of fuel cells.
Drawings
FIG. 1 is a nuclear magnetic spectrum of polymerization, grafting and bromination in the preparation of imidazole-functionalized polyaryletherketone sulfone in example 1 of the present invention.
FIG. 2 is an infrared spectrum of an imidazole side-chain anion exchange membrane prepared in example 1 of the present invention.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
The invention firstly provides an imidazole side chain type anion exchange membrane for a fuel cell, the anion exchange membrane is polymerized according to different molar ratios of monomers, the larger the proportion of the double bond-containing monomer is, the higher the double bond content in the polymer is, and the number of imidazole is increased:
wherein the molar ratio of the methyl hydroquinone monomer to the allyl bisphenol S monomer is as follows: a: b (a and b are both integers of 1-9, and a + b = 10);
the structural formula of the imidazole functionalized polyaryletherketone sulfone is shown as the formula I:
formula I
In the formula I, m and n are the number of repeating units, and m and n are integers more than or equal to 1.
The invention also provides a preparation method of the imidazole side chain type anion exchange membrane for the fuel cell, which comprises the following steps:
the method comprises the following steps: dissolving imidazole functionalized polyaryletherketone sulfone in a solvent to obtain a clear orange solution, adding 1-allyl-3-methylimidazole chloride, stirring for 8 hours, adding benzoyl peroxide, stirring for 3 hours at 80 ℃, and discharging in distilled water to obtain a gray solid;
step two: dissolving the gray solid obtained in the first step in tetrachloroethane, adding benzoyl peroxide and N-bromosuccinamide into an 80-DEG oil bath, stirring for 5 hours, and discharging in alcohol to obtain light yellow floccule;
step three: dissolving the light yellow floccule obtained in the second step into a solvent to obtain a clear orange solution;
step four: adding benzoyl peroxide and 1-vinyl imidazole into the solution obtained in the third step, stirring for 12-24 hours to obtain a deep yellow film forming solution, polymerizing an anion exchange membrane according to different molar ratios of a methyl hydroquinone monomer to an allyl bisphenol S monomer, wherein the molar ratio of the methyl hydroquinone monomer to the allyl bisphenol S monomer is as follows: a: b (a and b are both integers of 1-9, and a + b = 10);
step five: and D, performing casting film forming on the film forming solution obtained in the step four by adopting a tape casting method to obtain the imidazole side chain type anion exchange membrane for the fuel cell.
The preparation method of the imidazole functionalized polyaryletherketone sulfone comprises the following steps (taking the molar ratio of a methyl hydroquinone monomer to an allyl bisphenol S monomer as an example of 5: 5): under the protection of nitrogen, 0.02mol of 4, 4' -difluorobenzophenone, 0.01mol of allyl bisphenol S and 0.01mol of methylhydroquinone are added into a three-necked bottle, after uniform mixing, a salt forming agent, a water carrying agent and a solvent are added, the mixture is refluxed with water at 125-145 ℃ for 3-5 hours, then the water carrying agent is discharged, the temperature is raised to 185-190 ℃, and the reaction is continued for 2-3 hours, so that the polyaryletherketone sulfone with different molar ratios of the methylhydroquinone monomer and the allyl bisphenol S monomer is obtained. The bisphenol monomer is preferably allyl bisphenol S; the salt forming agent is preferably anhydrous potassium carbonate, the water-carrying agent is preferably toluene, and the solvent is preferably a high boiling point solvent with a boiling point of 150 ℃ or higher, including but not limited to N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), or Dimethylsulfoxide (DMSO).
The present invention will be described in further detail with reference to examples.
