CN1224119C - Humidity preservation composite film used for proton exchange film fuel battery and its preparation method - Google Patents
Humidity preservation composite film used for proton exchange film fuel battery and its preparation method Download PDFInfo
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- CN1224119C CN1224119C CNB021038325A CN02103832A CN1224119C CN 1224119 C CN1224119 C CN 1224119C CN B021038325 A CNB021038325 A CN B021038325A CN 02103832 A CN02103832 A CN 02103832A CN 1224119 C CN1224119 C CN 1224119C
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
- Y02A40/924—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation using renewable energies
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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 provides to a self-humidity preservation composite membrane for proton exchange membrane fuel batteries and a method for preparing the composite membrane, which relates to a thin polymer membrane structure for fuel batteries and a method for preparing the thin polymer membrane structure. The composite membrane is formed by the combination of a proton exchange organic membrane and a coating with a humidity preserving function, wherein the coating is formed by that inorganic matter or oxide powders thereof are added in organic solution of organic matter containing the same constituents as the organic membrane, and then, the organic solution is coated on one side or both sides of the organic membrane. The present invention has the preparing method that an organic membrane with a proton exchanging capability is selected as a basal body, inorganic matter or oxide thereof is pulverized into powders with the diameters of 0.1 to 10 micrometers, and the powders, organic matter having the same constituents as the organic membrane, and organic solvent are uniformly mixed to obtain slurry; the slurry is coated on the surface of the organic membrane basal body, dried and solidified, and then, the self-humidity preservation composite membrane can be obtained. The present invention can be used as a proton exchange membrane for fuel batteries and does not need additional humidification, and the present invention can effectively simplify components of fuel batteries and reduce the cost of fuel batteries.
Description
Technical field
The present invention relates to a kind of structure and preparation method thereof of polymer film of used in proton exchange membrane fuel cell.
Background technology
In Proton Exchange Membrane Fuel Cells, can carry out proton exchange in order to make polymer film, it is moistening to need film itself to remain.The way that solves in the prior art is in advance with fuel gas and oxidant humidification, so that film keeps is moistening, this just need be provided with damping device in fuel cell system.
Du pont company G draws " laminated diaphragm that is used for the fuel cell of direct fueling " patent of invention ([application number] 97180928.3) of Zhan Delan application, this patent relates to a kind of cation exchange membrane, and it has the laminated construction of at least three layers of cation exchange polymer.In barrier film according to this invention, cation exchange polymer in the lamination has main polymer chain and the cation exchange base that is stated from the repetition side chain, this side chain is attached on the main polymer chain with some relevant with the cation exchange base in main polymer chain carbon atoms, this exchange base is determined every layer ion exchange ratio (IXR), layer has different IXR values, it provides one or more layers high IXR layer and one or more layers low IXR layer, the IXR of this low IXR layer less than about 17 and the IXR of this high IXR layer be at least about 15.In the barrier film according to this invention, high and at least two positions of low layer on the membrane thicknesses direction also have and are at least about 2 IXR variation.This patent is the multilayer organic hybrid films, can be used for fuel cell, but does not have moisture-keeping function, has limited its range of application.
In " preparation method of the polyimides of ultra low heat expansion coefficient/clay nano composite membrane " of Zhejiang University's application ([application number] 00101315.7), a kind of prepare organic and method inorganic substances compound membrane are disclosed, promptly in reactor, use oxolane/methanol mixed dissolution with solvents aromatic diamines, add aromatic anhydride again and tertiary amine reacts, obtain the polyamic acid salting liquid; Organized clay poured in oxolane/methanol mixed solvent form the clayish solution that organises.Be poured on the glass plate after two solution are stirred into polyamic acid salt/organized clay solution; spread to the film of desired thickness with film forming device; temperature program(me) oven dry and curing to set under nitrogen protection; be cooled to room temperature; take off from glass plate, promptly do not contained the film that residual solvent has the super-low expansion coefficient.But this film can not be used for fuel cell fully as dielectric film.
