CN101867050A - Composite proton exchange membrane - Google Patents
Composite proton exchange membrane Download PDFInfo
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- CN101867050A CN101867050A CN201010195365A CN201010195365A CN101867050A CN 101867050 A CN101867050 A CN 101867050A CN 201010195365 A CN201010195365 A CN 201010195365A CN 201010195365 A CN201010195365 A CN 201010195365A CN 101867050 A CN101867050 A CN 101867050A
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- Prior art keywords
- ketone
- ether
- sulfonated polyether
- exchange membrane
- polyaniline
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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
Abstract
The invention discloses a composite proton exchange membrane which is prepared by taping mixed liquid of a sulfonated polyether ether ketone solution with a sulfonation degree of 50-70 percent, polyaniline filter liquid and heteropoly acid to form the membrane. The composite membrane is prepared by using SPEEK (Sulfonated Polyether Ether Ketone) as a basal body and PANI (Polyaniline) and HPA (Heteropoly acid) as dopants, the material source is wide and does not need to be imported, a preparation technology is simple, and instruments are simple, thereby the cost of the membrane is reduced; a hydrogen bond formed by PANI and SPEEK is used for avoiding the swelling of the SPEEK and reducing methanol penetration and the HPA dropout rate, and the proton conductivity of the composite membrane is improved by the HPA. By changing the composition and the ratio between an alkaline polymer and a proton conductor, the novel PEM (proton exchange membrane) reaches optimum balance among high proton conductivity, low methanol penetration and low HPA dropout rate, the proton conductivity reaches 10-2S/cm, the methanol penetration rate of the composite proton exchange membrane is a half lower than that of an Nafion 117 membrane, and the HPA wastage rate does not reach 5 percent.
Description
Technical field:
The present invention relates to a kind of proton exchange membrane.
Background technology:
Proton exchange membrane (Proton exchange membrane, PEM) be Proton Exchange Membrane Fuel Cells (Proton exchange membrane fuel cell, PEMFC) and directly one of core component of alcohol fuel battery (comprising DMFC and DEFC), its effect is: (1) separates anode and negative electrode, stops fuel and air (oxygen) directly to mix chemical reaction takes place; (2) proton conducting, proton conductivity are high more, and the internal resistance of film is more little, and the efficient of fuel cell is high more; (3) electrical insulator stops electronics to conduct in film, and by outside line road direction cathode flow, it is for people to use to produce foreign current by anode for electronics.Usually, fuel cell must satisfy following requirement with the PEM material: (1) low cost; (2) high proton conductivity; (3) good mechanical intensity (anti-swelling) and dimensional stability; (4) You Yi chemical stability and electrochemical stability; (5) very low gas or methanol permeability; (6) with the catalyst layer coupling; (7) the long-term use stablized.
At present, Nafion series perfluoro sulfonic acid membrane has been obtained successful Application in PEMFC.This class material has higher proton conductivity, good mechanical intensity, excellent chemistry and advantages such as electrochemical stability and sufficiently long useful life.But it still exists some shortcomings: (1) requires height to temperature and water content, and its optimum working temperature is 70 ℃～90 ℃, surpasses this temperature its water content is sharply reduced, and proton conductivity descends rapidly; (2) poor to the selection trafficability characteristic of first alcohol and water, alcohol-rejecting ability is poor, and the methyl alcohol more than 40% can see through this film in use, and this has just reduced battery performance and fuel availability, be not suitable for use in direct methanol fuel cell (Directmethanol fuel cell, PEM DMFC).The PEM that is used for DMFC is varied, and the DMFC that people developed so far is still lower with the proton conductivity of PEM, or methanol permeability is still higher, or cost is also expensive, thus the practical application that does not also reach DMFC.In order to overcome the shortcoming of existing P EM, be necessary the PEM of the high performance DMFC of being applicable to of developing low-cost.