Example 1
(1) Dissolving imidazole functionalized polyaryletherketone sulfone in an N-methylpyrrolidone (NMP) solvent (the molar ratio of a methyl hydroquinone monomer to an allyl bisphenol S monomer is 5: 5) to obtain a clear orange solution, adding 1-allyl-3-methylimidazole chloride, stirring for 8 hours, adding benzoyl peroxide, stirring for 3 hours at 80 ℃, discharging in distilled water to obtain a gray solid;
(2) dissolving the gray solid obtained in the step (1) in tetrachloroethane, adding benzoyl peroxide and N-bromosuccinamide into an 80-DEG oil bath, stirring for 5 hours, and discharging in alcohol to obtain yellow floccule;
(3) dissolving the yellow floccule obtained in the step (2) in a solvent to obtain a clear orange solution;
(4) adding benzoyl peroxide and 1-vinyl imidazole into the solution obtained in the step (3), stirring for 12-24 hours to obtain a deep yellow film forming solution, polymerizing an anion exchange membrane according to different molar ratios of a methyl hydroquinone monomer to an allyl bisphenol S monomer, wherein the molar ratio of the methyl hydroquinone monomer to the allyl bisphenol S monomer is as follows: a: b (a and b are both integers of 1-9, and a + b = 10);
(5) and (4) performing film extension on the dark yellow film-forming solution obtained in the step (4) to form a film, then placing the film into a thermostat, drying the film for 48 hours at the temperature of 80 ℃, naturally cooling the film to 25 ℃, and removing the film in distilled water to obtain the imidazole side-chain type anion exchange membrane for the fuel cell.
Soaking the imidazole side chain type anion exchange membrane for the fuel cell in a 1M NaOH solution for 24 hours, then soaking the imidazole side chain type anion exchange membrane in ionized water for 24 hours, changing water for washing for many times during the soaking period to wash away residual NaOH on the surface of the membrane, and soaking the pretreated imidazole side chain type anion exchange membrane in deionized water for later use. The imidazole side chain type anion-exchange membrane has the ion conductivity of 0.123S/cm and the membrane thickness of 22 mu m when tested at 80 ℃, the ion conductivity of 0.033S/cm when tested at 30 ℃, and the ion conductivity still maintains 0.078S/cm at 60 ℃ after the imidazole side chain type anion-exchange membrane is soaked in alkali for 400 hours, so that the good alkali-resistant stability is embodied. The infrared spectrum of the imidazole side chain type anion-exchange membrane obtained in example 1 is shown in fig. 2, and as can be seen from fig. 2, the imidazole side chain type anion-exchange membrane was successfully synthesized in the example.
Example 2
(1) Dissolving imidazole functionalized polyaryletherketone sulfone in an N-methylpyrrolidone (NMP) solvent (the molar ratio of a trimethylhydroquinone monomer to an allyl bisphenol S monomer is 3: 7 at the moment), then obtaining a clear orange solution, adding 1-allyl-3-methylimidazole chloride, stirring for 8 hours, adding benzoyl peroxide, stirring for 3 hours at the temperature of 80 ℃, discharging the mixture in distilled water, and obtaining a gray solid;
(2) dissolving the gray solid obtained in the step (1) in tetrachloroethane, adding benzoyl peroxide and N-bromosuccinamide into an 80-DEG oil bath, stirring for 5 hours, and discharging in alcohol to obtain yellow floccule;
(3) dissolving the yellow floccule obtained in the step (2) in a solvent to obtain a clear orange solution;
(4) adding benzoyl peroxide and 1-vinyl imidazole into the solution obtained in the step (3), stirring for 12-24 hours to obtain a deep yellow film forming solution, polymerizing an anion exchange membrane according to different molar ratios of a methyl hydroquinone monomer to an allyl bisphenol S monomer, wherein the molar ratio of the methyl hydroquinone monomer to the allyl bisphenol S monomer is as follows: a: b (a and b are both integers of 1-9, and a + b = 10);
(5) and (4) performing film extension on the dark yellow film-forming solution obtained in the step (4) to form a film, then placing the film into a thermostat, drying the film for 48 hours at the temperature of 80 ℃, naturally cooling the film to 25 ℃, and removing the film in distilled water to obtain the imidazole side-chain type anion exchange membrane for the fuel cell.
Soaking the imidazole side chain type anion exchange membrane for the fuel cell in a 1M NaOH solution for 24 hours, then soaking the imidazole side chain type anion exchange membrane in ionized water for 24 hours, changing water for washing for many times during the soaking period to wash away residual NaOH on the surface of the membrane, and soaking the pretreated imidazole side chain type anion exchange membrane in deionized water for later use. The imidazole side chain type anion exchange membrane has the ion conductivity of 0.147S/cm and the membrane thickness of 18 mu m when tested at 80 ℃, the ion conductivity of 0.042S/cm when tested at 30 ℃, and the ion conductivity of 0.088S/cm can be maintained at 60 ℃ after the imidazole side chain type anion exchange membrane is soaked in alkali for 400 hours, so that the good alkali-resistant stability is embodied.
