CN102983345A - High-temperature proton exchange membrane in hydrophobic gel base and preparation method and application thereof - Google Patents
High-temperature proton exchange membrane in hydrophobic gel base and preparation method and application thereof Download PDFInfo
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- CN102983345A CN102983345A CN2012105205403A CN201210520540A CN102983345A CN 102983345 A CN102983345 A CN 102983345A CN 2012105205403 A CN2012105205403 A CN 2012105205403A CN 201210520540 A CN201210520540 A CN 201210520540A CN 102983345 A CN102983345 A CN 102983345A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/50—Fuel cells
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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
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Abstract
The invention provides a high-temperature proton exchange membrane in a hydrophobic gel base and a preparation method and an application thereof, and particularly relates to a method in which a hydrophobic gel membrane is prepared from a hydrophilic monomer and amphiphilic macromolecules by graft modification, a methanol solution of a proton conductor is absorbed and the high-temperature proton exchange membrane can be prepared in the hydrophobic gel base in a vacuum drying manner. The proton conductivity of the synthetized hydrophobic gel base proton exchange membrane can achieve 0.001-0.02S.cm<-1> at the temperature of 180 DEG C and under a waterless environment. The preparation method disclosed by the invention is different from that of the proton exchange membrane doped with the conventional proton conductor. According to the preparation method, the unique adsorbability, a porous structure, and the retainability of the hydrophobic gel membrane are fully utilized to absorb the proton conductor into a three-dimensional net structure of the hydrophobic gel membrane so as to firmly seal the proton conductor. The high-temperature proton exchange membrane in the hydrophobic gel base, disclosed by the invention, is large in adsorption amount of the proton conductor, high in proton conductivity, wide in operating temperature range, low in cost, and large in improvement space, and the preparation method is simple and feasible.
Description
Technical field
The invention belongs to new material technology and new preparation process field, be specifically related to high temperature proton exchange film and its preparation method and application in a kind of new hydrophobic gel base.
Background technology
Proton exchange membrane is a kind of solid-state polymer electrolyte film with better proton conductivity, in order to transmit proton.Proton exchange membrane is by swelling, sulfonation or the class proton conductive film that is compounded to form with proton conductor by polymer or polymer composites.
Proton exchange membrane starts from U.S. GE company in the polyphenylacetylene sulfonate film of phase at the beginning of the sixties in last century, but stability and conductivity are relatively poor, and the very fast Nafion film of being developed by du pont company replaces.Because the problems such as Nafion film price is high, the low catalyst activity that causes of operating temperature is low, the battery power output is low are so that Nafion matrix proton exchange film fuel cell can't commercial application.Therefore, a kind of proton exchange membrane that can stable operation under middle hot conditions of exploitation becomes the necessary condition that Proton Exchange Membrane Fuel Cells is able to extensive use.
Present high temperature proton exchange film is mainly take phosphate-doped polybenzimidazoles (PBI) film as main, but PBI membrane molecule amount is lower, film forming is difficult, cost is higher and low to the adsorbance of phosphoric acid, and prepared proton exchange membrane conductivity is relatively low.But phosphate-doped PBI film can be 200 ℃ of stable operations, and mechanical strength is high.
At present, the preparation method of phosphate-doped PBI film mainly becomes embrane method, Interfacial coagulation method, graft reaction method and copolyreaction method as main take infusion method, mixed solution.The protonated degree and the retentivity that are limited to PBI, it is serious that the long-term washing of phosphoric acid load capacity water low and that generated by negative electrode in fuel cell causes phosphoric acid to run off.Therefore the middle high temperature proton exchange film of developing a kind of proton conductor good airproof performance is significant.
Summary of the invention
The object of the present invention is to provide high temperature proton exchange film and its preparation method and application in a kind of organophilic gel base, the high temperature proton exchange film cost is lower in the described organophilic gel base, and mechanical strength is higher, and operating temperature range is wide, applied widely, and the preparation method is simple and easy to do.
For achieving the above object, the present invention adopts following technical proposals to be achieved:
The invention provides the preparation method of high temperature proton exchange film in the organophilic gel base, may further comprise the steps:
(1), hydrophilic monomer is removed polymerization inhibitor through purification;
(2), by hydrophilic monomer: the mass ratio of water is 1:0.5～1.5, with the hydrophilic monomer dissolving, forms uniform monomer solution in water;
(3), by amphiphilic large molecule: the mass ratio of water is 1:1～1.5, its dissolving is formed the solution of homogeneous in water;
(4), under stirring state, 0.2～0.5% the initator that adds 0.02～0.08% crosslinking agent, the monomer weight of 5～30% the amphiphilic large molecule account for hydrophilic monomer weight, monomer weight, the control reaction temperature allows polymerization reaction carry out under stirring condition at 75～85 ℃;
(5), when treating that reactant liquor viscosity in the step (4) reaches 120～150 mPas reactant liquor is transferred in the flat vessel, allow polymerization reaction proceed in 10～30 ℃, form the higher organophilic gel film of water content;
(6), the organophilic gel film through peel off, wash, drying, obtain dry organophilic gel film;
(7), the organophilic gel film immersion concentration with drying is 0.1～10 molL
-1The proton conductor methanol solution saturated to swelling, through washing, drying, form high temperature proton exchange film in the end product organophilic gel base.