" method for making of composite porous polymetafluoroethylefilm film " ([application number] 98103152.8) patent of invention of Motianmo Tech. Engineering Co., Tianjin Textile Polytechnical College's application, this patent relates to the method for making of composite porous polymetafluoroethylefilm film.It is characterized in that with Kynoar or polyvinylidene blending thing be basement membrane, by chemical reaction or irradiation to its surface modification, make it to form C=C ,-OH ,-COOH ,-the active growth point of COOR or free radical, make basement membrane and functional high-polymer or polymer monomer carry out graft reaction again, make its surface form loose type composite bed; For itself had C=C ,-OH ,-the polyvinylidene blending thing basement membrane of COOH, COOR or free radical, directly carry out graft reaction, form loose type composite bed.The inventive method products obtained therefrom has better resistance tocrocking and selects separating effect.This patent is an organic hybrid films, but can not be used for fuel cell fully as dielectric film.
Summary of the invention
The purpose of this invention is to provide humidity preservation composite film of a kind of used in proton exchange membrane fuel cell and preparation method thereof, can be used for fuel cell, be intended to simplify the parts and the operational procedure of fuel cell, reduce the cost of fuel cell as dielectric film.
Technical scheme of the present invention is as follows: a kind of used in proton exchange membrane fuel cell humidity preservation composite film, comprise proton exchange organic membrane matrix, it is characterized in that: this composite membrane is to be composited by proton exchange organic membrane matrix and the coating with moisture-keeping functions, described coating is to add inorganic matter or its oxide powder in containing the organic organic solution identical with the organic membrane composition, is coated in the one or both sides of organic membrane.
The inorganic matter that adds in coating or its oxide are generally silicon, titanium, aluminium, manganese, nickel, cobalt, iron or its oxide.The thickness of coating should guarantee that contained inorganic matter or its oxide remain on 0.1～5 milligram/square centimeter.
A kind of method for preparing described used in proton exchange membrane fuel cell humidity preservation composite film may further comprise the steps:
(1) chooses organic membrane and make matrix with proton exchange ability;
(2) inorganic matter or its oxide are pulverized, made 0.1～10 micron powder;
(3) choose and the identical organic substance of organic membrane matrix composition, make organic solution, evenly mix with powder in the step (2), make slurry, wherein content of powder is 0.1～10%;
(4) mixture paste is coated in the surface of organic membrane matrix, under inert atmosphere, oven dry, solidifies;
(5) repeating step (4), the inorganic matter in coating layer thickness or its oxide remain on 0.1～5 milligram/square centimeter.
Used organic solvent can be any in isopropyl alcohol, benzene, dimethyl formamide, acetone or the chloroform.
The present invention compares with the employed common organic membrane of existing fuel cell, himself has the characteristics that keep moisture content, can be used for fuel cell as dielectric film, does not need other humidification; Thereby can effectively simplify the parts of fuel cell and the cost of reduction fuel cell.
Description of drawings
Fig. 1 is the cated humidity preservation composite film of a side.
Fig. 2 is the cated humidity preservation composite films in both sides.
Fig. 3 is the fuel cell performance curve that contains titanium dioxide composite film.
Fig. 4 is the stability test result who contains the fuel cell of titanium dioxide composite film.
Among the figure: 1-organic membrane matrix; The 2-coating
Embodiment
The present invention is matrix with the organic membrane 1 that uses in the fuel cell, is composited with the coating 2 with moisture-keeping functions.Coating is to mix the made slurry in back with containing organic substance, organic solution and the inorganic matter identical with organic membrane matrix composition or its oxide powder, then this slurry is coated in the one or both sides of matrix.Used organic solvent should be according to the organic difference that is adopted and is different, uses isopropyl alcohol, benzene, dimethyl formamide, acetone or chloroform to be organic solvent usually.The thickness of coating should be as the criterion with the amount of its every square centimeter inorganic matter that contains or its oxide, generally remains on 0.1～5 milligram/square centimeter, can repetitive coatings.
