CN1252842C - Process for preparing odified sulfonic acid lateral group polybenzimidazoles proton interchange films - Google Patents
Process for preparing odified sulfonic acid lateral group polybenzimidazoles proton interchange films Download PDFInfo
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- CN1252842C CN1252842C CNB2004100391143A CN200410039114A CN1252842C CN 1252842 C CN1252842 C CN 1252842C CN B2004100391143 A CNB2004100391143 A CN B2004100391143A CN 200410039114 A CN200410039114 A CN 200410039114A CN 1252842 C CN1252842 C CN 1252842C
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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 present invention discloses a preparation method of modified sulfonic acid lateral group polybenzimidazole proton interchange films for direct methanol fuel cells, which belongs to the technical field of fuel cell material preparation. The monomers, namely fouramine group compounds, 3-alkyl-isophthalic acid and fat diprotonic acid are condensed and polymerized to obtain a uniform solution; the solution is neutralized, washed by water, filtered and dried to obtain a polycondensate crude product; after the polycondensate crude product is dissolved in strong inorganic acid, settled out in the water, etc., a polycondensate pure product is obtained; the polycondensate pure product is dissolved in organic solvent to obtain a uniform polycondensate solution; a film is prepared by a pouring method or a flow casting method. The modified sulfonic acid lateral group polybenzimidazole proton interchange film has strong methanol permeation resistance and good proton conductivity and chemical stability and greatly improves the output characteristics of the fuel cells. The present invention can be used for the direct methanol fuel cells as proton exchange films, can widen the kinds of the proton exchange films for the direct methanol fuel cells and can promote the practical development and the commercialization of the direct methanol fuel cells.
Description
Technical field
The invention belongs to fuel cell material technology of preparing scope, the modification sulfonic acid lateral group polybenzimidazole that particularly is used for direct methanol fuel cell prepares the preparation method of proton exchange membrane.
Background technology
The proton exchange membrane of using in direct methanol fuel cell is at present used perfluorocarbon polymer sulfonic acid type ion exchange membrane (Nafion) more.When this perfluorocarbon polymer sulfonic acid proton exchange film is used for direct methanol fuel cell, exist methyl alcohol and be penetrated into the problem that negative electrode hinders the electrochemical cathode reaction from anode, limited the development and application of direct methanol fuel cell widely, in order to address this problem, people have carried out the research of non-fluorine proton-conductive films.
Polybenzimidazoles (PBI) is a class high thermal stability material, has alkaline structure.Mix with acid or after the grafting of sulfonic acid alkyl, can improve the proton exchange membrane of the proton conductivity of PBI as direct methanol fuel cell.The acid doping normally is dipped in the PBI film in the certain density acid solution or is dissolved in acid back directly cast or casting film-forming, and the PBI film after the acid treatment only is 1/300 of a Nafion film to the methanol permeation rate in the time of 80 ℃; The grafting of sulfonic acid alkyl is exactly sulfonation PBI, and sulfonic group (as the p-sulfonic acid benzyl) is incorporated on imidazoles nitrogen or the phenyl ring.No matter PBI mixes with acid or sulfonic acid alkyl grafting processing, and its aim all is to improve the proton-conducting of PBI, satisfies the requirement that direct methanol fuel cell is used with proton exchange membrane.But, produce swelling behind the acid treatment PBI, the pliability of PBI film is increased, the what is called that the crisp indissoluble of matter then takes place in the PBI sulfonation " is stablized PBI ", has reduced the mechanical performance of film, has reduced useful life.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of modification sulfonic acid lateral group polybenzimidazole proton exchange membrane, it is characterized in that: use tetra-amino compound, 3-alkyl acid-isophthalic acid, binary acid in polyphosphoric acids, to prepare the sulfonic acid lateral group polybenzimidazole proton exchange membrane of modification, in the PBI rigid chain segment, introduce flexible group, both guarantee the proton conductivity of proton exchange membrane, and can solve the problem of the crisp indissoluble of film again; This film has the characteristics of proton conductivity height, softness, solubility increase.Its preparation process is:
