CN110808394B - Preparation method of organic silane base proton exchange membrane - Google Patents
Preparation method of organic silane base proton exchange membrane Download PDFInfo
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- CN110808394B CN110808394B CN201910987167.4A CN201910987167A CN110808394B CN 110808394 B CN110808394 B CN 110808394B CN 201910987167 A CN201910987167 A CN 201910987167A CN 110808394 B CN110808394 B CN 110808394B
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- exchange membrane
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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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 technical field of fuel cells, and discloses a preparation method of an organic silane base proton exchange membrane, which comprises the following steps: uniformly mixing phosphonate functionalized silane and a photobase initiator, and coating the mixture on a substrate to form a liquid film; placing the liquid film under an LED lamp for irradiation polymerization to obtain a film containing phosphonate groups; the membrane is placed in trifluoroacetic acid to be boiled and hydrolyzed to obtain the proton exchange membrane with high phosphonate density. The invention creatively introduces the photoinduced alkali-initiated organosilane polymerization method into the preparation of the proton exchange membrane, has the advantages of simple and convenient operation, short preparation period, no solvent and the like, and is a green and efficient preparation method of the proton exchange membrane; in addition, phosphonic acid groups of the proton transfer medium are bonded in the proton exchange membrane through stable C-P bonds, and the phosphonic acid groups have high density, so that the proton transfer medium is a high-efficiency proton exchange membrane suitable for medium and high temperature, and has obvious application value in fuel cells.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a preparation method of an organic silane-based proton exchange membrane with high-density phosphonic acid groups as proton conduction elements.
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 widely used perfluorosulfonic acid proton exchange membrane has high proton conductivity only in the presence of water molecules, and when the temperature is higher than 80 ℃, the conductivity of the proton exchange membrane is greatly reduced due to the large volatilization of water, so that the proton exchange membrane loses use value. However, higher temperature (>80oC) Can activate the activity of the catalyst in the fuel cell, andthe catalyst CO poisoning is prevented, and the service performance of the battery is effectively improved. Therefore, the development of the proton exchange membrane suitable for medium and high temperature has remarkable application value.
The phosphonic acid group has high proton conductivity and can conduct electricity under non-aqueous conditions, so that the phosphonic acid group attracts great attention. However, phosphonic acid is often directly doped in the proton exchange membrane at the present stage, the doping amount is small, the density of phosphonic acid groups is low, and the loss of phosphonic acid is easily caused in the use process, so that the use safety and the long-term use stability of the fuel cell are influenced. In addition, the polyorganosiloxane is used as an organic-inorganic hybrid material, has excellent performances of high and low temperature resistance, weather aging resistance, flame resistance, no toxicity, no corrosion and the like, and has the characteristic of easy processing of organic high polymer materials, so that the preparation of the proton exchange membrane by using the polyorganosiloxane as a proton exchange membrane substrate and adding phosphonic acid type proton conduction elements is a good choice. Moreover, the traditional sol-gel method for preparing the organosilane hybrid material has the defects of long synthesis period, large amount of organic solvent and the like.
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 an organic silane base proton exchange membrane, the proton exchange membrane prepared by the method contains phosphonic acid groups with higher density, can keep higher proton conductivity at higher temperature, and has green and high-efficiency preparation process.
The technical scheme is as follows: the invention provides a preparation method of an organic silane base proton exchange membrane, which comprises the following steps: s1: uniformly mixing organic silane functionalized by phosphonate ester and a photobase initiator, and coating the mixture on a substrate to form a liquid film; s2: placing the liquid film under an LED lamp for irradiation polymerization for 30-60 minutes to obtain a film containing phosphonate groups; s3: and (3) boiling the film in trifluoroacetic acid for 2-5 h to obtain the organic silane-based proton exchange membrane with high phosphonic acid group density.
Preferably, the phosphonate functionalized organosilane is any one of: diethyl (trimethoxysilane) nonyl) phosphonate, dimethyl (trimethoxysilane) heptyl) phosphonate, dimethyl (triethoxysilane) hexyl) phosphonate. More preferably diethyl (trimethoxysilane) nonyl) phosphonate.