Embodiment 1:
(a) choose the full fluorin proton exchange film of selling in market and make matrix;
(b) the silica 1 gram is pulverized, sieved, getting particle mean size is 0.15 micron powder;
(c) SiO 2 powder and water, isopropyl alcohol, the perfluorinated sulfonic acid after will pulverizing mixes with homogenizer, makes slurry, and wherein the content of silicon dioxide is 5%;
(d) will make the surface that slurry evenly spreads upon the organic membrane matrix, spread to the film of desired thickness with film forming device; And in pure air stream, be warming up to 150 ℃ with 5 ℃ of/minute speed, dry 2 hours, naturally cool to room temperature then;
(e) the repetition previous step is rapid, remains on 2 milligrams/square centimeter up to dioxide-containing silica, promptly makes to have the used in proton exchange membrane fuel cell humidity preservation composite film.
Effect: when Hydrogen Vapor Pressure is 2atm, oxygen pressure is 2.4atm, and temperature is 80 ℃, and when the monocell operating pressure was 0.7V, its current density can reach 0.8A/cm
2More than.
Embodiment 2:
(a) get Kynoar (PVDF) organic membrane and make matrix;
(b) with 1 gram simple substance cobalt crushing screening, particle diameter is 5 microns a powder;
(c) above-mentioned cobalt dust, Kynoar organic substance and dimethyl formamide are stirred, make slurry, wherein cobalt dust content is 10%;
(d) slurry that makes is evenly spread upon the surface, one or both sides of organic membrane matrix, dry, be cooled to room temperature;
(e) the repetition previous step is rapid, and straight cobalt content remains on 5 milligrams/square centimeter, promptly makes to have the used in proton exchange membrane fuel cell humidity preservation composite film.
Effect: when Hydrogen Vapor Pressure is 2.4atm, oxygen pressure is 2.4atm, and temperature is 80 ℃, and when the monocell operating pressure was 0.7V, its current density can reach 0.7A/cm
2More than.
Embodiment 3:
(a) choose the full fluorin proton exchange film of selling in market and make matrix;
(b) titanium dioxide 1 gram is pulverized, sieved, getting particle mean size is 1 micron powder;
(c) titania powder and water, isopropyl alcohol, the perfluorinated sulfonic acid after will pulverizing mixes with homogenizer, makes slurry, and wherein the content of titanium dioxide is 3%;
(d) will make the surface that slurry evenly spreads upon the organic membrane matrix, spread to the film of desired thickness with film forming device; And in pure air stream, be warming up to 150 ℃ with 10 ℃ of/minute speed, dry 2 hours, naturally cool to room temperature then;
(e) the repetition previous step is rapid, remains on 0.1 milligram/square centimeter up to dioxide-containing silica, promptly makes to have the used in proton exchange membrane fuel cell humidity preservation composite film.
Effect: when Hydrogen Vapor Pressure is 2.6atm, oxygen pressure is 2.8atm, and temperature is 80 ℃, and when the monocell operating pressure was 0.7V, its current density can reach 1.5A/cm
2(seeing shown in Figure 3).And its stability is fine, long-time stable discharging between 0.55～0.6V, discharging current 2.34A/cm
2(see figure 4)
Claims (3)
1, a kind of humidity preservation composite film of used in proton exchange membrane fuel cell comprises proton exchange organic membrane matrix, it is characterized in that; This composite membrane is to be composited by proton exchange organic membrane matrix (1) and coating (2) with moisture-keeping functions, described coating is to add at least a in inorganic matter or its oxide powder in containing the organic organic solution identical with the organic membrane composition, is coated in the one or both sides of organic membrane; The inorganic material powders that adds in the described coating is silicon, titanium, aluminium, manganese, nickel, cobalt or iron; Described organic solution is to be solvent with in isopropyl alcohol, benzene, dimethyl formamide, acetone or the chloroform any.
