CN109193012A - A kind of compound proton exchange membrane and preparation method thereof for hydrogen fuel cell - Google Patents
A kind of compound proton exchange membrane and preparation method thereof for hydrogen fuel cell Download PDFInfo
- Publication number
- CN109193012A CN109193012A CN201810913971.3A CN201810913971A CN109193012A CN 109193012 A CN109193012 A CN 109193012A CN 201810913971 A CN201810913971 A CN 201810913971A CN 109193012 A CN109193012 A CN 109193012A
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- polymer
- fuel cell
- proton exchange
- exchange membrane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The compound proton exchange membrane and preparation method thereof that the invention discloses a kind of for hydrogen fuel cell, the membrane material is prepared by LBL self-assembly method, first Nafion membrane is immersed in the solution of polymer, then it is immersed in again in the solution of nanotube dispersion, obtains carbon nano-tube film/polymer/Nafion/ polymer/carbon nano-tube film hamburger structural membrane using the method.A kind of compound proton exchange membrane and preparation method thereof for hydrogen fuel cell proposed by the present invention, manufacturing process precision is high, the high performance compound proton exchange membrane applied to hydrogen fuel cell can be made, not only structural regularity is high for resulting membrane material, dimensionally stable is good, and the proton conductivity of film improves.
Description
Technical field
The present invention relates to hydrogen fuel cell field, especially a kind of compound proton exchange membrane for hydrogen fuel cell and its
Preparation method.
Background technique
Hydrogen fuel cell has energy conversion rate height, pollutant emission as one of 21 century most important green science and technology
The advantages that amount is less, fuel source is wide and safety coefficient is high, it is considered to be most possible substitution conventional fossil fuel etc. is non-renewable
Resource.The energy shortage faced for the current world and problem of environmental pollution, fuel cell have unrivaled advantage, energy
Enough the mankind is helped to solve problem of environmental pollution and the Dependence Problem for non-renewable resources such as petroleum.From last century 70 years
Generation, the research of China's fuel cell achieve breakthrough, and fuel cell is according to the difference of operating condition and electrolyte type
Can there are many, for example, the difference according to operating temperature can be divided into low-temperature fuel cell and high-temperature fuel cell, according to electrolyte
The difference of type can be divided into Proton Exchange Membrane Fuel Cells, phosphoric acid type fuel cell, solid oxide fuel cell, alkalinity
Fuel cell, fused carbonate type fuel cell, wherein Proton Exchange Membrane Fuel Cells is using proton exchange membrane as electrolyte；Pt,
The pith that Pt/C is formed as cathode, proton exchange membrane as Proton Exchange Membrane Fuel Cells as anode, Pt, Pt/C,
It mainly include low-temperature protonic exchange membrane, high temperature proton exchange film, perfluorosulfonic acid type proton exchange membrane, sulfonated poly aryl ether ketone/sulfone, sulphur
Change the polyarylether of polyarylether and surveyor's chain containing basic group of polyimides, polybenzimidazoles, main chain containing basic group.Existing matter
There are the defects such as small mechanical strength, poor dimensional stability, proton conductivity be low more in proton exchange, influence and limit proton exchange
A possibility that application of film.
Summary of the invention
In order to overcome the above-mentioned problems in the prior art, the dimensional stability and proton conduction of proton exchange membrane are improved
Rate, the compound proton exchange membrane and preparation method thereof that the invention proposes a kind of for hydrogen fuel cell.
The technical solution adopted by the present invention to solve the technical problems is: a kind of composite proton friendship for hydrogen fuel cell
Film and preparation method thereof, including Nafion membrane, polymer, carbon nanotube layer are changed, the polymer includes first polymer layer,
Dimerization nitride layer, the carbon nanotube layer include the first carbon nanotube layer and the second carbon nanotube layer；The composite proton exchange
Membrane material is prepared by LBL self-assembly method, and first Nafion membrane is immersed in the solution of polymer, is then immersed in again
In the solution of nanotube dispersion, carbon nano-tube film/polymer/Nafion/ polymer/carbon nano-tube is obtained using the method
The hamburger structural membrane of film.
A kind of above-mentioned compound proton exchange membrane and preparation method thereof for hydrogen fuel cell, the Nafion membrane are warp
Cross the Du Pont company of preprocessing process115 commercialization films.