Sulfonated polyether-ether-ketone (Sulfonated polyether ether ketone, SPEEK) film has good chemical stability, high-temperature stability and higher conductivity, and its hydrophilic channel is narrower than Nafion film, be unfavorable for that methyl alcohol passes through, this distinctive microstructure also makes its alcohol-rejecting ability be better than the Nafion film, has shown good prospects for application aspect DMFC.But (the degree of sulfonation DS) has much relations with serviceability temperature for the performance of SPEEK film and its sulfonation degree.When DS and temperature all when higher, the SPEEK film has good proton conductivity, but its alcohol-rejecting ability is poor, and the serious even dissolving of its swelling in methanol aqueous solution; When DS and temperature were low, the SPEEK film had alcohol-rejecting ability preferably, but its proton conductivity is poor.Cai Yuquan etc. are in " polymer material science and engineering " (2007,23 (1): deliver " research that DMFC uses sulfonated polyether-ether-ketone/polyaniline blending type proton exchange membrane " literary composition 246-249), they are with polyaniline (Polyaniline, PANI) add among the SPEEK, the hydrogen bond that utilizes the acid sulfonic group of the alkaline amido of PANI and SPEEK to take place to interact to form suppresses the swelling of SPEEK, though this can play the pure purpose of resistance, because the sulfonic group decreased number, proton conductivity reduces; Xue Song etc. are at " macromolecule journal " (2006, (9): deliver " conduction of sulfonated polyether-ether-ketone/phosphotungstic acid composite membrane and methanol crossover performance " literary composition 1083-1087), they will have phosphotungstic acid (the Phosphotungstic acid of high proton conductivity, PWA) join among the SPEEK, the proton conductivity of composite membrane has improved, but the problem that PWA runs off occurred, this has just influenced the performance of PEM.
Zhou Zhentao equals to disclose in 2007 preparation method's (publication number: CN101188301) of a kind of DMFC usefulness PEM.This method at first adds polyether-ether-ketone dense H
2SO
4In carry out sulfonating reaction and obtain SPEEK; Then SPEEK is dissolved in the organic solvent, add N, N '-carbonyl dimidazoles adds coupling agent stirring reaction 1.5h～4h after stirring 1h～3h, add inorganic crosslinking agent again 50 ℃～80 ℃ reactions down, add proton conductor then and continue under this temperature, to react the mixed solution that obtains sulfonated polyether-ether-ketone/inorganic crosslinking agent/proton conductor; At last with the mixture solution film forming of sulfonated polyether-ether-ketone/inorganic crosslinking agent/proton conductor, drying, demoulding promptly obtains DMFC PEM.Though this film cost is low, the swelling behavior of anti-water is good under the features good methanol diffusion resistance, proton conductivity height, higher temperature.But technology is comparatively complicated, does not consider N, and N '-carbonyl dimidazoles and coupling agent are to the influence of film properties.
Utilize the advantage of SPEEK film, select suitable multi-element doping thing that SPEEK is carried out doping vario-property, regulate the proportioning between them, solve the proton conductivity of SPEEK proton exchange membrane and the contradiction between the alcohol-rejecting ability, make it both have good proton conductive, having alcohol-rejecting ability preferably again, then is the important directions of DMFC with the research of SPEEK proton exchange membrane.
Summary of the invention:
The object of the present invention is to provide a kind of compound proton exchange membrane that can effectively solve the methanol crossover problem of direct methanol fuel cell.
Technical solution of the present invention is:
A kind of compound proton exchange membrane is characterized in that: the mixed liquor that by sulfonation degree is 50%～70% sulfonated polyether-ether-ketone solution, polyaniline filtrate and this three of heteropoly acid is made through casting film-forming; It is the following mass percent requirement of 50%～70% sulfonated polyether-ether-ketone solid, polyaniline powder, heteropoly acid particle that above-mentioned three's consumption meets by sulfonation degree:
Sulfonation degree is 50%～70% sulfonated polyether-ether-ketone solid 50%～90%
Polyaniline powder 5%～25%
Heteropoly acid particle 5%～25%.
Described sulfonation degree is that 50%～70% sulfonated polyether-ether-ketone solution is made by the following step:
(1),, places 95%～98% dense H then with the polyether-ether-ketone powder of drying with polyether-ether-ketone powder dried
2SO
4In, the two ratio is 1g: 20～30mL, add thermal agitation, behind reaction 2h～3h reactant liquor is poured in the mixture of ice and water of 5 times of volumes at least, after the stirring, standing over night, filter out the polymer of sedimentation, again repeatedly, near neutral, obtain sulfonation degree after the drying and be 50%～70% sulfonated polyether-ether-ketone solid up to the pH of solution value with deionized water wash;
(2) preparation sulfonated polyether-ether-ketone solution: the sulfonated polyether-ether-ketone solid is dissolved in the N-methyl pyrrole network alkane ketone, is made into the sulfonated polyether-ether-ketone mass percent and is 10% sulfonated polyether-ether-ketone solution.