1) tetra-amino compound, 3-alkyl acid-isophthalic acid, binary acid and polyphosphoric acids are 1: 0.5～1: 0.05～0.3: 18～22 by weight; After elder generation's tetra-amino compound, 3-alkyl acid-isophthalic acid and binary acid mix, be added to again in the polyphosphoric acids, form uniform mixture;
2) in inert atmosphere, under 100～250 ℃, stirring reaction 1～8 hour obtains homogeneous solution;
3) with in the 1N-2N sodium hydroxide solution and more than the homogeneous solution that obtains, be washed to neutrality, drying, the condensation polymer crude product after obtaining handling;
4) the above-mentioned condensation polymer that obtains is dissolved in the strong inorganic acid, precipitating, filtration in water then is washed to neutrality, and drying obtains the pure product of condensation polymer;
5) the pure product of the above-mentioned condensation polymer that obtains are dissolved in the organic solvent, obtain condensation polymer solution; With above-mentioned condensation polymer solution casting or the casting film-forming that obtains, solidified under the room temperature 2～6 hours, 100～300 ℃ down or in the 100pa vacuum, 60～150 ℃ solidified 2～8 hours down, are cooled to room temperature, demoulding in the water in inert atmosphere then.
Described tetra-amino compound is 2,3,4,5-tetramino benzene, 3,3 ', 4, and 4 '-tetramino connects benzene and 3, and 3 ', 4, any one in 4 '-tetramino diphenyl ether.
Described 3-alkyl acid-isophthalic acid is any one in 3-methanesulfonic acid-isophthalic acid, 3-ethyl sulfonic acid-isophthalic acid and the 3-N-morpholinopropanesulfonic acid-isophthalic acid.
Described binary acid is any one in malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and the decanedioic acid.
Used organic solvent is the equal amount of mixture of any one or two kinds in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO) and the N-methyl pyrrolidone.
The invention has the beneficial effects as follows and introduce flexible group in the PBI rigid chain segment, solve the problem of the crisp indissoluble of film, make film have the advantages that good anti-methanol crossover ability, proton conductivity height, softness and solubility increase, can be used for direct methanol fuel cell as proton exchange membrane, improve the electrochemical cathode activity, improve the output characteristic of fuel cell.
Concrete embodiment
The present invention is a kind of preparation method of modification sulfonic acid lateral group polybenzimidazole proton exchange membrane.Be 1: 0.5～1: 0.05～0.3: 18～22 ratio by weight with tetra-amino compound, 3-alkyl acid-isophthalic acid, binary acid and polyphosphoric acids, after elder generation's tetra-amino compound, 3-alkyl acid-isophthalic acid and binary acid mix, be added to again in the polyphosphoric acids, form uniform mixture; In inert atmosphere, under 100～250 ℃, stirring reaction 1～8 hour obtains homogeneous solution; Neutralization, washing, filtration, drying obtain the condensation polymer crude product; Condensation polymer is dissolved in the strong inorganic acid, and precipitating, filtration, washing, drying obtain the pure product of condensation polymer in the water; The pure product of condensation polymer are dissolved in the organic solvent, obtain condensation polymer solution; With condensation polymer solution casting or casting film-forming, solidified under the room temperature 2～6 hours, then in inert atmosphere, under 100～300 ℃ or in the 100pa vacuum, 60～150 ℃ solidified 2～8 hours down, were cooled to room temperature, and demoulding becomes modification sulfonic acid lateral group polybenzimidazole proton exchange membrane in the water
Described tetra-amino compound is 2,3,4,5-tetramino benzene, 3,3 ', 4, and 4 '-tetramino connects benzene and 3, and 3 ', 4, any one in 4 '-tetramino diphenyl ether.
Described 3-alkyl acid-isophthalic acid is any one in 3-methanesulfonic acid-isophthalic acid, 3-ethyl sulfonic acid-isophthalic acid and the 3-N-morpholinopropanesulfonic acid-isophthalic acid.