A kind of above-mentioned compound proton exchange membrane and preparation method thereof for hydrogen fuel cell, the preprocessing process is such as
Under:
(1) will115 commercialization films are placed in the H of 80 DEG C, 4~5wt.%2O2In solution handle 50~60min with
Remove metal and organic pollutant；
(2) above-mentioned steps (1) is handled resulting115 commercialization films are placed in the H of 80 DEG C, 0.5M2SO4Solution
Middle processing 1h removes the remaining a small amount of metal impurities of film surface, while being acidified to film；
(3) above-mentioned steps (2) are handled into resulting film and cleans boiling repeatedly in deionized water, until the pH in aqueous solution
>=6.5, with except striping memory excess acid；
(4) by above-mentioned steps (3), treated that film dries in 100 DEG C of vacuum oven that 24~36h obtains pre- place
Nafion membrane after reason.
A kind of above-mentioned compound proton exchange membrane and preparation method thereof for hydrogen fuel cell, the polymer are poly- two
Allyl dimethyl ammonium chloride or polydiallyldimethyl ammonium chloride.
A kind of above-mentioned compound proton exchange membrane and preparation method thereof for hydrogen fuel cell, the carbon nanotube dispersion
The preparation process of liquid solution includes:
(1) come into full contact with carbon nanotube with oxygenatedchemicals, and it is anti-to make the side wall of the carbon nanometer that functionalization occur
It answers；
(2) make functionalized carbon nanotube and at least one polymer reaction, polymer is sufficiently coupled to the carbon and is received
On the side wall of mitron；
(3) step (2) resulting carbon nanotube is dispersed in aprotic solvent, it is molten to obtain nanotube dispersion
Liquid.
A kind of above-mentioned compound proton exchange membrane and preparation method thereof for hydrogen fuel cell, the oxygenatedchemicals are
Peroxide, primary ozonide, secondary one of ozonide or carboxylic oxo-compound or two kinds of mixture.
A kind of above-mentioned compound proton exchange membrane and preparation method thereof for hydrogen fuel cell, the aprotic solvent by
The mixed solvent of one or both of halogenated solvent, carbonylation solvent, etherificate solvent, acid anhydrides solvent composition.
A kind of above-mentioned compound proton exchange membrane and preparation method thereof for hydrogen fuel cell, at least one polymerization
Object be poly- (styrene-isopropylene-alpha, alpha-dimethylbenzyl isocyanates), poly- (isocyanic acid-ethylmethyl acrylate) and
One of poly- (3- isopropenyl-alpha, alpha-dimethylbenzyl isocyanates) or two or more mixtures.
The invention has the advantages that the present invention proposes a kind of compound proton exchange membrane and its system for hydrogen fuel cell
Preparation Method, manufacturing process precision is high, and the high performance compound proton exchange membrane applied to hydrogen fuel cell, gained can be made
Membrane material not only structural regularity is high, dimensionally stable is good, and the proton conductivity of film improves.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is schematic structural view of the invention；
Fig. 2 is the ion exchange capacity figure of film in the present invention.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, with reference to the accompanying drawing and specific embodiment party
Formula elaborates to the present invention.
[embodiment 1]
A kind of compound proton exchange membrane and preparation method thereof for hydrogen fuel cell, including Nafion membrane 3, polymer,
Carbon nanotube layer, the polymer include first polymer layer 2, the second polymer layer 4, and the carbon nanotube layer includes the first carbon
Nanotube layer 1 and the second carbon nanotube layer 5；The composite proton exchange membrane material is prepared by LBL self-assembly method, first
Nafion membrane 3 is immersed in the solution of polymer, is then immersed in again in the solution of nanotube dispersion, utilizes the method
Obtain carbon nano-tube film/polymer/Nafion/ polymer/carbon nano-tube film hamburger structural membrane.Wherein, the Nafion
Film 3 is the Du Pont company by preprocessing process115 commercialization films, the preprocessing process are as follows:
(1) will115 commercialization films are placed in the H of 80 DEG C, 4wt.%2O260min is handled in solution to remove gold
Category and organic pollutant；
(2) above-mentioned steps (1) is handled resulting115 commercialization films are placed in the H of 80 DEG C, 0.5M2SO4Solution
Middle processing 1h removes the remaining a small amount of metal impurities of film surface, while being acidified to film；
(3) above-mentioned steps (2) are handled into resulting film and cleans boiling repeatedly in deionized water, until the pH in aqueous solution
>=6.5, with except striping memory excess acid；
(4) by above-mentioned steps (3), treated that film dries in 100 DEG C of vacuum oven after 36h obtains pretreatment
Nafion membrane.