Described polyaniline filtrate is made by following method: polyaniline is joined in the N-methyl pyrrole network alkane ketone, and stirring at room filters out undissolved polyaniline, obtains polyaniline filtrate.
Described heteropoly acid is phosphotungstic acid, phosphomolybdic acid or silico-tungstic acid.
The pH value of described solution is meant that near neutrality the pH value of solution is 6.5～7.5; It is dry 10h in 100 ℃ of vacuum drying chambers that the polyether-ether-ketone powder is carried out drying; The temperature that adds thermal agitation is 60 ℃.
The mixture of ice and water of at least 5 times of volumes described in the step (1) is meant the mixture of ice and water of 5～10 times of volumes.
The present invention is matrix with SPEEK, be the composite membrane of alloy preparation with PANI and HPA (heteropoly acid), material source is extensive, does not need import, and preparation technology is simple, used instrument is simple, has reduced the cost of film.The hydrogen bond that forms with PANI and SPEEK solves the swelling of SPEEK, reduces methanol crossover, improves the proton conductivity of composite membrane with HPA.By changing the composition proportioning between alkaline polymer and the proton conductor, make new PE M between high proton conductivity, low methanol crossover and low HPA turnover rate, arrive best balance, proton conductivity reaches 10
-2S/cm, methanol permeability is at half than Nafion 117 films, and the HPA turnover rate is less than 5%.
The proton exchange membrane of the present invention's preparation has solved the methanol crossover problem when the Nafion film is used for DMFC, and proton conductivity does not reduce yet, and has satisfied the requirement of DMFC with PEM.
The proton exchange membrane of the present invention's preparation both can be used for direct methanol fuel cell, also can be used for alcohol fuel batteries such as direct alcohol fuel cell.
The invention will be further described below in conjunction with embodiment.
Embodiment:
Embodiment 1:
(1) sulfonation to get rid of moisture, takes by weighing the polyether-ether-ketone powder with polyether-ether-ketone powder dry 10h in 100 ℃ of vacuum drying chambers then, places 95%～98% dense H
2SO
4In, the two ratio is 1g: 20～30mL, add thermal agitation under 60 ℃, behind reaction 2h～3h reactant liquor is slowly poured in the mixture of ice and water of 5 times of volumes (5～10 times) at least, behind the stirring at room 1h, standing over night filters out the polymer of sedimentation, again repeatedly, up to the pH of solution value approaching neutral (6.5～7.5) with deionized water wash.60 ℃ obtain down DS behind the dry 24h is 50%～70% SPEEK solid.
(2) preparation SPEEK solution is that 50%～70% SPEEK solid is dissolved in the N-methyl pyrrole network alkane ketone (NMP) with DS, is made into mass percent and is 10% sulfonation degree and be 50%～70% SPEEK solution.
(3) preparation PANI filtrate joins PANI among the NMP, and stirring at room 24h is dissolved among the NMP PANI as much as possible, filters out undissolved PANI.Take by weighing the filtrate of 10g～20g, behind 60 ℃ of following dry 48h, the quality of the dry thing of weighing (powder) is to calculate the content of PANI in the filtrate.
(4) the preparation preparation liquid is that 50%～70% SPEEK solid is 50% mass percent according to sulfonation degree, PANI powder 25% mass percent, the prescription requirement of HPA particle 25% mass percent, the sulfonated polyether-ether-ketone solution that calculating and weighing step (2) obtain, polyaniline filtrate and the heteropoly acid that step (3) obtains, the three is mixed, stirring at room 1.5h so just obtains the preparation liquid of proton exchange membrane.HPA is the heteropoly acid with high proton conductivity, and HPA is phosphotungstic acid, phosphomolybdic acid or silico-tungstic acid etc.
(5) in the glass plate pond, 30 ℃ of dryings lose flowability preparation liquid to casting film-forming with above-mentioned preparation liquid curtain coating, at 100 ℃ vacuum drying chamber inner drying 12h, naturally cool to room temperature at last, soak in deionized water, take off, promptly obtain proton exchange membrane.The proton conductivity of proton exchange membrane is 1.5 * 10
-2S/cm, methanol permeability are 1 * 10
-7Cm
2/ s, the heteropoly acid turnover rate is 3.0%.
