CN110010940A - A kind of method that sulfonated polyether-ether-ketone load single catalyst directly prepares proton exchange membrane - Google Patents

A kind of method that sulfonated polyether-ether-ketone load single catalyst directly prepares proton exchange membrane Download PDF

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Publication number
CN110010940A
CN110010940A CN201910265887.XA CN201910265887A CN110010940A CN 110010940 A CN110010940 A CN 110010940A CN 201910265887 A CN201910265887 A CN 201910265887A CN 110010940 A CN110010940 A CN 110010940A
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ether
ketone
sulfonated polyether
exchange membrane
proton exchange
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张成如
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Shandong Xinghuo Science Technology Institute
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Shandong Xinghuo Science Technology Institute
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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]
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Fuel Cell (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The present invention relates to the methods that a kind of sulfonated polyether-ether-ketone load single catalyst directly prepares proton exchange membrane, using sulfonated polyether-ether-ketone and graphene oxide as film-forming components, film liquid is mixed and made into platinum catalyst slurry, casting film-forming, the proton exchange membrane of sulfonated polyether-ether-ketone load single catalyst is directly made, the proton exchange membrane has good proton conductivity, alcohol-rejecting ability and mechanical performance, can be widely applied to direct methanol fuel cell field.

Description

A kind of sulfonated polyether-ether-ketone load single catalyst directly prepares proton exchange membrane Method
Technical field
The invention belongs to proton exchange membrane fields, and in particular to a kind of sulfonated polyether-ether-ketone load single catalyst is directly made The method of standby proton exchange membrane.
Background technique
Fuel cell as a kind of new energy system, with high effect cleaning low noise high reliablity and it is environmentally friendly the advantages that And by favor, especially direct methanol fuel cell.
Proton exchange membrane is one of the core component of Proton Exchange Membrane Fuel Cells and direct alcohol fuel cell, effect It is: (1) separates anode and cathode, fuel and air (oxygen) directly mixing is prevented to chemically react；(2) proton conducting, matter Electron conductivity is higher, and the internal resistance of film is smaller, and the efficiency of fuel cell is higher；(3) electrical insulator prevents electronics from conducting in film, Electronics, by outside line road direction cathode flow, it is for people to use to generate foreign current by anode.In general, fuel cell PEM material It must meet the following requirement: (1) inexpensive；(2) high proton conductivity；(3) good mechanical strength (anti-swelling) and size are steady It is qualitative；(4) excellent chemical stability and electrochemical stability；(5) very low gas or methanol permeability；(6) and catalyst Layer matching；(7) it is used for a long time and stablizes.Currently, platinum is widely used as due to having very high catalytic activity to catalytic oxidation-reduction Electrocatalyst for cathode.
A kind of macromolecule of the sulfonated polyether-ether-ketone as glassy state has good thermal stability and mechanical strength, gas Infiltration coefficient it is lower.In gas separation process, usually with the presence of vapor, and most of membrane material water-resistant stability by Limitation, and sulfonated polyether-ether-ketone has excellent water resistance, can be used as the high-molecular matrix material in hybridized film.
Summary of the invention
The purpose of the present invention is to provide a kind of sulfonated polyether-ether-ketone load single catalysts directly to prepare proton exchange membrane Method.
The technical solution adopted by the present invention to solve the technical problems is: a kind of sulfonated polyether-ether-ketone load single catalyst Directly prepare the method for proton exchange membrane, comprising the following steps:
1) with H2PtCl6As the presoma of Pt, carbon nanotube is as catalyst carrier, by H2PtCl6It is dissolved in ethylene glycol In, carbon nanotube stirring 1-2h is added into homogeneous slurry, it is 8-10 that NaOH, which is added, and adjusts pH value, is warming up to 125-150 DEG C, reflux To the precursor salt end of reaction of catalyst metals, catalyst pulp is obtained；
2) graphene oxide is dissolved in deionized water, ultrasonic disperse is configured to the dispersion liquid of 5-15wt%；
3) will sulfonated polyether-ether-ketone be added dimethylformamide in, be configured to concentration be 5-10wt% solution, then according to The catalyst pulp of the secondary dispersion liquid that step 2) is added and step 1), is cast on clean glass plate after being dispersed with stirring uniformly Film, 60 DEG C of vacuum drying 12-24h are impregnated 1-2 hours in the sulfuric acid solution of 1mol/L after taking off film, are sufficiently soaked with deionized water Bubble, washing, vacuum drying obtain proton exchange membrane.
Specifically, H in the step 1)2PtCl6Mass ratio with carbon nanotube is 3-7:5-10.
Specifically, the preparation step of sulfonated polyether-ether-ketone is as follows in the step 3): according to polyether-ether-ketone and the concentrated sulfuric acid Mass ratio is that dry polyether-ether-ketone particle is added in the concentrated sulfuric acid in 45~50 DEG C of reactions, through precipitating, mistake by 0.11-0.15:1 Filter, washing, obtain sulfonated polyether-ether-ketone.
Specifically, sulfonated polyether-ether-ketone in the step 3), graphene oxide, carbon nanotube mass ratio be 10-15:2- 3:4-10。
The invention has the following advantages: the present invention is using sulfonated polyether-ether-ketone and graphene oxide as film-forming components, It is mixed and made into film liquid with platinum catalyst slurry, the matter of sulfonated polyether-ether-ketone load single catalyst is directly made in casting film-forming Proton exchange, the proton exchange membrane have good proton conductivity, alcohol-rejecting ability and mechanical performance, can be widely applied to straight Connect methanol fuel cell field.
Specific embodiment