2, according to the humidity preservation composite film of the described used in proton exchange membrane fuel cell of claim 1, it is characterized in that: inorganic matter or its oxide contained in the described coating remain on 0.1～5 milligram/square centimeter.
3, a kind of preparation method of humidity preservation composite film according to claim 1 may further comprise the steps:
(1) chooses organic membrane and make matrix with proton exchange ability;
(2) inorganic matter or its oxide are pulverized, made 0.1～10 micron powder, described inorganic matter is silicon, aluminium, manganese, nickel, cobalt or iron and their oxide;
(3) choose and the identical organic substance of organic membrane matrix composition, make organic solution with isopropyl alcohol, benzene, dimethyl formamide, acetone or chloroform as solvent, evenly mix with powder in the step (2), make slurry, wherein content of powder is 0.1～10%:
(4) slurry is coated in the surface of organic membrane matrix, under inert atmosphere, oven dry, solidifies;
(5) repeating step (4), the inorganic matter in coating layer thickness or its oxide reach 0.1～5 milligram/square centimeter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021038325A CN1224119C (en) | 2002-03-29 | 2002-03-29 | Humidity preservation composite film used for proton exchange film fuel battery and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021038325A CN1224119C (en) | 2002-03-29 | 2002-03-29 | Humidity preservation composite film used for proton exchange film fuel battery and its preparation method |
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| CN1442913A CN1442913A (en) | 2003-09-17 |
| CN1224119C true CN1224119C (en) | 2005-10-19 |
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| CNB021038325A Expired - Fee Related CN1224119C (en) | 2002-03-29 | 2002-03-29 | Humidity preservation composite film used for proton exchange film fuel battery and its preparation method |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345326C (en) * | 2004-05-14 | 2007-10-24 | 武汉理工大学 | Unit combined high temperature proton exchange film fuel cell membrane electrode and preparation |
| KR101135479B1 (en) | 2005-01-26 | 2012-04-13 | 삼성에스디아이 주식회사 | A polymer electrolyte membrane for fuel cell, a method for preparing the same, and a fuel cell system comprising the same |
| KR100670284B1 (en) | 2005-02-04 | 2007-01-16 | 삼성에스디아이 주식회사 | Fuel cell |
| CN100336257C (en) * | 2005-05-20 | 2007-09-05 | 武汉理工大学 | Composite proton exchange film for anti-gas osmosising fuel cell and production thereof |
| CN100446314C (en) * | 2005-06-17 | 2008-12-24 | 新源动力股份有限公司 | Multilayer composite proton exchange membrane for self-humidifying fuel cell and synthesis method |
| CN100356623C (en) * | 2005-07-01 | 2007-12-19 | 清华大学 | Self-humidifying method for fuel cell |
| US20070275291A1 (en) * | 2006-05-10 | 2007-11-29 | Horizon Fuel Cell Technologies Pte. Ltd | Novel membrane electrode assembly and its manufacturing process |
| CN101235268B (en) * | 2007-12-27 | 2010-04-21 | 中国科学院长春应用化学研究所 | Moisture-absorbing and water-retaining composite film and its preparation method |
| CN109921077A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院大连化学物理研究所 | An organic-inorganic composite membrane and its preparation and application |
| CN111146482A (en) * | 2019-12-10 | 2020-05-12 | 一汽解放汽车有限公司 | Self-humidifying proton exchange membrane and preparation method and application thereof |
| CN112038674A (en) * | 2020-08-20 | 2020-12-04 | 珠海格力电器股份有限公司 | Proton exchange membrane, method for making the same, and fuel cell |
| CN114108017B (en) * | 2021-12-03 | 2022-11-08 | 中国科学院大连化学物理研究所 | Enhanced PEM water electrolysis proton exchange membrane and continuous preparation method thereof |
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Granted publication date: 20051019 Termination date: 20120329 |