CN107623138A - A kind of compound proton exchange membrane and preparation method thereof - Google Patents
A kind of compound proton exchange membrane and preparation method thereof Download PDFInfo
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- CN107623138A CN107623138A CN201710690319.5A CN201710690319A CN107623138A CN 107623138 A CN107623138 A CN 107623138A CN 201710690319 A CN201710690319 A CN 201710690319A CN 107623138 A CN107623138 A CN 107623138A
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- exchange membrane
- proton exchange
- alcohol
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- sulfonated polyethylene
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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 discloses a kind of compound proton exchange membrane, it is made up of sulfonation degree of 10%~25% sulfonated polyethylene alcoholic solution and the mixed solution of polyamic acid through casting film-forming, it is a kind of composite membrane using polyimides as matrix, prepared using sulfonated polyethylene alcohol as dopant.It is extensive to prepare material source, preparation technology is easy, and apparatus for preparation is simple, reduces the cost of film.The present invention is compound using sulfonated polyethylene alcohol and polyimides, the decline of proton conductivity can be weakened, effectively reduce the methanol permeability of compound proton exchange membrane, improve the combination property of PEM, high methanol infiltration problem be present for DMFC in the Nafion membrane for solving the production of Dupont companies, proton conductivity can also meet requirement of the DMFC to PEM simultaneously, it can be not only used for DMFC, it can also be used to the alcohol fuel battery such as Direct Ethanol Fuel Cell.
Description
Technical field：
The invention belongs to field of fuel cell technology, and in particular to a kind of to prevent in a fuel cell for isolating positive and negative electrode
Only short-circuit PEM and preparation method thereof.
Background technology：
At present, fuel cell has turned into the focus of international energy area research exploitation, and its development will promote whole with exploitation
The fast development of individual electric automobile, submarine and power generation industries.As one of critical component of fuel cell, it is tied PEM
Structure decides the efficiency of fuel cell with performance.PEM, which will not only play isolation positive and negative electrode, prevents the effect of short circuit,
Also being played during its use allows charge carrier from it by completing electrochemical reaction.
Perfluorosulfonic acid type PEM is now widely used commodity PEM, wherein most representational be
The Nafion series membranes of Dupont companies of U.S. production.Perfluorosulfonic acid type PEM has high mechanical strength, chemically stable
Property it is good, proton conductivity is high when water content is high the advantages that, be widely used in Proton Exchange Membrane Fuel Cells, PEM electricity
Xie Shui and ion-exchange membrane electrolyzer caustic soda, but perfluorosulfonic acid type PEM also has the shortcomings that obvious：Price too expensive,
Proton conductivity is very low in the case of relatively low moisture content, and the methanol permeability in methanol fuel cell is too high, the above
Problem is all the major obstacle of perfluoro sulfonic acid membrane widespread adoption.
In order to solve above mentioned problem existing for perfluoro sulfonic acid membrane, researcher once attempts to prepare matter using part fluorine material
Proton exchange, such as early stage polytriflurostyrene sulphonic film, but because mechanical strength and chemical stability are bad, it is impossible to meet fuel
The long-term use of requirement of battery.Canadian Ballard companies obtain BAM3G films after making improvements, its sulfonic group content is low,
Operating efficiency is high, and the life-span of monocell can bring up to 15000h.Oozed to effectively reduce the methanol of DMFC film
Saturating problem, people are from inorganic matter as filler., can because inorganic material has good solvent resistant, high-temperature stability
Effectively suppress the surface dissolving of membrane material, prevent methanol molecules from permeating, for example, by ZrP, SiO2Filled by ion-exchange reactions
Into in the micro-structural of Nafion membrane, membrane material methanol leakage is effectively reduced.But the proton membrane is not due to abandoning using perfluor
Nafion membrane is still difficult for people and received as substrate, its preparation cost.
The content of the invention：
For the state of the art of the PEM of prior art a kind of proton is aimed to provide with deficiency, the purpose of the present invention
Conductivity is high, methanol permeability is low, satisfactory mechanical property, prepares cost low compound proton exchange membrane and its preparation method, with
The defects of making up prior art PEM.
Compound proton exchange membrane provided by the invention, by the combination for including sulfonated polyethylene alcoholic solution and polyamic acid solution
Thing is made through casting film-forming, wherein the mass percent of the sulfonated polyethylene alcohol solid and polyamic acid solid is (30：70)
~(70：30).
In the above-mentioned technical proposal of the present invention, the sulfonation of the preferred sulfonation degree 10%~25% of sulfonated polyethylene alcohol gathers
Vinyl alcohol；Further preferably there is the sulfonated polyethylene alcohol of following molecular structure：
Wherein m is vinyl alcohol chain length, and span is integer 960-1890, and preferably 1360-1530, n are sulfonation second
Enol chain length, span are integer 120-420, preferably 170-340.