Example 3
(1) Dissolving imidazole functionalized polyaryletherketone sulfone in an N-methylpyrrolidone (NMP) solvent (the molar ratio of a methyl hydroquinone monomer to an allyl bisphenol S monomer is 2: 8), then obtaining a clear orange solution, adding 1-allyl-3-methylimidazole chloride, stirring for 8 hours, adding benzoyl peroxide, stirring for 3 hours at 80 ℃, discharging in distilled water, and obtaining a gray solid;
(2) dissolving the gray solid obtained in the step (1) in tetrachloroethane, adding benzoyl peroxide and N-bromosuccinamide into an 80-DEG oil bath, stirring for 5 hours, and discharging in alcohol to obtain yellow floccule;
(3) dissolving the yellow floccule obtained in the step (2) in a solvent to obtain a clear orange solution;
(4) adding benzoyl peroxide and 1-vinyl imidazole into the solution obtained in the step (3), stirring for 12-24 hours to obtain a reddish brown film forming solution, polymerizing an anion exchange membrane according to different molar ratios of a methyl hydroquinone monomer to an allyl bisphenol S monomer, wherein the molar ratio of the methyl hydroquinone monomer to the allyl bisphenol S monomer is as follows: a: b (a and b are both integers of 1-9, and a + b = 10);
(5) and (4) performing film extension on the dark yellow film-forming solution obtained in the step (4) to form a film, then placing the film into a thermostat, drying the film for 48 hours at the temperature of 80 ℃, naturally cooling the film to 25 ℃, and removing the film in distilled water to obtain the imidazole side-chain type anion exchange membrane for the fuel cell.
Soaking the imidazole side chain type anion exchange membrane for the fuel cell in a 1M NaOH solution for 24 hours, then soaking the imidazole side chain type anion exchange membrane in ionized water for 24 hours, changing water for washing for many times during the soaking period to wash away residual NaOH on the surface of the membrane, and soaking the pretreated imidazole side chain type anion exchange membrane in deionized water for later use. The imidazole side chain type anion-exchange membrane has the ionic conductivity of 0.157S/cm and the membrane thickness of 25 μm when tested at 80 ℃, the ionic conductivity of 0.043S/cm when tested at 30 ℃, and the ionic conductivity of 0.092S/cm can be maintained at 60 ℃ after the imidazole side chain type anion-exchange membrane is soaked in alkali for 400 hours, so that good alkali-resistant stability is embodied.
The above description of the embodiments is only for the purpose of helping understanding the method of the present invention and the core idea thereof, and it should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (5)
1. The imidazole side chain type anion exchange membrane for the fuel cell is characterized in that the anion exchange membrane is polymerized according to different molar ratios of monomers, the larger the proportion of the double bond-containing monomer is, the content of double bonds in the polymer is increased, and the number of imidazole is also increased:
wherein the molar ratio of the methyl hydroquinone monomer to the allyl bisphenol S monomer is as follows: x: y, x and y are integers from 1 to 9, and x + y is 10;
the structural formula of the anion exchange membrane is shown as formula I:
formula I
In the formula I, m and n are the number of repeating units, and m and n are integers more than or equal to 1.
