CN109560311A - Proton exchange membrane and preparation method thereof for methanol fuel cell - Google Patents
Proton exchange membrane and preparation method thereof for methanol fuel cell Download PDFInfo
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- CN109560311A CN109560311A CN201811334323.9A CN201811334323A CN109560311A CN 109560311 A CN109560311 A CN 109560311A CN 201811334323 A CN201811334323 A CN 201811334323A CN 109560311 A CN109560311 A CN 109560311A
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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
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
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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
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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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
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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
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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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
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- Y02E60/50—Fuel cells
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Abstract
The proton exchange membrane and preparation method thereof that the invention discloses a kind of for methanol fuel cell, middle layer is polyvinylidene fluoride layer, Kynoar is up and down sulfonated polyether-ether-ketone layer, and the mass ratio of sulfonated polyether-ether-ketone layer and polyvinylidene fluoride layer is 1:(0.3~0.4).Polyvinylidene fluoride layer is used to inhibit the methanol permeability of proton exchange membrane in the present invention, sulfonated polyether-ether-ketone layer is used to improve the proton conductivity of proton exchange membrane, so that proton exchange membrane while keeping high proton conductivity, also has low methanol permeability.
Description
Technical field
The present invention relates to fuel cell field more particularly to a kind of proton exchange membrane and its system for methanol fuel cell
Preparation Method.
Background technique
Methanol fuel cell belongs to one of Proton Exchange Membrane Fuel Cells (PEMFC) class, directly uses methanol aqueous solution
Or steam methane is that fuel supplies source, without the reformation hydrogen production by methanol, gasoline and natural gas for power generation.In fuel
Inside battery, proton exchange membrane provide channel for the migration and conveying of proton, so that proton reaches cathode from anode by film, with
The electronics transfer of external circuit constitutes circuit, outwardly provides electric current, therefore the performance of proton exchange membrane is to the performance of fuel cell
Very important effect is played, its quality directly affects the service life of battery.But the methanol of proton exchange membrane seeps at present
Saturating rate is relatively high, leverages the development and application of direct methanol fuel cell.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of for the proton exchange membrane of methanol fuel cell and its preparation side
Method while the proton exchange membrane has high proton conductivity, also has low methanol permeability.
To achieve the goals above, the invention provides the following technical scheme:
A kind of proton exchange membrane for methanol fuel cell, middle layer are polyvinylidene fluoride layer, the Kynoar
It is up and down sulfonated polyether-ether-ketone layer；
The sulfonated polyether-ether-ketone layer, the raw material including following parts by weight:
The mass ratio of the polyvinylidene fluoride layer and the polyvinylidene fluoride layer is 1:(0.3~0.4).
Preferably, the polyvinylidene fluoride layer, the raw material including following parts by weight:
10~20 parts of Kynoar；
2~4 parts of starch-acrylate graft copolymer.
Preferably, the sulfonation degree 50%~80% of the sulfonated polyether-ether-ketone.
The present invention also provides a kind of above-mentioned preparation method of the proton exchange membrane for methanol fuel cell, including it is following
Step:
A) Kynoar and starch-acrylate graft copolymer are added in organic solvent, after mixing evenly, are poured into
In culture dish, be subsequently placed in 60~80 DEG C of baking oven and be dried, and control solvent residual amount be 30~40wt%, by film from
Culture dish surface is uncovered, and is put into the sodium hydroxide solution that concentration is 1mol/L and is boiled 1~2h, place into water and boil 20~
30min, drying obtain polyvinylidene fluoride layer；
B) by sulfonated polyether-ether-ketone, butadiene-styrene rubber, polyacrylonitrile-based carbon fibre, stearic acid pentaerythritol ester, silicon carbide, oxidation
Graphene, lithium phosphate are added in organic solvent, are obtained sulfonated polyether-ether-ketone solution after mixing evenly, are poured into culture dish；
C) step a) polyvinylidene fluoride layer is put into the sulfonated polyether-ether-ketone solution that step b) is obtained, 60~80 DEG C of drying
10~12h to obtain the final product.