The sulfonated polyethylene alcohol can be prepared by following methods：
100 parts of polyvinyl alcohol are placed in 60-90 DEG C of water heating stirring until polyvinyl alcohol is completely dissolved, are made into quality
Fraction is 8~12% solution, poly-vinyl alcohol solution is placed in ice bath cooled thereafter, when temperature is cooled to not higher than 0 DEG C,
10-130 part concentrated sulfuric acids are added dropwise into system, after being sufficiently stirred under condition of ice bath, adds deionized water, system is diluted to poly- second
Enol mass percent is 5~10%, finally pours into 200-2000 part acetone dilution and precipitates, sediment is in 60~80 DEG C
Vacuum is fully dried, that is, sulfonated polyethylene alcohol is made.
The polyvinyl alcohol is preferably selected from but is not limited to：The trade mark be 1799,1788,1778,0588,0578,2088,
2099th, 2488 and 2499 polyvinyl alcohol.
In the above-mentioned technical proposal of the present invention, the polyamic acid, which is preferentially selected, passes through polyamide made of following methods
Acid：
By diamines in dissolved solution in organic solvent, add dianhydride stirring fully reaction after, add organic solvent it is dilute
System is released to solid content 5~10%, system is added in deionized water and slowly precipitated, fully after precipitation separating, washing after
60~80 DEG C of vacuum are fully dried, that is, polyamic acid is made.
The diamines preferably has the diamines of following structure：
H2N-R1-NH2
Wherein R1 is disposable substituted radical.Further, diamines is preferably selected from but is not limited to：P-phenylenediamine, 1,3-
Double (4- amino-benzene oxygens) benzene of double (4- amino-benzene oxygens) benzene, 1,4-, 2,2'- double (4- aminophenoxy phenyls) propane, 4,4'-
Diaminodiphenyl ether and 3,3'- diaminodiphenyl ethers.
The dianhydride preferably has the dianhydride of following structure：
Wherein R2For disposable substituted radical；Further, dianhydride is preferably selected from but is not limited to：Pyromellitic Acid two
Acid anhydride, diphenyl ether tetraformic dianhydride, Bisphenol A Type Diether Dianhydride, 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides, 2,3,3', 4- biphenyl four
Formic acid dianhydride, cyclobutanetetracarboxylic dianhydride and hexafluorodianhydride (6FDA).
The organic solvent is preferably selected from but is not limited to：1-METHYLPYRROLIDONE, N,N-dimethylformamide, γ-Ding Nei
Ester, ethoxy monobutyl ether and metacresol.
Compound proton exchange membrane provided by the invention can be prepared by the method comprised the following steps that：
(1) polyamic acid of formula ratio is added in the deionized water solution containing triethylamine, fills it in stirring at normal temperature
Point dissolving, obtain polyamic acid mass percent be 10~20% the polyamic acid triethylamine salt aqueous solution, the triethylamine with
Hydroxy-acid group molar equivalent ratio in polyamic acid is 1：(0.9~1.1)；By the sulfonated polyethylene alcohol of formula ratio be dissolved into from
The sulfonated polyethylene alcohol solution that sulfonated polyethylene alcohol mass percent is 10~20% is obtained in sub- water；
(2) after two kinds of solution are uniformly mixed under normal temperature, coated on cleaning glass plate on film forming, in 12h~
Taken off after 24h, it is after being dried in vacuo at 48~70 DEG C, membranes submerged is molten in 56~80 DEG C of toluene containing acetic anhydride, pyridine
Chemical imidization is carried out in liquid, after abundant chemical imidization, is immersed in the solution containing glutaraldehyde and is crosslinked, finally will
Film is immersed in 0.5~1.5mol/L hydrochloric acid solution, the compound proton exchange membrane activated after fully immersion.
Compound proton exchange membrane provided by the invention, it is using polyimides as matrix, using sulfonated polyethylene alcohol as dopant
The composite membrane of preparation, it is extensive to prepare material source, and preparation technology is easy, and apparatus for preparation is simple, reduces the cost of film.This hair
It is bright compound using sulfonated polyethylene alcohol and polyimides, the decline of proton conductivity can be weakened, composite proton is effectively reduced and hand over
Change the methanol permeability of film.By changing the sulfonation degree of polyvinyl alcohol, PEM is set to be oozed in high proton conductivity, low methanol
Reach optimum balance between saturating rate, proton conductivity can reach 10-2S/cm, methanol permeability number lower than Nafion115
Magnitude.
Compound proton exchange membrane prepared by the present invention solve Nafion membrane be used for it is existing during DMFC
The problem of methanol crossover is high, while proton conductivity can also meet the requirement of DMFC PEMs.
