CN110828871A - Preparation method of proton exchange membrane with ordered multi-stage pore channels - Google Patents
Preparation method of proton exchange membrane with ordered multi-stage pore channels Download PDFInfo
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- CN110828871A CN110828871A CN201910987026.2A CN201910987026A CN110828871A CN 110828871 A CN110828871 A CN 110828871A CN 201910987026 A CN201910987026 A CN 201910987026A CN 110828871 A CN110828871 A CN 110828871A
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- exchange membrane
- proton exchange
- organosilane
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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
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1037—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having silicon, e.g. sulfonated crosslinked polydimethylsiloxanes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- 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
The invention relates to the field of fuel cells, and discloses a preparation method of a proton exchange membrane with an ordered multi-stage pore passage structure, which comprises the following steps: uniformly mixing sulfydryl functionalized single-head silane, disulfide bond functionalized double-head organosilane, a template agent and a photoacid generator, and coating the mixture on a substrate to form a liquid film; placing the liquid film under a high-pressure mercury lamp for irradiation polymerization to obtain a mesoporous organic silicon film with mercapto groups in the pore canal and disulfide bonds on the wall of the pore canal; soaking the mesoporous organic silicon film in absolute ethyl alcohol overnight to obtain a mesoporous organic silicon film without a template agent; and finally, respectively treating the mesoporous organic silicon film in hydrogen peroxide and dilute sulfuric acid to obtain the sulfonic acid functionalized proton exchange membrane with the hierarchical pore channel. The method uses the synchronous self-assembly of the single-head organosilane and the double-head organosilane to form the proton exchange membrane with ordered multi-stage pore canals, effectively increases a proton transfer channel, improves the proton conductivity, and has potential application value in a proton exchange membrane fuel cell.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a preparation method of a proton exchange membrane with an ordered hierarchical pore channel.
Background
Proton exchange membrane fuel cells are a type of fuel cell system that uses a proton exchange membrane as a solid electrolyte. Among them, the proton exchange membrane is a core component of the fuel cell, which directly affects the performance and life of the cell. At present, the most main proton exchange membranes comprise perfluorosulfonic acid membranes, polyarylether membranes, polybenzimidazole membranes and the like, the heat resistance and the aging resistance of the organic membranes are poor, and the preparation of the organic-inorganic composite proton exchange membrane is an important means for solving the problems. The organosilane hybrid material has the advantages of strong structural design, various preparation processes, excellent comprehensive performance of the material and the like, and is an important material of a proton exchange membrane substrate. In addition, the ordered pore channel structure in the proton exchange membrane can effectively increase the conduction rate of protons.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides a preparation method of a proton exchange membrane with an ordered multi-stage pore passage structure.
The technical scheme is as follows: the invention provides a preparation method of a proton exchange membrane with an ordered multi-stage pore passage structure, which comprises the following steps: s1: uniformly mixing sulfydryl functionalized single-head organosilane, disulfide bond functionalized double-head organosilane, a template agent and a photoacid generator, and coating the mixture on a substrate to form a liquid film; s2, placing the liquid film under a high-pressure mercury lamp for irradiation polymerization for 30-60 minutes to obtain a mesoporous organic silicon film with mercapto groups inside the pore canal and disulfide bonds on the wall of the pore canal; s3: soaking the mesoporous organic silicon film in absolute ethyl alcohol overnight to obtain a template-free mesoporous organic silicon film; s4: and (3) sequentially treating the mesoporous organic silicon film in hydrogen peroxide and dilute sulfuric acid for 2 hours to obtain the sulfonic acid functionalized proton exchange membrane with the ordered multi-stage pore channel. (ii) a
Preferably, the mass ratio of the sulfydryl functionalized single-head organosilane to the disulfide-bond functionalized double-head organosilane to the template to the photoacid generator is 2: 1: 0.2-0.5: 0.02-0.05.