To further improvement in the technical proposal: hydrophilic monomer is acrylic monomer and/or propane sulfonic acid class monomer in the described step (2).
To further improvement in the technical proposal: amphiphilic large molecule is one or more mixtures in softex kw, polyethylene glycol or the gelatin in the described step (3).
To further improvement in the technical proposal: the crosslinking agent in the described step (4) is N, the N'-methylene-bisacrylamide.
To further improvement in the technical proposal: the initator in the described step (4) is potassium peroxydisulfate or ammonium persulfate.
To further improvement in the technical proposal: the proton conductor in the described step (7) is phosphoric acid or ionic liquid.
The present invention also provides high temperature proton exchange film in the described organophilic gel base, and described proton exchange membrane proton conductivity under 180 ℃ and water-less environment is 0.001-0.02 Scm
-1
The present invention also provides the application of high temperature proton exchange film in fuel cell in the described organophilic gel base.
Compared with prior art, advantage of the present invention and good effect are: the preparation method who the invention provides high temperature proton exchange film in a kind of organophilic gel base, specifically a kind of with hydrophilic monomer by preparing the organophilic gel film and adsorb the proton conductor methanol solution with amphiphilic large molecule graft modification, prepare the method for high temperature proton exchange film in the organophilic gel base by vacuumize.Hydrophilic monomer is acrylic monomer or propane sulfonic acid class monomer among the present invention, amphiphilic large molecule is softex kw, polyethylene glycol, gelatin, proton conductor is phosphoric acid or ionic liquid, and the proton conductivity of the organophilic gel matrix proton exchange that is synthesized under 180 ℃ and water-less environment can reach 0.001-0.02 Scm
-1Preparation method of the present invention is different from the preparation method of the proton exchange membrane of traditional proton conductor doping, and unique adsorptivity, loose structure and retentivity that the present invention takes full advantage of the organophilic gel film adsorb proton conductor three-dimensional net structure and the secure seal that enters the organophilic gel film.High temperature proton exchange film proton conductor adsorbance is large in the organophilic gel base of the present invention, proton conductivity is higher, operating temperature is wide, the preparation method is simple and easy to do, with low cost, room for improvement is large.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described in further detail.
Embodiment 1
The preparation method of high temperature proton exchange film may further comprise the steps in the organophilic gel base of the present invention:
1, the purifying of hydrophilic monomer: adopt the purifying of chemical pure hydrophilic monomer, remove polymerization inhibitor through vacuum decompression distillation or absorption purification.Described hydrophilic monomer is acrylic monomer and propane sulfonic acid class monomer.
2, the preparation of the hydrophilic monomer aqueous solution: by hydrophilic monomer: the mass ratio of water is 1:0.5～1.5, with the hydrophilic monomer dissolving, forms uniform monomer solution in water.
3, the preparation of amphiphilic macromolecular aqueous solution: by amphiphilic large molecule: the mass ratio of water is 1:1～1.5, with its dissolving, forms the amphiphilic large molecular solution of homogeneous in water.Described amphiphilic large molecule is softex kw, polyethylene glycol, gelatin etc.
4, the organophilic gel material is synthetic: under certain mixing speed, 0.2～0.5% the initator that adds 0.02～0.08% crosslinking agent, the monomer weight of 5～30% amphiphilic large molecule, the monomer weight of hydrophilic monomer weight, the control reaction temperature allows polymerization reaction carry out under stirring condition at 75～85 ℃.Crosslinking agent is N in the present embodiment, and N'-methylene-bisacrylamide, described initator are potassium peroxydisulfate, also can be ammonium persulfate.
5, organophilic gel thin film technology: when treating that reactant liquor viscosity in the step 4 reaches 120～150 mPas reactant liquor is transferred in the flat culture dish, allows polymerization reaction proceed in 10～30 ℃, form the higher organophilic gel film of water content.
6, dry organophilic gel thin film technology: the organophilic gel film through peel off, wash, drying, obtain dry organophilic gel film.
7, high temperature proton exchange film synthetic in the organophilic gel base: it is 0.1～10 molL that the organophilic gel film of drying is immersed concentration
-1The proton conductor methanol solution saturated to swelling, through washing, drying, form high temperature proton exchange film in the final products organophilic gel base.Described proton conductor is phosphoric acid or ionic liquid.
By said method, can obtain under 180 ° of C and water-less environment proton conductivity greater than 0.02 Scm
-1The organophilic gel base in the high temperature proton exchange.