Preferably, in step a) and step b), the organic solvent is respectively selected from as n,N-dimethylacetamide, tetrahydro furan
It mutters, one of N,N-dimethylformamide, dimethyl sulfoxide and methylene chloride.
A kind of proton exchange membrane and preparation method thereof for methanol fuel cell provided by the invention, middle layer are poly- inclined
Vinyl fluoride layer, Kynoar are up and down sulfonated polyether-ether-ketone layer, the quality of sulfonated polyether-ether-ketone layer and polyvinylidene fluoride layer
Than for 1:(0.3~0.4).Polyvinylidene fluoride layer is used to inhibit the methanol permeability of proton exchange membrane, sulfonated polyether in the present invention
Ether ketone layer is used to improve the proton conductivity of proton exchange membrane, so that proton exchange membrane is keeping high proton conductivity
Meanwhile also there is low methanol permeability.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are described below with reference to embodiment, but
It is it should be appreciated that these descriptions only require the invention patent to further illustrate the features and advantages of the present invention
Limitation.
The present invention provides a kind of proton exchange membrane for methanol fuel cell, middle layer is polyvinylidene fluoride layer, is gathered
Vinylidene is up and down sulfonated polyether-ether-ketone layer；
Sulfonated polyether-ether-ketone layer, the raw material including following parts by weight:
Sulfonated polyether-ether-ketone layer and the mass ratio of polyvinylidene fluoride layer are 1:(0.3~0.4).
In above-mentioned technical proposal, polyvinylidene fluoride layer is used to inhibit the methanol permeability of proton exchange membrane, sulfonated polyether ether
Ketone layer is used to improve the proton conductivity of proton exchange membrane, so that proton exchange membrane is keeping the same of high proton conductivity
When, also there is low methanol permeability.
In the present invention, sulfonated polyether-ether-ketone layer, including sulfonated polyether-ether-ketone, butadiene-styrene rubber, polyacrylonitrile-based carbon fibre, tristearin
Sour pentaerythritol ester, silicon carbide, graphene oxide, lithium phosphate.Above-mentioned sulfonated polyether-ether-ketone layer can be improved for methanol fuel
The proton conductivity of the proton exchange membrane of battery.
In an embodiment of the present invention, the sulfonation degree 50%~80% of sulfonated polyether-ether-ketone.The sulfonated polyether-ether-ketone can
So that proton exchange membrane has high proton conductivity.
It should be noted that in the present invention, the parts by weight of sulfonated polyether-ether-ketone are 30~50 parts；In reality of the invention
It applies in example, the parts by weight of sulfonated polyether-ether-ketone are 35~45 parts.
Butadiene-styrene rubber is used to improve the mechanical property of proton exchange membrane.In the present invention, the parts by weight of butylbenzene are 10~20
Part；In an embodiment of the present invention, the parts by weight of butadiene-styrene rubber are 13~17 parts.
Polyacrylonitrile-based carbon fibre is used to improve the dimensional stability of proton exchange membrane.In the present invention, polyacrylonitrile-radical
The parts by weight of carbon fiber are 4~7 parts；In an embodiment of the present invention, the parts by weight of polyacrylonitrile-based carbon fibre are 5~6
Part.
Stearic acid pentaerythritol ester is conducive to film forming.In the present invention, the parts by weight of stearic acid pentaerythritol ester are 5~10
Part；In an embodiment of the present invention, the parts by weight of stearic acid pentaerythritol ester are 6.5~8.5 parts.
Silicon carbide is used to improve the high temperature resistance of proton exchange membrane.In the present invention, the parts by weight of silicon carbide are 10
~20 parts；In an embodiment of the present invention, the parts by weight of silicon carbide are 13~16 parts.
Graphene oxide is used to improve the alcohol-rejecting ability of proton exchange membrane.In the present invention, the parts by weight of graphene oxide
Number is 5~10 parts；In an embodiment of the present invention, the parts by weight of graphene oxide are 7~9 parts.
Lithium phosphate is conducive to proton conduction.In the present invention, the parts by weight of lithium phosphate are 5~10 parts；In reality of the invention
It applies in example, the parts by weight of lithium phosphate are 6.5~8.5 parts.