PEM prepared by the present invention can be not only used for DMFC, it can also be used to direct alcohol fuel electricity
The alcohol fuel batteries such as pond.
Brief description of the drawings
Fig. 1 is the made film proton conductivity variation with temperature figure of the present invention.
Fig. 2 is film-made alcohol-rejecting ability figure by the present invention.
Embodiment：
Embodiment 1：
(1) sulfonation：90mL deionized waters, 10g polyvinyl alcohol (PVA), at 60 DEG C are added in 500mL three-necked flask
2h is stirred, 90 DEG C is warming up to and continues stirring until PVA is completely dissolved.Thereafter PVA solution is placed in ice bath and cooled, treat that temperature is cold
When but to 0 DEG C, the 2mL concentrated sulfuric acids are added dropwise into system, mechanical agitation about 2h under condition of ice bath.And add 100mL in backward system
Deionized water dilutes.Then it is poured into 1000mL acetone and precipitates, repeatedly washing obtains sulphur after vacuum drying 8h at 40 DEG C
Change degree is 10% sulfonated polyethylene alcohol (SPVA) solid.
(2) yellow poly-vinyl alcohol solution is prepared：SPVA is dissolved in deionized water, obtaining SPVA mass percents is
The 10% SPVA aqueous solution.
(3) polyamic acid solution is prepared：The deionized water solution containing triethylamine will be added with the PAA of the quality such as SPVA
In, stirring at normal temperature makes its dissolving, obtains polyamic acid triethylamine salt (PAA-salt) aqueous solution of mass percent 10%；It is described
Hydroxy-acid group molar equivalent ratio in the content and polyamic acid of triethylamine is 1：1.
(4) casting film-forming：After two kinds of solution are uniformly mixed under normal temperature, coated on clean glass plate into
Film, film is taken off after 24h and is dried in vacuum overnight at 50 DEG C.By dry membranes submerged in the toluene containing acetic anhydride, pyridine
In solution, about 4h is soaked at 60 DEG C and carries out chemical imidization, obtains PI/SPVA composite membranes.The proton conduction of PEM
Rate is 1.2mS/cm, and methanol permeability is 0.95 × 10-7cm2/s。
Embodiment 2：
The concentrated sulfuric acid dosage added in step (1) is 3mL, and remaining is the same as example 1.The proton conductivity of PEM is
7.1mS/cm, methanol permeability are 0.75 × 10-7cm2/s。
Embodiment 3：
The concentrated sulfuric acid dosage added in step (1) is 5mL, and remaining is the same as example 1.The proton conductivity of PEM is
7.4mS/cm, methanol permeability are 0.67 × 10-7cm2/s。
Embodiment 4：
The concentrated sulfuric acid dosage added in step (1) is 7mL, and remaining is the same as example 1.The proton conductivity of PEM is
1.88×10-2S/cm, methanol permeability are 0.60 × 10-7cm2/s。
The preferred embodiment of the present invention is the foregoing is only, is not intended to limit the invention, for the technology of this area
For personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is done any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (10)
1. a kind of compound proton exchange membrane, it is characterised in that by the mixed of sulfonated polyethylene alcohol solution and the polyamic acid aqueous solution
Close liquid to be made through casting film-forming, the mass percent of the sulfonated polyethylene alcohol and polyamic acid is (30：70)~(70：30).
2. compound proton exchange membrane according to claim 1, it is characterised in that：The sulfonated polyethylene alcohol is sulfonation degree
10%~25% sulfonated polyethylene alcohol.
3. compound proton exchange membrane according to claim 2, it is characterised in that：The sulfonated polyethylene alcohol has following point
Minor structure：
Wherein m is vinyl alcohol chain length, and value is that integer 960-1890, n are sulfonated ethylene alcohol chain length, and value is integer
120-420。
4. compound proton exchange membrane according to claim 3, it is characterised in that：The sulfonated polyethylene alcohol passes through following sides
Method is made：
100 parts of polyvinyl alcohol are placed in 60-90 DEG C of water heating stirring until polyvinyl alcohol is completely dissolved, are made into polyvinyl alcohol
Mass fraction is 8~12% solution, poly-vinyl alcohol solution is placed in ice bath cooled thereafter, treat that temperature is cooled to not higher than 0
DEG C when, 10-130 part concentrated sulfuric acids are added dropwise into system, after being sufficiently stirred under condition of ice bath, adds deionized water and is diluted to polyethylene
Alcohol mass percent is 5~10%, finally pours into 200-2000 part acetone dilution and precipitates, and sediment is true in 60~80 DEG C
It is empty fully to dry, that is, sulfonated polyethylene alcohol is made.
5. according to the compound proton exchange membrane described in Claims 2 or 3 or 4, it is characterised in that：The polyvinyl alcohol is selected from the trade mark
For 1799,1788,1778,0588,0578,2088,2099,2488 and 2499 polyvinyl alcohol.