Described binary acid is any one in malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and the decanedioic acid.
Solvent for use is the equal amount of mixture of any one or two kinds in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO) and the N-methyl pyrrolidone.
Give an actual example below the present invention illustrated:
Example 1:
1) with 1 part 2,3,4,5-tetramino benzene or 3,3 ', 4,4 '-tetramino connects benzene, 0.58 part of 3-methanesulfonic acid-isophthalic acid and 0.31 part of adipic acid and is dissolved in 22 parts of polyphosphoric acids, forms uniform mixture;
2) in nitrogen atmosphere, 150 ℃ were reacted 2 hours down, obtain brown solution;
3) brown solution is neutralized to neutrality with the 2N sodium hydroxide solution after, filter, drying, obtain buff condensation polymer crude product;
4) with the above-mentioned condensation polymer dissolving crude product that obtains in 1N sulfuric acid, precipitating in the water, filter, be washed to neutrality, the following 80 ℃ of dryings of vacuum 24 hours, obtain the pure product of condensation polymer;
5) in the 12 parts of pure product to 100 of above-mentioned condensation polymer part dimethyl sulfoxide (DMSO)s of dissolving, obtain uniform condensation polymer solution;
6) with behind above condensation polymer solution casting or the casting film-forming, solidified under the room temperature 2 hours, solidifying 4 hours down for 100 ℃, be cooled to room temperature then at 1～3 liter of/minute nitrogen atmosphere, demoulding in the water obtains the sulfonic acid lateral group polybenzimidazole proton exchange membrane of modification.
Example 2:
1) 1 part 3,3 ', 4,4 '-tetramino diphenyl ether, 0.78 a part of 3-N-morpholinopropanesulfonic acid-benzene two, 0.1 part of adipic acid are dissolved in 18 parts of polyphosphoric acids, form uniform mixture;
2) in argon gas atmosphere, 250 ℃ were reacted 1 hour down, obtain deep brown solution;
3) deep brown solution is neutralized to neutrality with the 2N sodium hydroxide solution after, filter, drying, obtain yellow condensation polymer crude product;
4) with the above-mentioned yellow condensation polymer dissolving crude product that obtains in 1N sulfuric acid, precipitating in the water, filter, be washed to neutrality, the following 80 ℃ of dryings of vacuum 24 hours, obtain the pure product of condensation polymer;
5) in the 12 parts of pure product to 100 of above-mentioned condensation polymer part dimethylacetylamides of dissolving, obtain uniform condensation polymer solution;
6) with behind above condensation polymer solution casting or the casting film-forming, solidified under the room temperature 2 hours, then 1～3 liter of/minute argon gas atmosphere, 180 ℃ solidified 6 hours down, were cooled to room temperature, and demoulding in the water obtains the sulfonic acid lateral group polybenzimidazole proton exchange membrane of modification.
Only lift above-mentioned 2 examples, the sulfonic acid lateral group polybenzimidazole proton exchange membrane of all the other modifications, its technology is basic identical, is come to the same thing.
Claims (6)
1. the preparation method of modification sulfonic acid lateral group polybenzimidazole proton exchange membrane, it is characterized in that: the preparation process of the sulfonic acid lateral group polybenzimidazole proton exchange membrane of modification is:
1) tetra-amino compound, 3-alkyl acid-isophthalic acid, binary acid and polyphosphoric acids are 1: 0.5～1: 0.05～0.3: 18～22 by weight; After elder generation's tetra-amino compound, 3-alkyl acid-isophthalic acid and binary acid mix, be added to again in the polyphosphoric acids, form uniform mixture;
2) in 1～3 liter/minute inert atmosphere, under 100～250 ℃, stirring reaction 1～8 hour obtains homogeneous solution;
3) above-mentioned homogeneous solution is neutralized to neutrality with sodium hydroxide solution after, filter, drying, obtain the condensation polymer crude product;
4) with the above-mentioned condensation polymer dissolving crude product that obtains in 1N or 2N sulfuric acid, in deionized water precipitating, filtration, with deionized water be washed to neutrality, drying obtains the pure product of condensation polymer;
5) the pure product of the above-mentioned condensation polymer that obtains are dissolved in the organic solvent, obtain condensation polymer solution;
6) with above-mentioned condensation polymer solution casting or the casting film-forming that obtains, solidified under the room temperature 2～6 hours, then in inert atmosphere, under 100～300 ℃ or in the 100pa vacuum, 60～150 ℃ solidified 2～8 hours down, be cooled to room temperature, demoulding in the water obtains the sulfonic acid lateral group polybenzimidazole proton exchange membrane of modification.