Polyvinylidene fluoride layer, including Kynoar and starch-acrylate graft copolymer.Above-mentioned polyvinylidene fluoride layer is used
In the methanol crossover for inhibiting proton exchange membrane.
It should be noted that in the present invention, the parts by weight of Kynoar are 10~20 parts；In implementation of the invention
In example, the parts by weight of Kynoar are 13~17 parts.
In the present invention, the parts by weight of starch-acrylate graft copolymer are 2~4 parts；In the embodiment of the present invention
In, the parts by weight of starch-acrylate graft copolymer are 2.5~3.5 parts.
It should be noted that sulfonated polyether-ether-ketone layer and the mass ratio of polyvinylidene fluoride layer are 1:(0.3~0.4), when, energy
Enough so that proton exchange membrane is while keeping high proton conductivity, methanol permeability is minimum.
The present invention also provides a kind of preparation methods of proton exchange membrane for methanol fuel cell, including following step
It is rapid:
A) Kynoar and starch-acrylate graft copolymer are added in organic solvent, after mixing evenly, are poured into
In culture dish, be subsequently placed in 60~80 DEG C of baking oven and be dried, and control solvent residual amount be 30~40wt%, by film from
Culture dish surface is uncovered, and is put into the sodium hydroxide solution that concentration is 1mol/L and is boiled 1~2h, place into water and boil 20~
30min, drying obtain polyvinylidene fluoride layer；
B) by sulfonated polyether-ether-ketone, butadiene-styrene rubber, polyacrylonitrile-based carbon fibre, stearic acid pentaerythritol ester, silicon carbide, oxidation
Graphene, lithium phosphate are added in organic solvent, are obtained sulfonated polyether-ether-ketone solution after mixing evenly, are poured into culture dish；
C) step a) polyvinylidene fluoride layer is put into the sulfonated polyether-ether-ketone solution that step b) is obtained, 60~80 DEG C of drying
10~12h to obtain the final product.
Wherein, sulfonated polyether-ether-ketone, butadiene-styrene rubber, polyacrylonitrile-based carbon fibre, stearic acid pentaerythritol ester, silicon carbide, oxygen
Graphite alkene, lithium phosphate, Kynoar, starch-acrylate graft copolymer are same as above, and details are not described herein.
In above-mentioned technical proposal, by controlling the dissolvent residual of Kynoar and starch-acrylate graft copolymer, and
It will be boiled in sodium hydroxide, and so that there are holes in polyvinylidene fluoride layer, then polyvinylidene fluoride layer will be put into sulfonated polyether-ether-ketone
In solution, drying, so that proton exchange membrane is while keeping high proton conductivity, methanol permeability is minimum.
It should be noted that by the dissolvent residual of control Kynoar and starch-acrylate graft copolymer, and will
It is boiled in sodium hydroxide, so that there are holes in polyvinylidene fluoride layer；The presence of its Hole enables to sulfonated polyether-ether-ketone
Solution is filled up wherein, is passed through conducive to proton, and proton conductivity is improved.
In an embodiment of the present invention, in step a) and step b), organic solvent is respectively selected from as N, N- dimethylacetamide
One of amine, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide and methylene chloride.
In order to further illustrate the present invention, below with reference to embodiment to the matter provided by the present invention for methanol fuel cell
Proton exchange and preparation method thereof is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Raw material used in following embodiment is commercially available.