6. the compound proton exchange membrane according to one of Claims 1-4, it is characterised in that：The polyamic acid is under
The method of stating is made：
By diamines in dissolved solution in organic solvent, add dianhydride stirring fully reaction after, add organic solvent diluting body
System is poured into deionized water and slowly precipitated to solid content 5~10% by system, fully after precipitation after separating, washing, in 60~
80 DEG C of vacuum drying, that is, be made polyamic acid.
7. compound proton exchange membrane according to claim 6, it is characterised in that：The diamines is two with following structure
Amine：
H2N-R1-NH2
Wherein R1For disposable substituted radical.
8. compound proton exchange membrane according to claim 6, it is characterised in that：The dianhydride is two with following structure
Acid anhydride：
Wherein R2For disposable substituted radical.
9. compound proton exchange membrane according to claim 6, it is characterized in that：The organic solvent is selected from N- crassitudes
Ketone, N,N-dimethylformamide, gamma-butyrolacton, ethoxy monobutyl ether and metacresol.
10. according to the preparation method of one of claim 1 to 9 compound proton exchange membrane, it is characterised in that including following work
Skill step：
(1) polyamic acid of formula ratio is added in the deionized water solution containing triethylamine, makes its dissolving in stirring at normal temperature, obtain
To the polyamic acid triethylamine salt aqueous solution that polyamic acid mass percent is 10~20%, in the triethylamine and polyamic acid
Hydroxy-acid group molar equivalent ratio be 1：(0.9~1.1)；The sulfonated polyethylene alcohol of formula ratio is dissolved into deionized water and obtained
Sulfonated polyethylene alcohol mass percent is 10~20% sulfonated polyethylene alcohol solution；
(2) after two kinds of solution are uniformly mixed under normal temperature, film forming on the glass plate coated on cleaning, after 12~24h
Take off, at 48~70 DEG C be dried in vacuo after, by membranes submerged 56~80 DEG C containing acetic anhydride, pyridine toluene solution in enter
Row chemical imidization, after abundant chemical imidization, it is immersed in the solution containing glutaraldehyde and is crosslinked, finally soak film
Steep in 0.5~1.5mol/L hydrochloric acid solution, the compound proton exchange membrane activated after fully immersion.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752614A (en) * | 2018-06-20 | 2018-11-06 | 四川大学 | A kind of blending proton exchange membrane and preparation method thereof containing compatilizer |
| CN108832160A (en) * | 2018-06-20 | 2018-11-16 | 四川大学 | Polyimide grafted sulfonated polyethylene alcohol copolymer proton exchange membrane and preparation method thereof |
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| CN101864085A (en) * | 2010-03-10 | 2010-10-20 | 合肥科振实业发展有限公司 | Method for manufacturing covalent cross-linked proton exchange membrane (PEM) for fuel cell |
| CN102477162A (en) * | 2010-11-25 | 2012-05-30 | 比亚迪股份有限公司 | Preparation method of proton exchange membrane and polyimide perfluorosulfonic acid resin proton exchange membrane obtained thereby |
| CN102716680A (en) * | 2012-06-05 | 2012-10-10 | 中国科学院化学研究所 | Polyamide microporous membrane and preparation method thereof |
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2017
- 2017-08-14 CN CN201710690319.5A patent/CN107623138B/en active Active
Patent Citations (3)
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| CN101864085A (en) * | 2010-03-10 | 2010-10-20 | 合肥科振实业发展有限公司 | Method for manufacturing covalent cross-linked proton exchange membrane (PEM) for fuel cell |
| CN102477162A (en) * | 2010-11-25 | 2012-05-30 | 比亚迪股份有限公司 | Preparation method of proton exchange membrane and polyimide perfluorosulfonic acid resin proton exchange membrane obtained thereby |
| CN102716680A (en) * | 2012-06-05 | 2012-10-10 | 中国科学院化学研究所 | Polyamide microporous membrane and preparation method thereof |
Non-Patent Citations (2)
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| SHUAI LIU等: ""Novel sulfonated polyimide/polyvinyl alcohol blend membranes for vanadium redoxflow battery applications"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 程海龙 等: ""侧链型磺化聚芳醚酮/磺化聚乙烯醇复合型直接甲醇燃料电池用质子交换膜"", 《物理化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752614A (en) * | 2018-06-20 | 2018-11-06 | 四川大学 | A kind of blending proton exchange membrane and preparation method thereof containing compatilizer |
| CN108832160A (en) * | 2018-06-20 | 2018-11-16 | 四川大学 | Polyimide grafted sulfonated polyethylene alcohol copolymer proton exchange membrane and preparation method thereof |
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| CN107623138B (en) | 2020-12-29 |
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