The preparation process of the nanotube dispersion solution includes:
(1) come into full contact with carbon nanotube with oxygenatedchemicals, and it is anti-to make the side wall of the carbon nanometer that functionalization occur
It answers, the oxygenatedchemicals is the mixture in peroxide and carboxylic oxo-compound；
(2) make functionalized carbon nanotube and poly- (styrene-isopropylene-alpha, alpha-dimethylbenzyl isocyanates) anti-
It answers, polymer is sufficiently coupled on the side wall of the carbon nanotube；
(3) step (2) resulting carbon nanotube is dispersed in aprotic solvent, it is molten to obtain nanotube dispersion
Liquid, the aprotic solvent are mixed by halogenated solvent, carbonylation two kinds of solvents of solvent.
[embodiment 2]
A kind of compound proton exchange membrane and preparation method thereof for hydrogen fuel cell, including Nafion membrane 3, polymer,
Carbon nanotube layer, the polymer include first polymer layer 2, the second polymer layer 4, and the carbon nanotube layer includes the first carbon
Nanotube layer 1 and the second carbon nanotube layer 5；The composite proton exchange membrane material is prepared by LBL self-assembly method, first
Nafion membrane 3 is immersed in the solution of polymer, is then immersed in again in the solution of nanotube dispersion, utilizes the method
Obtain carbon nano-tube film/polymer/Nafion/ polymer/carbon nano-tube film hamburger structural membrane.The wherein Nafion membrane
3 is by the Du Pont companies of preprocessing process115 commercialization films, the preprocessing process are as follows:
(1) will115 commercialization films are placed in the H of 80 DEG C, 5wt.%2O250min is handled in solution to remove metal
And organic pollutant；
(2) above-mentioned steps (1) is handled resulting115 commercialization films are placed in the H of 80 DEG C, 0.5M2SO4Solution
Middle processing 1h removes the remaining a small amount of metal impurities of film surface, while being acidified to film；
(3) above-mentioned steps (2) are handled into resulting film and cleans boiling repeatedly in deionized water, until the pH in aqueous solution
>=6.5, with except striping memory excess acid；
(4) by above-mentioned steps (3), treated that film dries in 100 DEG C of vacuum oven after 30h obtains pretreatment
Nafion membrane.
The preparation process of the nanotube dispersion solution includes:
(1) come into full contact with carbon nanotube with oxygenatedchemicals, and it is anti-to make the side wall of the carbon nanometer that functionalization occur
It answers；The oxygenatedchemicals is the mixture of peroxide and secondary ozonide；
(2) make functionalized carbon nanotube and poly- (isocyanic acid-ethylmethyl acrylate), poly- (3- isopropenyl-α, α-
Dimethyl benzyl isocyanate) reaction, polymer is sufficiently coupled on the side wall of the carbon nanotube；
(3) step (2) resulting carbon nanotube is dispersed in aprotic solvent, it is molten to obtain nanotube dispersion
Liquid, wherein aprotic solvent is carbonylation solvent.
Above embodiments are only exemplary embodiment of the present invention, are not used in the limitation present invention, protection scope of the present invention
It is defined by the claims.Those skilled in the art can within the spirit and scope of the present invention make respectively the present invention
Kind modification or equivalent replacement, this modification or equivalent replacement also should be regarded as being within the scope of the present invention.
Claims (8)
1. a kind of compound proton exchange membrane and preparation method thereof for hydrogen fuel cell, including Nafion membrane (3), polymer,
Carbon nanotube layer, it is characterised in that: the polymer includes first polymer layer (2), the second polymer layer (4), and the carbon is received
Mitron layer includes the first carbon nanotube layer (1) and the second carbon nanotube layer (5)；The composite proton exchange membrane material is by layer by layer
Prepared by self-assembly method, first Nafion membrane (3) is immersed in the solution of polymer, is then immersed in carbon nanotube dispersion again
In the solution of body, carbon nano-tube film/polymer/Nafion/ polymer/carbon nano-tube film hamburger inclusion is obtained using the method
Structure film.
2. a kind of compound proton exchange membrane and preparation method thereof for hydrogen fuel cell according to claim 1, special
Sign is that the Nafion membrane (3) is the Du Pont company by preprocessing process115 commercialization films.