2. The method for preparing an imidazole side-chain type anion exchange membrane for a fuel cell according to claim 1, comprising the steps of:
the method comprises the following steps: dissolving imidazole functionalized polyaryletherketone sulfone in a solvent to obtain a clear orange solution, adding 1-allyl-3-methylimidazole chloride, stirring for 8 hours, adding benzoyl peroxide, stirring for 3 hours at 80 ℃, and discharging in distilled water to obtain a gray solid;
step two: dissolving the gray solid obtained in the first step in tetrachloroethane, adding benzoyl peroxide and N-bromosuccinamide into an 80-DEG oil bath, stirring for 5 hours, and discharging in alcohol to obtain light yellow floccule;
step three: dissolving the light yellow floccule obtained in the second step into a solvent to obtain a clear orange solution;
step four: adding benzoyl peroxide and 1-vinyl imidazole into the solution obtained in the third step, stirring for 12-24 hours to obtain a deep yellow film forming solution, polymerizing an anion exchange membrane according to different molar ratios of methyl hydroquinone monomers to allyl bisphenol S monomers, wherein the molar ratio of the methyl hydroquinone monomers to the allyl bisphenol S monomers is as follows: x: y, x and y are integers from 1 to 9, and x + y is 10;
step five: and casting the film-forming solution obtained in the fourth step into a film by adopting a tape casting method, thus obtaining the imidazole side chain type anion exchange membrane for the fuel cell.
3. The method for preparing the imidazole side-chain anion-exchange membrane for the fuel cell according to claim 2, wherein the method for preparing the imidazole functionalized polyaryletherketone sulfone comprises the following steps: under the protection of nitrogen, 0.02mol of 4, 4' -difluorobenzophenone, 0.01mol of allyl bisphenol S and 0.01mol of methylhydroquinone are added into a three-necked bottle, after uniform mixing, a salt forming agent, a water carrying agent and a solvent are added, the mixture is refluxed with water at 125-145 ℃ for 3-5 hours, then the water carrying agent is discharged, the temperature is raised to 185-190 ℃, and the reaction is continued for 2-3 hours, so that the polyaryletherketone sulfone with different molar ratios of the methylhydroquinone monomer and the allyl bisphenol S monomer is obtained.
4. The method of claim 3, wherein the solvent is one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, or dimethylsulfoxide.
5. The method of claim 3, wherein the water-carrying agent is toluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911127496.8A CN110760038B (en) | 2019-11-18 | 2019-11-18 | Imidazole side chain type anion exchange membrane for fuel cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911127496.8A CN110760038B (en) | 2019-11-18 | 2019-11-18 | Imidazole side chain type anion exchange membrane for fuel cell and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110760038A CN110760038A (en) | 2020-02-07 |
| CN110760038B true CN110760038B (en) | 2022-05-31 |
Family
ID=69338193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911127496.8A Active CN110760038B (en) | 2019-11-18 | 2019-11-18 | Imidazole side chain type anion exchange membrane for fuel cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110760038B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111276724B (en) * | 2020-02-15 | 2022-11-22 | 西北工业大学 | Half-interpenetrating-network anion exchange membrane based on polyphenyl ether/polyvinyl alcohol and preparation method thereof |
| CN111607117B (en) * | 2020-06-18 | 2022-11-29 | 长春工业大学 | Multi-side-chain type anion exchange membrane for fuel cell and preparation method thereof |
| CN112300391A (en) * | 2020-09-21 | 2021-02-02 | 长春工业大学 | Different side chain type anion exchange membranes for fuel cell and preparation method thereof |
| CN113717418B (en) * | 2021-08-30 | 2022-07-08 | 浙江工业大学 | Preparation method of side-chain type pyridinium functionalized polyether sulphone anion exchange membrane |
| CN115894922A (en) * | 2022-11-29 | 2023-04-04 | 上海毅镤新能源科技有限公司 | Imidazole functionalized polyether sulphone block copolymer, anion exchange membrane and preparation method thereof |
| CN117567729A (en) * | 2024-01-19 | 2024-02-20 | 固碳新能源科技(苏州)有限公司 | Ion-conducting polymer and preparation method thereof, ion-conducting cross-linked substance and preparation method thereof, anion exchange membrane and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784946A (en) * | 2016-12-01 | 2017-05-31 | 长春工业大学 | Fuel cell polyfluorene ether nitrile cross-linking type anion exchange membrane material of cation group functionalization and preparation method thereof |