The following is specific embodiments of the present invention, is described further to technical solution of the present invention, but of the invention Protection scope is not limited to these examples.It is all to be included in the present invention without departing substantially from the change of present inventive concept or equivalent substitute Protection scope within.
Embodiment 1
A kind of method that sulfonated polyether-ether-ketone load single catalyst directly prepares proton exchange membrane, comprising the following steps:
1) with H2PtCl6As the presoma of Pt, carbon nanotube is as catalyst carrier, by H2PtCl6It is dissolved in ethylene glycol In, carbon nanotube stirring 2h is added into homogeneous slurry, H2PtCl6Mass ratio with carbon nanotube is 5:8, and NaOH is added and adjusts pH Value is 8, is warming up to 140 DEG C, is back to the precursor salt end of reaction of catalyst metals, obtains catalyst pulp；
2) graphene oxide is dissolved in deionized water, ultrasonic disperse is configured to the dispersion liquid of 8wt%；
3) dry polyether-ether-ketone particle is added to dense sulphur for 0.15:1 according to the mass ratio of polyether-ether-ketone and the concentrated sulfuric acid It is reacted in acid in 50 DEG C, is precipitated, is filtered, washed, obtain sulfonated polyether-ether-ketone.Dimethylformamide is added in sulfonated polyether-ether-ketone In, it is configured to the solution that concentration is 7wt%, then sequentially adds the dispersion liquid of step 2) and the catalyst pulp of step 1), sulphur Change polyether-ether-ketone, graphene oxide, carbon nanotube mass ratio be 12:2:7, after being dispersed with stirring uniformly on clean glass plate Casting film-forming, 60 DEG C of vacuum drying for 24 hours, are impregnated 1 hour in the sulfuric acid solution of 1mol/L after taking off film, are sufficiently soaked with deionized water Bubble, washing, vacuum drying obtain proton exchange membrane.
Embodiment 2
A kind of method that sulfonated polyether-ether-ketone load single catalyst directly prepares proton exchange membrane, comprising the following steps:
1) with H2PtCl6As the presoma of Pt, carbon nanotube is as catalyst carrier, by H2PtCl6It is dissolved in ethylene glycol In, carbon nanotube stirring 1h is added into homogeneous slurry, H2PtCl6Mass ratio with carbon nanotube is 3:7, and NaOH is added and adjusts pH Value is 9, is warming up to 150 DEG C, is back to the precursor salt end of reaction of catalyst metals, obtains catalyst pulp；
2) graphene oxide is dissolved in deionized water, ultrasonic disperse is configured to the dispersion liquid of 10wt%；
3) dry polyether-ether-ketone particle is added to dense sulphur for 0.11:1 according to the mass ratio of polyether-ether-ketone and the concentrated sulfuric acid It is reacted in acid in 45 DEG C, is precipitated, is filtered, washed, obtain sulfonated polyether-ether-ketone.Dimethylformamide is added in sulfonated polyether-ether-ketone In, it is configured to the solution that concentration is 5wt%, then sequentially adds the dispersion liquid of step 2) and the catalyst pulp of step 1), sulphur Change polyether-ether-ketone, graphene oxide, carbon nanotube mass ratio be 10:3:10, in clean glass plate after being dispersed with stirring uniformly Upper casting film-forming, 60 DEG C of vacuum drying 18h impregnate 2 hours in the sulfuric acid solution of 1mol/L after taking off film, abundant with deionized water It impregnates, washing, vacuum drying obtains proton exchange membrane.
Embodiment 3
A kind of method that sulfonated polyether-ether-ketone load single catalyst directly prepares proton exchange membrane, comprising the following steps:
1) with H2PtCl6As the presoma of Pt, carbon nanotube is as catalyst carrier, by H2PtCl6It is dissolved in ethylene glycol In, carbon nanotube stirring 1h is added into homogeneous slurry, H2PtCl6Mass ratio with carbon nanotube is 7:5, and NaOH is added and adjusts pH Value is 10, is warming up to 125 DEG C, is back to the precursor salt end of reaction of catalyst metals, obtains catalyst pulp；
2) graphene oxide is dissolved in deionized water, ultrasonic disperse is configured to the dispersion liquid of 15wt%；
3) dry polyether-ether-ketone particle is added to dense sulphur for 0.13:1 according to the mass ratio of polyether-ether-ketone and the concentrated sulfuric acid It is reacted in acid in 48 DEG C, is precipitated, is filtered, washed, obtain sulfonated polyether-ether-ketone.Dimethylformamide is added in sulfonated polyether-ether-ketone In, it is configured to the solution that concentration is 8wt%, then sequentially adds the dispersion liquid of step 2) and the catalyst pulp of step 1), sulphur Change polyether-ether-ketone, graphene oxide, carbon nanotube mass ratio be 15:2:4, after being dispersed with stirring uniformly on clean glass plate Casting film-forming, 60 DEG C of vacuum drying 12h are impregnated 1 hour in the sulfuric acid solution of 1mol/L after taking off film, are sufficiently soaked with deionized water Bubble, washing, vacuum drying obtain proton exchange membrane.
Embodiment 4
A kind of method that sulfonated polyether-ether-ketone load single catalyst directly prepares proton exchange membrane, comprising the following steps:
1) with H2PtCl6As the presoma of Pt, carbon nanotube is as catalyst carrier, by H2PtCl6It is dissolved in ethylene glycol In, carbon nanotube stirring 1.5h is added into homogeneous slurry, H2PtCl6Mass ratio with carbon nanotube is 6:10, and NaOH is added and adjusts PH value is 9, is warming up to 135 DEG C, is back to the precursor salt end of reaction of catalyst metals, obtains catalyst pulp；
2) graphene oxide is dissolved in deionized water, ultrasonic disperse is configured to the dispersion liquid of 5wt%；
3) dry polyether-ether-ketone particle is added to dense sulphur for 0.12:1 according to the mass ratio of polyether-ether-ketone and the concentrated sulfuric acid It is reacted in acid in 45 DEG C, is precipitated, is filtered, washed, obtain sulfonated polyether-ether-ketone.Dimethylformamide is added in sulfonated polyether-ether-ketone In, it is configured to the solution that concentration is 10wt%, then sequentially adds the dispersion liquid of step 2) and the catalyst pulp of step 1), sulphur Change polyether-ether-ketone, graphene oxide, carbon nanotube mass ratio be 14:3:8, after being dispersed with stirring uniformly on clean glass plate Casting film-forming, 60 DEG C of vacuum drying 18h impregnate 1.5 hours in the sulfuric acid solution of 1mol/L after taking off film, abundant with deionized water It impregnates, washing, vacuum drying obtains proton exchange membrane.