Above embodiment is only in order to illustrating technical scheme of the present invention, but not limits it; Although with reference to previous embodiment the present invention is had been described in detail, for the person of ordinary skill of the art, still can make amendment to the technical scheme that previous embodiment is put down in writing, perhaps part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution break away from the spirit and scope of the present invention's technical scheme required for protection.
Claims (9)
1. the preparation method of high temperature proton exchange film in the organophilic gel base is characterized in that may further comprise the steps::
(1), hydrophilic monomer is removed polymerization inhibitor through purification;
(2), by hydrophilic monomer: the mass ratio of water is 1:0.5～1.5, with the hydrophilic monomer dissolving, forms uniform monomer solution in water;
(3), by amphiphilic large molecule: the mass ratio of water is 1:1～1.5, its dissolving is formed the solution of homogeneous in water;
(4), under stirring state, 0.2～0.5% the initator that adds 0.02～0.08% crosslinking agent, the monomer weight of 5～30% the amphiphilic large molecule account for hydrophilic monomer weight, monomer weight, the control reaction temperature allows polymerization reaction carry out under stirring condition at 75～85 ℃;
(5), when treating that reactant liquor viscosity in the step (4) reaches 120～150 mPas reactant liquor is transferred in the flat vessel, allow polymerization reaction proceed in 10～30 ℃, form the higher organophilic gel film of water content;
(6), the organophilic gel film through peel off, wash, drying, obtain dry organophilic gel film;
(7), the organophilic gel film immersion concentration with drying is 0.1～10 molL
-1The proton conductor methanol solution saturated to swelling, through washing, drying, form high temperature proton exchange film in the end product organophilic gel base.
2. the preparation method of high temperature proton exchange film in the organophilic gel base according to claim 1 is characterized in that: hydrophilic monomer is acrylic monomer and/or propane sulfonic acid class monomer in the described step (2).
3. the preparation method of high temperature proton exchange film in the organophilic gel base according to claim 2, it is characterized in that: amphiphilic large molecule is one or more mixtures in softex kw, polyethylene glycol or the gelatin in the described step (3).
4. the preparation method of high temperature proton exchange film in the organophilic gel base according to claim 1, it is characterized in that: the crosslinking agent in the described step (4) is N, the N'-methylene-bisacrylamide.
5. the preparation method of high temperature proton exchange film in the organophilic gel base according to claim 1, it is characterized in that: the initator in the described step (4) is potassium peroxydisulfate or ammonium persulfate.
6. the preparation method of high temperature proton exchange film in the organophilic gel base according to claim 3, it is characterized in that: the proton conductor in the described step (7) is phosphoric acid or ionic liquid.
7. high temperature proton exchange film in the organophilic gel base that makes of each described preparation method according to claim 1-6.
8. high temperature proton exchange film in the organophilic gel base according to claim 7 is characterized in that: described proton exchange membrane proton conductivity under 180 ℃ and water-less environment is 0.001-0.02 Scm
-1
9. the application of high temperature proton exchange film in fuel cell in the organophilic gel base according to claim 7.
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| CN201210520540.3A CN102983345B (en) | 2012-12-07 | 2012-12-07 | High temperature proton exchange film and its preparation method and application in hydrophobic gel base |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108039498A (en) * | 2017-12-26 | 2018-05-15 | 成都新柯力化工科技有限公司 | A kind of method of modifying of polyphenylacetylene modification fuel battery proton exchange film |
| CN110797554A (en) * | 2019-11-08 | 2020-02-14 | 重庆大学 | Hydrogel solid electrolyte micro fuel cell with built-in fuel tank |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101842931A (en) * | 2007-08-29 | 2010-09-22 | 科学与工业研究委员会 | Proton conducting polymer electrolyte membrane useful in polymer electrolyte fuel cells |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101842931A (en) * | 2007-08-29 | 2010-09-22 | 科学与工业研究委员会 | Proton conducting polymer electrolyte membrane useful in polymer electrolyte fuel cells |
Non-Patent Citations (1)
| Title |
|---|
| QUNWEI TANG ET.AL: "High- temperature proton exchange membranes from ionic liquid absorbed/doped superabsorbents", 《JOURNAL OF MATERIALS CHEMISTRY》, vol. 22, no. 31, 17 May 2012 (2012-05-17), pages 15836 - 15844 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108039498A (en) * | 2017-12-26 | 2018-05-15 | 成都新柯力化工科技有限公司 | A kind of method of modifying of polyphenylacetylene modification fuel battery proton exchange film |
| CN108039498B (en) * | 2017-12-26 | 2020-08-07 | 成都新柯力化工科技有限公司 | Modification method for fuel cell proton exchange membrane modified by polyphenylacetylene |
| CN110797554A (en) * | 2019-11-08 | 2020-02-14 | 重庆大学 | Hydrogel solid electrolyte micro fuel cell with built-in fuel tank |
| CN110797554B (en) * | 2019-11-08 | 2020-12-29 | 重庆大学 | Hydrogel solid electrolyte micro fuel cell with built-in fuel tank |
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