| CN108110290A (en) * | 2017-12-19 | 2018-06-01 | 长春工业大学 | Fuel cell crosslinking imidazole type polyether-ether-ketone anion-exchange membrane and preparation method thereof |
-
2019
- 2019-11-18 CN CN201911127496.8A patent/CN110760038B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784946A (en) * | 2016-12-01 | 2017-05-31 | 长春工业大学 | Fuel cell polyfluorene ether nitrile cross-linking type anion exchange membrane material of cation group functionalization and preparation method thereof |
| CN108110290A (en) * | 2017-12-19 | 2018-06-01 | 长春工业大学 | Fuel cell crosslinking imidazole type polyether-ether-ketone anion-exchange membrane and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《Octa-imidazolium POSS/quaternized polysulfone composite anion exchange membrane for alkaline fuel cell》;Vijayakumar Elumalai, Sangeetha Dharmalingam;《polymer composites》;20180506;第40卷(第4期);第1536-1544页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110760038A (en) | 2020-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110760038B (en) | Imidazole side chain type anion exchange membrane for fuel cell and preparation method thereof | |
| CN111607117B (en) | Multi-side-chain type anion exchange membrane for fuel cell and preparation method thereof | |
| CN110224166B (en) | Phosphoric acid-doped cross-linked polybenzimidazole high-temperature proton exchange membrane and preparation method thereof | |
| CN110862516B (en) | Cardo structure-containing isatin aromatic hydrocarbon copolymer, and preparation method and application thereof | |
| CN101367903B (en) | Enhancement type composite proton exchanging film based on semi-interpenetrating network and preparation method thereof | |
| CN111718504B (en) | ZIF-67-based polyaryletherketone anion exchange membrane and preparation method thereof | |
| CN101844042B (en) | Preparation method of anion-exchange membranes based on ionic liquid | |
| Lin et al. | Thermoplastic interpenetrating polymer networks based on polybenzimidazole and poly (1, 2-dimethy-3-allylimidazolium) for anion exchange membranes | |
| CN105566665A (en) | Preparation method of blended cross-linked anion exchange membrane | |
| CN114276505B (en) | Poly (arylene piperidine) copolymer containing polyethylene glycol flexible hydrophilic side chain, preparation method, anion exchange membrane and application | |
| CN108659243B (en) | Branched polyether-ether-ketone anion exchange membrane and preparation method thereof | |
| CN112778558A (en) | Polyether bond-free anion exchange membrane of polyarylpiperidine for fuel cell and preparation method thereof | |
| Du et al. | Improved conductivity and stability of anion exchange membranes by introducing steric hindrance and crosslinked structure | |
| CN101463129B (en) | Method for synthesizing sulphonation polyetheretherketone for proton exchange membrane by three-step process | |
| CN105566884A (en) | Anion-exchange membrane containing xanthene structure and preparation method and application of anion-exchange membrane | |
| CN112300391A (en) | Different side chain type anion exchange membranes for fuel cell and preparation method thereof | |
| Wang et al. | Adamantane-based block poly (arylene ether sulfone) s as anion exchange membranes | |
| CN101931086B (en) | Interpenetrated reticular proton exchange membrane, forming method thereof and proton exchange membrane fuel cell | |
| CN112290068A (en) | Two quaternary ammonium side chain type anion exchange membranes for fuel cell and preparation method thereof | |
| CN101219349A (en) | Exchange membrane containing modified maleimide low polymer | |
| Hao et al. | Poly (fluorenyl ether ketone) s with densely distributed multi-cationic side chains for anion exchange membranes | |
| CN111403785A (en) | Sulfonated polyaryletherketone sulfone composite membrane and preparation method thereof | |
| CN112349940A (en) | Quaternary ammonium and imidazole cross-linked anion exchange membrane for fuel cell and preparation method thereof | |
| CN113185738B (en) | Amino-containing polyaryletherketone sulfone/cationic metal-organic framework anion exchange membrane and preparation method thereof | |
| CN108039441A (en) | A kind of fluorine-containing diblock polymer anion fuel cell membranes and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221221 Address after: 528200 No. 1, Unit 905, 9th Floor, Chengye Building, No. 13, Nanping West Road, Guicheng Street, Nanhai District, Foshan City, Guangdong Province Patentee after: Huahydrogen (Guangdong) New Energy Technology Co.,Ltd. Address before: 130012 No. 2055 Yan'an Street, Chaoyang District, Changchun City, Jilin Province Patentee before: Changchun University of Technology |