Preferably, the mercapto-functionalized single-headed organosilane is any one of: 3-mercaptopropyltrimethoxysilane, 8-mercaptooctane-trimethoxysilane and 11-mercaptoundecyltrimethoxysilane. More preferably 8-mercaptooctane trimethoxysilane.
Preferably, the disulfide-bond functionalized double-headed organosilane is bis- [3- (triethoxysilyl) propyl ] -disulfide.
Preferably, the photoacid generator is any one of: 4-isobutylphenyl-4' -methylphenyliodohexafluorophosphate, diphenyl- (4-phenylsulfide) phenylsulfonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate. More preferably 4-isobutylphenyl-4' -methylphenyliodohexafluorophosphate.
Preferably, the template agent is any one of the following: octadecyl polyoxyethylene ether, polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer, and hexadecyl trimethyl ammonium bromide. More preferred are polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymers.
Preferably, the mass fraction of the hydrogen peroxide is 20-30%; the concentration of the dilute sulfuric acid is 0.1-0.5 mol/L; the power of the high-pressure mercury lamp was 100 w.
Has the advantages that: the invention utilizes a high-pressure mercury lamp to induce the decomposition of a light acid generator to generate an acid catalyst, and in situ catalyzes the hydrolysis of organosilane to generate a hydrophilic silanol structure, wherein at the moment, the organosilane at a single end forms a silanol structure with one hydrophilic end and a mercaptoalkyl structure with the other hydrophobic end; meanwhile, the double-headed organosilane forms a silanol structure with hydrophilic two ends and a disulfide structure with hydrophobic middle. Meanwhile, the template agent is self-assembled into a hexahedral pore structure with the interior of the hexahedral pore structure being a hydrophobic structure and the exterior of the hexahedral pore structure being a hydrophilic structure. The hydrolyzed hydrophilic end of the single-end organosilane is condensed to a cross-linked Si-O-Si pore wall structure on the outside, and the hydrophobic end extends into the hexahedral pore channel; meanwhile, the hydrophilic end of the hydrolyzed double-headed organosilane is condensed to form a cross-linked Si-O-Si pore wall structure on the outside, the hydrophobic end is forcibly limited on the pore wall due to the size domain limiting effect, and an organic silicon film with an ordered structure, wherein a mercapto group is arranged in the pore wall, and a disulfide bond group is arranged on the pore wall. After the template agent is removed and the disulfide bond and the sulfhydryl group are oxidized into the sulfonate group, a multi-level pore proton transmission channel with a pore wall being a micropore (formed by microphase separation after the disulfide bond is broken and oxidized into the sulfonate group) and a pore channel being a mesopore (formed after the template agent is removed) is formed.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1) the invention uses the single-head organosilane and the double-head organosilane to be synchronously self-assembled under the induction of the template agent to form the proton exchange membrane with ordered multi-stage pore canals, can effectively increase a proton transfer channel and improve the proton conductivity, and has potential application value in a proton exchange membrane fuel cell.
2) The method for preparing the proton exchange membrane by the photoinduction self-assembly method has the advantages of no solvent participation in the preparation process, high reaction rate and green and high efficiency.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Embodiment 1:
mixing 0.5 g of 8-mercaptooctane trimethoxy silane, 0.25g of bis- [3- (triethoxy silicon) propyl ] -disulfide, 0.1g of polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer and 0.02 g of photoacid generator α -benzoyl benzyl carbamate, placing the mixture on a stirrer, stirring and mixing uniformly to obtain a coating solution, uniformly coating the obtained coating solution on a polytetrafluoroethylene substrate to form a liquid film, irradiating the liquid film on the substrate by using a high-pressure mercury lamp for 30 minutes to obtain an organic silicon film with an ordered pore structure, removing the organic silicon film with the ordered pore structure from the substrate, sequentially placing the organic silicon film in 30% hydrogen peroxide and 0.2mol/L dilute sulfuric acid, treating for 2 hours, and drying to obtain the proton exchange membrane with the ordered multi-pore structure.