Preferably, the photobase initiator is any one of the following: alpha-benzoylbenzyl carbamate, bis 4-acetamidophenylmethane, 9-fluorenylmethyl carbamate. More preferred is alpha-benzoylbenzylcarbamate.
Preferably, the mass percentage of the photobase in the photobase initiator is 2% -8%. Preferably, the percentage content of the photobase is 4%, the irradiation polymerization time is preferably 40 minutes, and the boiling hydrolysis time in trifluoroacetic acid is preferably 3 hours.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) according to the invention, phosphonate functionalized organosilane is used as a precursor, a phosphonate functionalized organic silicon film is obtained through polymerization, then the phosphonate functionalized organic silicon film is subjected to boiling in trifluoroacetic acid and in-situ hydrolysis to obtain the phosphonate proton exchange membrane, and the phosphonate group is bonded in the proton exchange membrane through a stable C-P bond and has higher density. Because the preparation process of the method does not involve solvent (water), the polyorganosiloxane hybrid proton exchange membrane prepared by the method can not reduce the proton transmission capability caused by the evaporation of water under the medium-high temperature condition; in addition, the phosphonic acid group has high proton conductivity and can conduct electricity under a non-aqueous condition, and the polyorganosiloxane hybrid proton exchange membrane prepared by the method contains the phosphonic acid group with higher density, so that the polyorganosiloxane hybrid proton exchange membrane prepared by the method can still keep good conductivity under medium-high temperature conditions.
(2) The method has the advantages of high curing speed, high silane crosslinking density, short preparation period, no solvent and the like by initiating organosilane polymerization through photobase, and is a green and efficient preparation method of the proton exchange membrane.
(3) The phosphonic acid group of the proton transfer medium is bonded in the proton exchange membrane through a stable C-P bond, and the phosphonic acid group has high density, so that the proton transfer medium is a high-efficiency proton exchange membrane suitable for medium and high temperature, and has obvious application value in a fuel cell.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Embodiment 1:
mixing 0.5 g diethyl (trimethoxy silane) nonyl phosphonate and 0.02 g photobase initiator α -benzoyl benzyl carbamate, placing on a stirrer, stirring and mixing uniformly to obtain a coating solution, uniformly coating the coating solution on a polytetrafluoroethylene substrate to form a liquid film, irradiating the substrate with the liquid film for 30 minutes by using an LED lamp with the wavelength of 365nm, wherein the illumination intensity is 20 mw/cm2Obtaining a film containing phosphonate groups; removing the phosphonate functionalized film from the substrate, boiling and hydrolyzing the film in trifluoroacetic acid with the concentration of 0.5mol/L for 3 hours, and finally drying in vacuum to obtain the organic silane based proton exchange membrane taking the phosphonic acid group as a conducting medium.
Embodiment 2:
mixing 0.5 g of dimethyl (trimethoxy silane) heptyl phosphonate and 0.02 g of a photobase initiator bis-4-acetamidophenylmethane, and then placing the mixture on a stirrer to be stirred and mixed uniformly to obtain a coating solution; uniformly coating the obtained solution on a polytetrafluoroethylene substrate to form a liquid film; irradiating the substrate with the liquid film for 40 minutes using an LED lamp having a wavelength of 395 nm at an intensity of 20 mw/cm2Obtaining a film containing phosphonate groups; removing the phosphonate functionalized film from the substrate, putting the film in trifluoroacetic acid with the concentration of 0.5mol/L for boiling for 4 hours, and finally drying in vacuum to obtain the organic silane based proton exchange membrane taking the phosphonate group as a conducting medium.