Claims (4)

1. a kind of method that sulfonated polyether-ether-ketone load single catalyst directly prepares proton exchange membrane, which is characterized in that including Following steps:
1) with H2PtCl6As the presoma of Pt, carbon nanotube is as catalyst carrier, by H2PtCl6It is dissolved in ethylene glycol, adds Enter carbon nanotube stirring 1-2h into homogeneous slurry, it is 8-10 that NaOH, which is added, and adjusts pH value, is warming up to 125-150 DEG C, is back to and urges The precursor salt end of reaction of agent metal, obtains catalyst pulp；
2) graphene oxide is dissolved in deionized water, ultrasonic disperse is configured to the dispersion liquid of 5-15wt%；
3) sulfonated polyether-ether-ketone is added in dimethylformamide, is configured to the solution that concentration is 5-10wt%, then successively adds Enter the dispersion liquid of step 2) and the catalyst pulp of step 1), after being dispersed with stirring uniformly on clean glass plate casting film-forming, 60 DEG C of vacuum drying 12-24h impregnate 1-2 hours in the sulfuric acid solution of 1mol/L after taking off film, sufficiently impregnated with deionized water, Washing, vacuum drying, obtains proton exchange membrane.
2. the method that sulfonated polyether-ether-ketone load single catalyst as described in claim 1 directly prepares proton exchange membrane, It is characterized in that, H in the step 1)2PtCl6Mass ratio with carbon nanotube is 3-7:5-10.
3. the method that sulfonated polyether-ether-ketone load single catalyst as described in claim 1 directly prepares proton exchange membrane, It is characterized in that, the preparation step of sulfonated polyether-ether-ketone is as follows in the step 3): according to the mass ratio of polyether-ether-ketone and the concentrated sulfuric acid Dry polyether-ether-ketone particle is added in the concentrated sulfuric acid for 0.11-0.15:1 and is reacted in 45~50 DEG C, through precipitating, filters, wash It washs, obtains sulfonated polyether-ether-ketone.
4. the method that sulfonated polyether-ether-ketone load single catalyst as described in claim 1 directly prepares proton exchange membrane, Be characterized in that, sulfonated polyether-ether-ketone in the step 3), graphene oxide, carbon nanotube mass ratio be 10-15:2-3:4- 10。
CN201910265887.XA 2019-04-03 2019-04-03 A kind of method that sulfonated polyether-ether-ketone load single catalyst directly prepares proton exchange membrane Withdrawn CN110010940A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111193054A (en) * 2020-01-09 2020-05-22 安徽师范大学 Preparation method of proton exchange membrane

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111193054A (en) * 2020-01-09 2020-05-22 安徽师范大学 Preparation method of proton exchange membrane

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Application publication date: 20190712