Embodiment 2:
mixing 0.5 g of 3-mercaptooctane trimethoxy silane, 0.25g of bis- [3- (triethoxy silicon) propyl ] -disulfide, 0.1g of octadecyl polyoxyethylene ether and 0.02 g of a photo-acid generator diphenyl- (4-phenyl sulfur) phenyl sulfonium hexafluorophosphate, and then placing the mixture on a stirrer to stir and mix uniformly to obtain a coating solution; uniformly coating the obtained coating solution on a polytetrafluoroethylene substrate to form a liquid film; irradiating the liquid film on the substrate by using a high-pressure mercury lamp for 40 minutes to obtain an organic silicon film with an ordered pore structure; and (3) taking off the organic silicon film from the substrate to obtain the organic silicon film with the ordered pore structure, sequentially placing the organic silicon film in 25% hydrogen peroxide and 0.3mol/L dilute sulfuric acid for treatment for 2 hours, and drying to obtain the proton exchange membrane with the ordered multi-stage pore structure.
Embodiment 3:
mixing 0.5 g of 11-mercapto undecyl trimethoxy silane, 0.25g of bis- [3- (triethoxy silicon) propyl ] -disulfide, 0.2 g of hexadecyl trimethyl ammonium bromide and 0.02 g of a photo-acid generator diphenyl- (4-phenyl sulfur) phenyl sulfonium hexafluorophosphate, and then placing the mixture on a stirrer to stir and mix uniformly to obtain a coating solution; uniformly coating the obtained coating solution on a polytetrafluoroethylene substrate to form a liquid film; irradiating the liquid film on the substrate by using a high-pressure mercury lamp for 30 minutes to obtain an organic silicon film with an ordered pore structure; and (3) taking off the organic silicon film with the ordered porous structure from the substrate, sequentially placing the organic silicon film in 30% hydrogen peroxide and 0.4 mol/L dilute sulfuric acid for treatment for 2 hours, and drying to obtain the proton exchange membrane with the ordered multi-stage porous structure.
Table 1 results of performance test of proton exchange membranes prepared in embodiments 1 to 3
From table 1, it can be seen that the proton exchange membrane prepared by the method has better mechanical strength and dimensional stability, higher ion exchange capacity and proton conductivity. The proton exchange membrane prepared in the embodiment 1 has outstanding comprehensive performance and potential application value.
The above embodiments are merely illustrative of the technical concepts and features of the present invention, and the purpose of the embodiments is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. A preparation method of a proton exchange membrane with ordered multi-stage pore channels is characterized by comprising the following steps:
s1: uniformly mixing sulfydryl functionalized single-head organosilane, disulfide bond functionalized double-head organosilane, a template agent and a photoacid generator, and coating the mixture on a substrate to form a liquid film;
s2: irradiating and polymerizing the liquid film for 30-60 minutes under a high-pressure mercury lamp to obtain a mesoporous organic silicon film with mercapto groups in the pore canal and disulfide bonds on the wall of the pore canal;
s3: soaking the mesoporous organic silicon film in absolute ethyl alcohol overnight to obtain a mesoporous organic silicon film without a template agent;
s4: and (3) sequentially treating the mesoporous organic silicon film in hydrogen peroxide and dilute sulfuric acid for 2 hours to obtain the sulfonic acid functionalized proton exchange membrane with the ordered multi-stage pore channel.
2. The preparation method of the proton exchange membrane with the ordered multi-stage pore channels as claimed in claim 1, wherein the mass ratio of the mercapto-functionalized single-headed organosilane, the disulfide-bond functionalized double-headed organosilane, the templating agent and the photoacid generator is 2: 1: 0.2-0.5: 0.02-0.05.
3. The method for preparing a proton exchange membrane having ordered multi-stage pore channels as claimed in claim 1, wherein the mercapto-functionalized single-headed organosilane is any one of the following:
3-mercaptopropyltrimethoxysilane, 8-mercaptooctane-trimethoxysilane and 11-mercaptoundecyltrimethoxysilane.