Embodiment 1
For the proton exchange membrane of methanol fuel cell, middle layer is polyvinylidene fluoride layer, and Kynoar is up and down
Sulfonated polyether-ether-ketone layer；The mass ratio of polyvinylidene fluoride layer and polyvinylidene fluoride layer is 1:0.4；
Wherein, sulfonated polyether-ether-ketone layer includes the raw material of following parts by weight:
Sulfonated polyether-ether-ketone that 45 parts of sulfonation degrees are 0.5,17 parts of butadiene-styrene rubbers, 6 parts of polyacrylonitrile-based carbon fibres, 6.5 parts it is hard
Resin acid pentaerythritol ester, 20 parts of silicon carbide, 7 parts of graphene oxides, 5 parts of lithium phosphates；
Polyvinylidene fluoride layer includes the raw material of following parts by weight:
20 parts of Kynoar, 3.5 parts of starch-acrylate graft copolymers；
The preparation method of proton exchange membrane for methanol fuel cell, comprising the following steps:
A) it by Kynoar and starch-acrylate graft copolymer adding into dichloromethane, after mixing evenly, pours into
It in culture dish, is subsequently placed in 60 DEG C of baking oven and is dried, and controlling solvent residual amount is 35wt%, by film from culture dish table
Face is uncovered, and is put into the sodium hydroxide solution that concentration is 1mol/L and is boiled 2h, places into and boil 20min in water, and drying obtains poly- inclined
Vinyl fluoride layer；
B) by sulfonated polyether-ether-ketone, butadiene-styrene rubber, polyacrylonitrile-based carbon fibre, stearic acid pentaerythritol ester, silicon carbide, oxidation
Graphene, lithium phosphate adding into dichloromethane, obtain sulfonated polyether-ether-ketone solution after mixing evenly, pour into culture dish；
C) step a) polyvinylidene fluoride layer is put into the sulfonated polyether-ether-ketone solution that step b) is obtained, 60 DEG C of drying 12h
To obtain the final product.
Embodiment 2
For the proton exchange membrane of methanol fuel cell, middle layer is polyvinylidene fluoride layer, and Kynoar is up and down
Sulfonated polyether-ether-ketone layer；The mass ratio of polyvinylidene fluoride layer and polyvinylidene fluoride layer is 1:0.35；
Wherein, sulfonated polyether-ether-ketone layer includes the raw material of following parts by weight:
Sulfonated polyether-ether-ketone, 10 part butadiene-styrene rubbers, 5 part polyacrylonitrile-based carbon fibres, 10 part tristearin of 50 parts of sulfonation degrees for 0.8
Sour pentaerythritol ester, 13 parts of silicon carbide, 5 parts of graphene oxides, 10 parts of lithium phosphates；
Polyvinylidene fluoride layer includes the raw material of following parts by weight:
13 parts of Kynoar, 4 parts of starch-acrylate graft copolymers；
The preparation method of proton exchange membrane for methanol fuel cell, comprising the following steps:
A) it by Kynoar and starch-acrylate graft copolymer adding into dichloromethane, after mixing evenly, pours into
It in culture dish, is subsequently placed in 70 DEG C of baking oven and is dried, and controlling solvent residual amount is 35wt%, by film from culture dish table
Face is uncovered, and is put into the sodium hydroxide solution that concentration is 1mol/L and is boiled 2h, places into and boil 30min in water, and drying obtains poly- inclined
Vinyl fluoride layer；
B) by sulfonated polyether-ether-ketone, butadiene-styrene rubber, polyacrylonitrile-based carbon fibre, stearic acid pentaerythritol ester, silicon carbide, oxidation
Graphene, lithium phosphate are added in dimethyl sulfoxide, are obtained sulfonated polyether-ether-ketone solution after mixing evenly, are poured into culture dish；
C) step a) polyvinylidene fluoride layer is put into the sulfonated polyether-ether-ketone solution that step b) is obtained, 70 DEG C of drying 10h
To obtain the final product.