Embodiment 3:
mixing 0.5 g of dimethyl (triethoxysilane) hexyl) phosphonate and 0.02 g of photobase initiator 9-fluorenylmethyl carbamate, and then placing the mixture on a stirrer to be stirred and mixed uniformly to obtain a coating solution; uniformly coating the obtained solution on a polytetrafluoroethylene substrate to form a liquid film; irradiating the substrate with the liquid film for 30 minutes by using an LED lamp with a wavelength of 425nm at an intensity of 20 mw/cm2To obtain a phosphonate groupA film of (a); removing the phosphonate functionalized film from the substrate, putting the film in trifluoroacetic acid with the concentration of 0.5mol/L for boiling for 3 hours, and finally drying in vacuum to obtain the organic silane based proton exchange membrane taking the phosphonate group as a conducting medium.
Table 1 results of performance testing of organosilyl proton exchange membranes prepared in examples 1 to 3
As can be seen from Table 1, the proton exchange membrane prepared by the method is a hybrid membrane, has higher thermal decomposition temperature and mechanical strength, and can meet the requirements of the proton exchange membrane; in addition, the prepared proton exchange membrane still keeps higher proton conductivity at higher temperature and lower humidity; the proton exchange membrane prepared in the embodiment 3 has excellent mechanical property, thermal property and proton conductivity, and has a certain application prospect.
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 (7)
1. A preparation method of an organic silane base proton exchange membrane is characterized by comprising the following steps:
s1: uniformly mixing organic silane functionalized by phosphonate ester and a photobase initiator, and coating the mixture on a substrate to form a liquid film;
s2: placing the liquid film under an LED lamp for irradiation polymerization for 30-60 minutes to obtain a film containing phosphonate groups;
s3: and (3) boiling the film in trifluoroacetic acid for 2-5 h to obtain the organic silane-based proton exchange membrane with high phosphonic acid group density.
2. The method of claim 1, wherein the phosphonate functionalized organosilane is any one of the following:
diethyl (trimethoxysilane) nonyl phosphonate, dimethyl (trimethoxysilane) heptyl phosphonate, and dimethyl (triethoxysilane) hexyl phosphonate.
3. The method of claim 1, wherein the photobase initiator is any one of the following:
alpha-benzoylbenzyl carbamate, bis 4-acetamidophenylmethane, 9-fluorenylmethyl carbamate.
4. The preparation method of the organo-silane based proton exchange membrane according to claim 1, wherein the mass percentage of the photobase in the photobase initiator is 2-8%.
5. The method of claim 1, wherein the LED lamp has a wavelength of 365nm, 395 nm or 425nm and an illumination intensity of 20 mw/cm2。
6. The method of claim 1, wherein the concentration of trifluoroacetic acid is 0.2-1 mol/L.
7. The process for the preparation of an organosilyl proton exchange membrane according to any one of claims 1 to 6, characterized in that the substrate is polytetrafluoroethylene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101792470B (en) * | 2010-03-18 | 2012-03-07 | 武汉理工大学 | Preparation method of phosphonic acid group alkoxysilane for intermediate-temperature proton exchange membrane |
| FR3002859A1 (en) * | 2013-03-07 | 2014-09-12 | Commissariat Energie Atomique | USE OF A FUNCTIONALIZED POLYSILOXANE NETWORK FOR CHEMICALLY STABILIZING A POLYMER, MEMBRANE SO STABILIZED, PROCESS FOR PREPARING THE SAME AND USES THEREOF |
| CN105017545B (en) * | 2015-05-29 | 2018-10-09 | 武汉理工大学 | A kind of polysiloxane grafted phosphonic acid base Copolymer proton exchange membrane and preparation method thereof |
| CN108376791B (en) * | 2018-02-02 | 2020-08-11 | 武汉理工大学 | Organic-inorganic composite proton exchange membrane containing double proton conductors and preparation method thereof |
| CN108777314B (en) * | 2018-05-29 | 2020-08-07 | 中国科学院上海有机化学研究所 | Composite organic phosphonic acid high-temperature proton exchange membrane and preparation method thereof |
| CN108767299B (en) * | 2018-05-29 | 2020-03-10 | 中国科学院上海有机化学研究所 | Composite organic phosphonic acid high-temperature proton exchange membrane for fuel cell and preparation method thereof |
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