Embodiment 2:
The formula rate of step (4) is: sulfonation degree is that 50%～70% SPEEK solid is 60% mass percent, PANI powder 15% mass percent, HPA particle 25% mass percent; All the other are with embodiment 1.The proton conductivity of proton exchange membrane is 2 * 10
-2S/cm, methanol permeability are 1.8 * 10
-8Cm
2/ s, the heteropoly acid turnover rate is 2.7%.
Embodiment 3:
The formula rate of step (4) is: sulfonation degree is that 50%～70% SPEEK solid is 70% mass percent, PANI powder 10% mass percent, HPA particle 20% mass percent; All the other are with embodiment 1.The proton conductivity of proton exchange membrane is 2.4 * 10
-2S/cm, methanol permeability are 2.5 * 10
-7Cm
2/ s, the heteropoly acid turnover rate is 2.8%.
Embodiment 4:
The formula rate of step (4) is: sulfonation degree is that 50%～70% SPEEK solid is 80% mass percent, PANI powder 10% mass percent, HPA particle 10% mass percent; All the other are with embodiment 1.The proton conductivity of proton exchange membrane is 1.5 * 10
-2S/cm, methanol permeability are 2.8 * 10
-7Cm
2/ s, the heteropoly acid turnover rate is 1.5%.
Embodiment 5:
The formula rate of step (4) is: sulfonation degree is that 50%～70% SPEEK solid is 90% mass percent, PANI powder 5% mass percent, HPA particle 5% mass percent; All the other are with embodiment 1.The proton conductivity of proton exchange membrane is 2 * 10
-2S/cm, methanol permeability are 1 * 10
-7Cm
2/ s, the heteropoly acid turnover rate is 1.5%.
Claims (4)
1. compound proton exchange membrane is characterized in that: the mixed liquor that by sulfonation degree is 50%～70% sulfonated polyether-ether-ketone solution, polyaniline filtrate and this three of heteropoly acid is made through casting film-forming; It is the following mass percent requirement of 50%～70% sulfonated polyether-ether-ketone solid, polyaniline powder, heteropoly acid particle that above-mentioned three's consumption meets by sulfonation degree:
Sulfonation degree is 50%～70% sulfonated polyether-ether-ketone solid 50%～90%
Polyaniline powder 5%～25%
Heteropoly acid particle 5%～25%.
2. compound proton exchange membrane according to claim 1 is characterized in that: described sulfonation degree is that 50%～70% sulfonated polyether-ether-ketone solution is made by the following step:
(1),, places 95%～98% dense H then with the polyether-ether-ketone powder of drying with polyether-ether-ketone powder dried
2SO
4In, the two ratio is 1g: 20～30mL, add thermal agitation, behind reaction 2h～3h reactant liquor is poured in the mixture of ice and water of 5 times of volumes at least, after the stirring, standing over night, filter out the polymer of sedimentation, again repeatedly, near neutral, obtain sulfonation degree after the drying and be 50%～70% sulfonated polyether-ether-ketone solid up to the pH of solution value with deionized water wash;
(2) preparation sulfonated polyether-ether-ketone solution: the sulfonated polyether-ether-ketone solid is dissolved in the N-methyl pyrrole network alkane ketone, is made into the sulfonated polyether-ether-ketone mass percent and is 10% sulfonated polyether-ether-ketone solution.
3. compound proton exchange membrane according to claim 1 and 2 is characterized in that: described polyaniline filtrate is made by following method: polyaniline is joined in the N-methyl pyrrole network alkane ketone, and stirring at room filters out undissolved polyaniline, obtains polyaniline filtrate.
4. compound proton exchange membrane according to claim 1 and 2 is characterized in that: described heteropoly acid is phosphotungstic acid, phosphomolybdic acid or silico-tungstic acid.