2. according to the sulfonic acid lateral group polybenzimidazole proton exchange membrane preparation method of the described modification of claim 1, it is characterized in that: described tetra-amino compound is 2,3,4,5-tetramino benzene, 3,3 ', 4,4 '-tetramino connects benzene and 3,3 ', 4, any one in 4 '-tetramino diphenyl ether.
3. according to the preparation method of the described modification sulfonic acid lateral group polybenzimidazole of claim 1 proton exchange membrane, it is characterized in that: described 3-alkyl acid-isophthalic acid is any one in 3-methanesulfonic acid-isophthalic acid, 3-ethyl sulfonic acid-isophthalic acid and the 3-N-morpholinopropanesulfonic acid-isophthalic acid.
4. according to the preparation method of the described modification sulfonic acid lateral group polybenzimidazole of claim 1 proton exchange membrane, it is characterized in that: described binary acid is any one in malonic acid, succinic acid, glutaric acid, hexanedioic acid, pimelic acid, suberic acid, azelaic acid and the decanedioic acid.
5. according to the preparation method of the described modification sulfonic acid lateral group polybenzimidazole of claim 1 proton exchange membrane, it is characterized in that: solvent for use is the mixture of any one or two kinds in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO) and the N-methyl pyrrolidone.
6. according to the preparation method of the described modification sulfonic acid lateral group polybenzimidazole of claim 1 proton exchange membrane, it is characterized in that: described inert gas is nitrogen or argon gas.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100391143A CN1252842C (en) | 2004-02-06 | 2004-02-06 | Process for preparing odified sulfonic acid lateral group polybenzimidazoles proton interchange films |
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| CNB2004100391143A CN1252842C (en) | 2004-02-06 | 2004-02-06 | Process for preparing odified sulfonic acid lateral group polybenzimidazoles proton interchange films |
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| CN1252842C true CN1252842C (en) | 2006-04-19 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100365858C (en) * | 2005-04-05 | 2008-01-30 | 新源动力股份有限公司 | Composite proton exchange membrane for high-temperature fuel battery and producing method thereof |
| CN101392060B (en) * | 2008-10-21 | 2011-01-12 | 东华大学 | Quaternized polybenzimidazoles and preparation method thereof |
| CN101709029B (en) * | 2009-11-16 | 2013-01-02 | 清华大学 | Polybenzimidazole material and midbody organic diacid thereof as well as preparation methods thereof |
| US9048478B2 (en) | 2010-04-22 | 2015-06-02 | Basf Se | Polymer electrolyte membrane based on polyazole |
| EP2561572A4 (en) * | 2010-04-22 | 2014-03-05 | Basf Se | Improved polymer electrolyte membrane based on polyazole |
| CN103086999B (en) * | 2011-11-03 | 2014-09-17 | 清华大学 | Novel fluorine-containing polybenzimidazole polymer, fluorinated organic diacid monomer as intermediate of the fluorine-containing polybenzimidazole polymer, and their preparation method |
| CN108400362B (en) * | 2018-02-05 | 2020-06-16 | 大连理工大学 | Side chain type alkyl sulfonated polybenzimidazole ion exchange membrane and preparation method thereof |
| CN114536915B (en) * | 2022-03-11 | 2023-05-23 | 福建师范大学 | Alkali-resistant bipolar membrane with main chain fluorocarbon-ferrocene catalytic layer and preparation method thereof |
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