4. The method of claim 1, wherein the disulfide-functionalized double-headed organosilane is bis- [3- (triethoxysilyl) propyl ] -disulfide.
5. The method for preparing a proton exchange membrane having an ordered multi-stage pore channel as claimed in claim 1, wherein the photoacid generator is any one of:
4-isobutylphenyl-4' -methylphenyliodohexafluorophosphate, diphenyl- (4-phenylsulfide) phenylsulfonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate.
6. The method for preparing a proton exchange membrane with ordered multi-stage pore channels according to claim 1, wherein the template is any one of the following:
octadecyl polyoxyethylene ether, polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer, and hexadecyl trimethyl ammonium bromide.
7. The preparation method of the proton exchange membrane with the ordered multi-stage pore channels according to any one of claims 1 to 6, wherein the mass fraction of the hydrogen peroxide is 20-30%.
8. The method for preparing a proton exchange membrane having an ordered multi-stage pore channel as claimed in any one of claims 1 to 6, wherein the concentration of the dilute sulfuric acid is 0.1-0.5 mol/L.
9. The process for the preparation of a proton exchange membrane with ordered multi-stage pore channels according to any one of claims 1 to 6, wherein the power of the mercury high-pressure lamp is 100 w.
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| CN201910987026.2A CN110828871A (en) | 2019-10-17 | 2019-10-17 | Preparation method of proton exchange membrane with ordered multi-stage pore channels |
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| CN201910987026.2A CN110828871A (en) | 2019-10-17 | 2019-10-17 | Preparation method of proton exchange membrane with ordered multi-stage pore channels |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060035129A1 (en) * | 2003-02-06 | 2006-02-16 | Shigeki Nomura | Proton conducting membrane, method for producing the same and fuel cell using the same |
| CN102658200A (en) * | 2012-04-25 | 2012-09-12 | 上海师范大学 | Sulfonic acid-functionalized ordered mesoporous polymer-silicon oxide composite material and synthetic method thereof |
| US20140356623A1 (en) * | 2013-05-29 | 2014-12-04 | Korea University Research And Business Foundation | Thioether-bridged organic/inorganic composite and method for preparing hollow or porous carbon structures and silica structures using the same |
| CN109126727A (en) * | 2018-10-12 | 2019-01-04 | 淮阴工学院 | The preparation method of the mesoporous molecular sieve membrane of amino functional |
| CN109232934A (en) * | 2018-10-12 | 2019-01-18 | 淮阴工学院 | The preparation method of the mesoporous molecular sieve membrane of sulfonic acid funtionalized |
-
2019
- 2019-10-17 CN CN201910987026.2A patent/CN110828871A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060035129A1 (en) * | 2003-02-06 | 2006-02-16 | Shigeki Nomura | Proton conducting membrane, method for producing the same and fuel cell using the same |
| CN102658200A (en) * | 2012-04-25 | 2012-09-12 | 上海师范大学 | Sulfonic acid-functionalized ordered mesoporous polymer-silicon oxide composite material and synthetic method thereof |
| US20140356623A1 (en) * | 2013-05-29 | 2014-12-04 | Korea University Research And Business Foundation | Thioether-bridged organic/inorganic composite and method for preparing hollow or porous carbon structures and silica structures using the same |
| CN109126727A (en) * | 2018-10-12 | 2019-01-04 | 淮阴工学院 | The preparation method of the mesoporous molecular sieve membrane of amino functional |
| CN109232934A (en) * | 2018-10-12 | 2019-01-18 | 淮阴工学院 | The preparation method of the mesoporous molecular sieve membrane of sulfonic acid funtionalized |
Non-Patent Citations (2)
| Title |
|---|
| CONGMING LI等: "Mesoporous organosilicas containing disulfide moiety: Synthesis and generation of sulfonic acid functionality through chemical transformation in the pore wall", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| LINGLI NI等: "Light-induced crystallization-driven formation of hierarchically ordered superhydrophobic sol-gel coatings", 《PROGRESS IN ORGANIC COATINGS》 * |
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Application publication date: 20200221 |