Embodiment 3
For the proton exchange membrane of methanol fuel cell, middle layer is polyvinylidene fluoride layer, and Kynoar is up and down
Sulfonated polyether-ether-ketone layer；The mass ratio of polyvinylidene fluoride layer and polyvinylidene fluoride layer is 1:0.4；
Wherein, sulfonated polyether-ether-ketone layer includes the raw material of following parts by weight:
Sulfonated polyether-ether-ketone, 13 part butadiene-styrene rubbers, 4 part polyacrylonitrile-based carbon fibres, 5 part tristearin of 35 parts of sulfonation degrees for 0.6
Sour pentaerythritol ester, 16 parts of silicon carbide, 9 parts of graphene oxides, 8.5 parts of lithium phosphates；
Polyvinylidene fluoride layer includes the raw material of following parts by weight:
17 parts of Kynoar, 2.5 parts of starch-acrylate graft copolymers；
The preparation method of proton exchange membrane for methanol fuel cell, comprising the following steps:
A) Kynoar and starch-acrylate graft copolymer are added in n,N-Dimethylformamide, stirring is equal
It after even, pours into culture dish, is subsequently placed in 80 DEG C of baking oven and is dried, and controlling solvent residual amount is 40wt%, by film
It is uncovered from culture dish surface, is put into the sodium hydroxide solution that concentration is 1mol/L and boils 2h, place into and boil 30min in water, dry
It is dry to obtain polyvinylidene fluoride layer；
B) by sulfonated polyether-ether-ketone, butadiene-styrene rubber, polyacrylonitrile-based carbon fibre, stearic acid pentaerythritol ester, silicon carbide, oxidation
Graphene, lithium phosphate are added in n,N-Dimethylformamide, obtain sulfonated polyether-ether-ketone solution after mixing evenly, pour into culture
Ware；
C) step a) polyvinylidene fluoride layer is put into the sulfonated polyether-ether-ketone solution that step b) is obtained, 80 DEG C of drying 12h
To obtain the final product.
Embodiment 4
For the proton exchange membrane of methanol fuel cell, middle layer is polyvinylidene fluoride layer, and Kynoar is up and down
Sulfonated polyether-ether-ketone layer；The mass ratio of polyvinylidene fluoride layer and polyvinylidene fluoride layer is 1:0.3；
Wherein, sulfonated polyether-ether-ketone layer includes the raw material of following parts by weight:
Sulfonated polyether-ether-ketone that 30 parts of sulfonation degrees are 0.7,20 parts of butadiene-styrene rubbers, 7 parts of polyacrylonitrile-based carbon fibres, 8.5 parts it is hard
Resin acid pentaerythritol ester, 10 parts of silicon carbide, 10 parts of graphene oxides, 6.5 parts of lithium phosphates；
Polyvinylidene fluoride layer includes the raw material of following parts by weight:
10 parts of Kynoar, 2 parts of starch-acrylate graft copolymers；
The preparation method of proton exchange membrane for methanol fuel cell, comprising the following steps:
A) Kynoar and starch-acrylate graft copolymer are added in tetrahydrofuran, after mixing evenly, are poured into
It in culture dish, is subsequently placed in 70 DEG C of baking oven and is dried, and controlling solvent residual amount is 30wt%, by film from culture dish table
Face is uncovered, and is put into the sodium hydroxide solution that concentration is 1mol/L and is boiled 1h, places into and boil 20min in water, and drying obtains poly- inclined
Vinyl fluoride layer；
B) by sulfonated polyether-ether-ketone, butadiene-styrene rubber, polyacrylonitrile-based carbon fibre, stearic acid pentaerythritol ester, silicon carbide, oxidation
Graphene, lithium phosphate are added in tetrahydrofuran, are obtained sulfonated polyether-ether-ketone solution after mixing evenly, are poured into culture dish；
C) step a) polyvinylidene fluoride layer is put into the sulfonated polyether-ether-ketone solution that step b) is obtained, 60 DEG C of drying 10h
To obtain the final product.
Embodiment 5
For the proton exchange membrane of methanol fuel cell, middle layer is polyvinylidene fluoride layer, and Kynoar is up and down
Sulfonated polyether-ether-ketone layer；The mass ratio of polyvinylidene fluoride layer and polyvinylidene fluoride layer is 1:0.35；
Wherein, sulfonated polyether-ether-ketone layer includes the raw material of following parts by weight:
Sulfonated polyether-ether-ketone, 14 part butadiene-styrene rubbers, 5.5 part polyacrylonitrile-based carbon fibres, 7.5 part of 40 parts of sulfonation degrees for 0.65
Stearic acid pentaerythritol ester, 15 parts of silicon carbide, 8 parts of graphene oxides, 7.5 parts of lithium phosphates；
Polyvinylidene fluoride layer includes the raw material of following parts by weight:
14 parts of Kynoar, 3 parts of starch-acrylate graft copolymers；
The preparation method of proton exchange membrane for methanol fuel cell, comprising the following steps:
A) Kynoar and starch-acrylate graft copolymer are added in n,N-dimethylacetamide, stirring is equal
It after even, pours into culture dish, is subsequently placed in 70 DEG C of baking oven and is dried, and controlling solvent residual amount is 350wt%, by film
It is uncovered from culture dish surface, is put into the sodium hydroxide solution that concentration is 1mol/L and boils 1.5h, place into and boil 30min in water,
Drying obtains polyvinylidene fluoride layer；
B) by sulfonated polyether-ether-ketone, butadiene-styrene rubber, polyacrylonitrile-based carbon fibre, stearic acid pentaerythritol ester, silicon carbide, oxidation
Graphene, lithium phosphate are added in n,N-dimethylacetamide, obtain sulfonated polyether-ether-ketone solution after mixing evenly, pour into culture
Ware；
C) step a) polyvinylidene fluoride layer is put into the sulfonated polyether-ether-ketone solution that step b) is obtained, 70 DEG C of drying 12h
To obtain the final product.