3. a kind of compound proton exchange membrane and preparation method thereof for hydrogen fuel cell according to claim 2, special
Sign is that the preprocessing process is as follows:
(1) will115 commercialization films are placed in the H of 80 DEG C, 4~5wt.%2O250~60min is handled in solution to remove
Metal and organic pollutant；
(2) above-mentioned steps (1) is handled resulting115 commercialization films are placed in the H of 80 DEG C, 0.5M2SO4In solution
It manages 1h and removes the remaining a small amount of metal impurities of film surface, while film is acidified；
(3) above-mentioned steps (2) are handled into resulting film and clean boiling repeatedly in deionized water, until the pH in aqueous solution >=
6.5, with except striping memory excess acid；
(4) by above-mentioned steps (3), treated that film dries in 100 DEG C of vacuum oven after 24~36h obtains pretreatment
Nafion membrane.
4. a kind of compound proton exchange membrane and preparation method thereof for hydrogen fuel cell according to claim 1, special
Sign is that the polymer is diallyl dimethyl ammoniumchloride or polydiallyldimethyl ammonium chloride.
5. a kind of compound proton exchange membrane and preparation method thereof for hydrogen fuel cell according to claim 1, special
Sign is that the preparation process of the nanotube dispersion solution includes:
(1) it comes into full contact with carbon nanotube with oxygenatedchemicals, and makes the side wall of the carbon nanometer that functionalization occur；
(2) make functionalized carbon nanotube and at least one polymer reaction, polymer is sufficiently coupled to the carbon nanotube
Side wall on；
(3) step (2) resulting carbon nanotube is dispersed in aprotic solvent, to obtain nanotube dispersion solution.
6. a kind of compound proton exchange membrane and preparation method thereof for hydrogen fuel cell according to claim 5, special
Sign is that the oxygenatedchemicals is one in peroxide, primary ozonide, secondary ozonide or carboxylic oxo-compound
The mixtures of kind or two kinds of compositions.
7. a kind of compound proton exchange membrane and preparation method thereof for hydrogen fuel cell according to claim 5, special
Sign is that the aprotic solvent is by one of halogenated solvent, carbonylation solvent, etherificate solvent, acid anhydrides solvent or two kinds
Mixed solvent.
8. a kind of compound proton exchange membrane and preparation method thereof for hydrogen fuel cell according to claim 5, special
Sign is that at least one polymer is poly- (styrene-isopropylene-alpha, alpha-dimethylbenzyl isocyanates), poly- (isocyanide
Acid-ethylmethyl acrylate) and one of poly- (3- isopropenyl-alpha, alpha-dimethylbenzyl isocyanates) or two kinds with
On mixture.
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| CN201810913971.3A CN109193012A (en) | 2018-08-13 | 2018-08-13 | A kind of compound proton exchange membrane and preparation method thereof for hydrogen fuel cell |
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| CN201810913971.3A CN109193012A (en) | 2018-08-13 | 2018-08-13 | A kind of compound proton exchange membrane and preparation method thereof for hydrogen fuel cell |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2007089550A2 (en) * | 2006-01-26 | 2007-08-09 | Nanoselect, Inc. | Cnt-based sensors: devices, processes and uses thereof |
| CN101970550A (en) * | 2007-11-23 | 2011-02-09 | 奈诺莱吉公司 | Polymer carbon nanotube composites |
| CN103358612A (en) * | 2012-03-26 | 2013-10-23 | 上海中科高等研究院 | Methanol rejective membrane for direct methanol fuel cell as well as preparation method and application thereof |
| CN104701549A (en) * | 2013-12-06 | 2015-06-10 | 中国科学院上海高等研究院 | A carbon-free membrane electrode assembly |
-
2018
- 2018-08-13 CN CN201810913971.3A patent/CN109193012A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007089550A2 (en) * | 2006-01-26 | 2007-08-09 | Nanoselect, Inc. | Cnt-based sensors: devices, processes and uses thereof |
| CN101970550A (en) * | 2007-11-23 | 2011-02-09 | 奈诺莱吉公司 | Polymer carbon nanotube composites |
| CN103358612A (en) * | 2012-03-26 | 2013-10-23 | 上海中科高等研究院 | Methanol rejective membrane for direct methanol fuel cell as well as preparation method and application thereof |
| CN104701549A (en) * | 2013-12-06 | 2015-06-10 | 中国科学院上海高等研究院 | A carbon-free membrane electrode assembly |
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