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| CN201010195365A CN101867050A (en) | 2010-06-08 | 2010-06-08 | Composite proton exchange membrane |
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| CN201010195365A CN101867050A (en) | 2010-06-08 | 2010-06-08 | Composite proton exchange membrane |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683732A (en) * | 2012-05-16 | 2012-09-19 | 南通大学 | Proton exchange membrane made from high polymer-metal complex-heteropoly acid material and preparation method thereof |
| CN104091907A (en) * | 2014-06-12 | 2014-10-08 | 苏州经贸职业技术学院 | Fuel cell membrane material and preparation method thereof |
| CN104130433A (en) * | 2014-07-12 | 2014-11-05 | 太原理工大学 | Preparation method of cross-linked polyphenyl ether composite proton exchange membrane |
| CN104701560A (en) * | 2015-02-05 | 2015-06-10 | 成都新柯力化工科技有限公司 | Fuel cell proton exchange membrane and preparation method of fuel cell proton exchange membrane |
| CN105680077A (en) * | 2016-01-13 | 2016-06-15 | 山东星火科学技术研究院 | Proton exchange membrane |
| CN104448771B (en) * | 2014-09-17 | 2017-01-25 | 上海大学 | P-aminobenzene sulfonic acid graphene oxide grafted sulfonated polyetheretherketone proton exchange membrane material and preparation method thereof |
| CN106887628A (en) * | 2017-01-13 | 2017-06-23 | 杭州聚力氢能科技有限公司 | Polyamide/sulfonated polyether-ether-ketone compound proton exchange membrane |
| CN109912928A (en) * | 2019-03-18 | 2019-06-21 | 山东星火科学技术研究院 | The preparation method of sulfonated polyether-ether-ketone and phosphotungstic acid composite membrane |
| CN113745615A (en) * | 2021-08-30 | 2021-12-03 | 中汽创智科技有限公司 | Filler and preparation method and application thereof |
-
2010
- 2010-06-08 CN CN201010195365A patent/CN101867050A/en active Pending
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|---|
| 《高分子学报》 20061231 薛松等 《磺化聚醚醚酮/磷钨酸复合膜的导电和甲醇渗透性能》 第1083-1087页 1-4 , 第9期 2 * |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683732B (en) * | 2012-05-16 | 2014-03-12 | 南通大学 | Proton exchange membrane made from high polymer-metal complex-heteropoly acid material and preparation method thereof |
| CN102683732A (en) * | 2012-05-16 | 2012-09-19 | 南通大学 | Proton exchange membrane made from high polymer-metal complex-heteropoly acid material and preparation method thereof |
| CN104091907A (en) * | 2014-06-12 | 2014-10-08 | 苏州经贸职业技术学院 | Fuel cell membrane material and preparation method thereof |
| CN104130433B (en) * | 2014-07-12 | 2016-11-23 | 太原理工大学 | A kind of preparation method of cross-linking type polyphenylene oxide compound proton exchange membrane |
| CN104130433A (en) * | 2014-07-12 | 2014-11-05 | 太原理工大学 | Preparation method of cross-linked polyphenyl ether composite proton exchange membrane |
| CN104448771B (en) * | 2014-09-17 | 2017-01-25 | 上海大学 | P-aminobenzene sulfonic acid graphene oxide grafted sulfonated polyetheretherketone proton exchange membrane material and preparation method thereof |
| WO2016124052A1 (en) * | 2015-02-05 | 2016-08-11 | 成都新柯力化工科技有限公司 | Proton exchange membrane for fuel cells and preparation method therefor |
| CN104701560B (en) * | 2015-02-05 | 2016-10-19 | 成都新柯力化工科技有限公司 | A kind of fuel battery proton exchange film and preparation method thereof |
| CN104701560A (en) * | 2015-02-05 | 2015-06-10 | 成都新柯力化工科技有限公司 | Fuel cell proton exchange membrane and preparation method of fuel cell proton exchange membrane |
| CN105680077A (en) * | 2016-01-13 | 2016-06-15 | 山东星火科学技术研究院 | Proton exchange membrane |
| CN106887628A (en) * | 2017-01-13 | 2017-06-23 | 杭州聚力氢能科技有限公司 | Polyamide/sulfonated polyether-ether-ketone compound proton exchange membrane |
| CN109912928A (en) * | 2019-03-18 | 2019-06-21 | 山东星火科学技术研究院 | The preparation method of sulfonated polyether-ether-ketone and phosphotungstic acid composite membrane |
| CN113745615A (en) * | 2021-08-30 | 2021-12-03 | 中汽创智科技有限公司 | Filler and preparation method and application thereof |
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Application publication date: 20101020 |