Proton exchange membrane made from Examples 1 to 5 is measured, the results are shown in Table 1.
The experimental result of 1 Examples 1 to 5 of table
A kind of proton exchange membrane for methanol fuel cell provided by the invention and preparation method thereof is carried out above
Detailed introduction, used herein a specific example illustrates the principle and implementation of the invention, above embodiments
Explanation be merely used to help understand method and its core concept of the invention, it is noted that for the common of the art
, without departing from the principle of the present invention, can be with several improvements and modifications are made to the present invention for technical staff, these
Improvement and modification are also fallen within the protection scope of the claims of the present invention.
Claims (5)
1. a kind of proton exchange membrane for methanol fuel cell, which is characterized in that middle layer is polyvinylidene fluoride layer, described poly-
Vinylidene is up and down sulfonated polyether-ether-ketone layer；
The sulfonated polyether-ether-ketone layer, the raw material including following parts by weight:
The mass ratio of the polyvinylidene fluoride layer and the polyvinylidene fluoride layer is 1:(0.3~0.4).
2. being used for the proton exchange membrane of methanol fuel cell as described in claim 1, which is characterized in that the Kynoar
Layer, the raw material including following parts by weight:
10~20 parts of Kynoar；
2~4 parts of starch-acrylate graft copolymer.
3. being used for the proton exchange membrane of methanol fuel cell as described in claim 1, which is characterized in that the sulfonated polyether ether
The sulfonation degree 50%~80% of ketone.
4. a kind of preparation method for the proton exchange membrane of methanol fuel cell as described in claim 1, which is characterized in that
The following steps are included:
A) Kynoar and starch-acrylate graft copolymer are added in organic solvent, after mixing evenly, pour into culture
It in ware, is subsequently placed in 60~80 DEG C of baking oven and is dried, and controlling solvent residual amount is 30~40wt%, by film from culture
Ware surface is uncovered, and is put into the sodium hydroxide solution that concentration is 1mol/L and is boiled 1~2h, place into and boil 20~30min in water, dries
It is dry to obtain polyvinylidene fluoride layer；
B) by sulfonated polyether-ether-ketone, butadiene-styrene rubber, polyacrylonitrile-based carbon fibre, stearic acid pentaerythritol ester, silicon carbide, graphite oxide
Alkene, lithium phosphate are added in organic solvent, are obtained sulfonated polyether-ether-ketone solution after mixing evenly, are poured into culture dish；
C) step a) polyvinylidene fluoride layer is put into the sulfonated polyether-ether-ketone solution that step b) is obtained, 60~80 DEG C of drying 10~
12h to obtain the final product.
5. preparation method as claimed in claim 4, which is characterized in that in step a) and step b), the organic solvent difference
Selected from for one in DMAC N,N' dimethyl acetamide, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide and methylene chloride
Kind.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114447382A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Proton exchange membrane containing concentric axis microstructure and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114447382A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Proton exchange membrane containing concentric axis microstructure and preparation method thereof |
| CN114447382B (en) * | 2020-10-31 | 2024-05-31 | 中国石油化工股份有限公司 | Proton exchange membrane containing concentric shaft microstructure and preparation method thereof |
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Application publication date: 20190402 |