CN108232262A - High-barrier, high tolerance compound proton exchange membrane and preparation method thereof - Google Patents
High-barrier, high tolerance compound proton exchange membrane and preparation method thereof Download PDFInfo
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- CN108232262A CN108232262A CN201711485481.XA CN201711485481A CN108232262A CN 108232262 A CN108232262 A CN 108232262A CN 201711485481 A CN201711485481 A CN 201711485481A CN 108232262 A CN108232262 A CN 108232262A
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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
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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
- H01M8/1016—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
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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
Abstract
The present invention relates to a kind of high-barriers, high tolerance compound proton exchange membrane and preparation method thereof, belong to proton exchange technical field of membrane.The compound proton exchange membrane is made of the ion exchange resin of 95 99.5wt.% and the oriented layer of 0.5 5wt.%；Wherein, ion exchange resin is one kind in perfluorinated sulfonic resin, sulfonated polyether, sulfonated poly aryl ether ketone, sulfonated poly thioether ketone or sulfonated polyether sulphone ketone；Orientation layer component is one kind in redox graphene, single-walled carbon nanotube or modified montmorillonoid.Compound proton exchange membrane obtained possesses efficient proton conducting power, while also has high mechanical resistance and high barrier.The present invention also provides preparation methods, scientific and reasonable comprising four steps, simple and practicable, of low cost, safety and environmental protection.
Description
Technical field
The present invention relates to a kind of high-barriers, high tolerance compound proton exchange membrane and preparation method thereof, belong to proton exchange membrane
Technical field.
Background technology
Fuel cell can reach no pollution in terms of environmental protection, and have the energy recharge time is short, energy density is high etc.
Advantage becomes and substitutes the maximally efficient dynamic origin of internal combustion engine.The performance of fuel cell is heavily dependent on its core
One of component proton exchange membrane, it provides effectively conduction pathway in addition to being needed as proton, it is also necessary to have efficient barrier property
And mechanical resistance.It is unnecessary that high barrier can effectively prevent methanol or hydrogen from being generated from anode diffusion to cathode directly by film
By-product, prevent catalyst poisoning；Good mechanical resistance can ensure that it is not easy out in membrane electrode (MEA) preparation process
Existing mechanical damage, so as to improve the chemical property of fuel cell.At present, it is U.S. Dupont that proton exchange membrane is most commonly used
Nafion membrane, the membrane material of the type has good proton-conducting and chemical stability, but high cost and high-permeability
Become it in the widely applied major obstacle of fuel cell field.
In the research for improving proton exchange film properties, the emphasis as research is modified using compound method.Its
In, the materials such as redox graphene, single-walled carbon nanotube, modified montmorillonoid can form lamellar structure, and be provided simultaneously with excellent
The performances such as electricity, mechanics, calorifics, be considered as ideal reinforcement so that membrane material possesses the same of efficient proton conducting power
When, show good barrier property and mechanical resistance.
Invention content
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of high-barrier, height to be resistant to compound proton exchange membrane,
Possess efficient proton conducting power, while also have high mechanical resistance and high barrier.
Meanwhile the present invention also provides preparation methods, scientific and reasonable, simple and practicable, of low cost, safety and environmental protection.
High-barrier of the present invention, high tolerance compound proton exchange membrane, the amberlite comprising 95-99.5wt.%
The oriented layer of fat and 0.5-5wt.%；
Wherein, ion exchange resin is perfluorinated sulfonic resin, sulfonated polyether, sulfonated poly aryl ether ketone, sulfonated poly thioether ketone
Or one kind in sulfonated polyether sulphone ketone；
Orientation layer component is one kind in redox graphene, single-walled carbon nanotube or modified montmorillonoid.
The compound proton exchange membrane, comprising single-layer or multi-layer oriented layer, oriented layer is located at compound proton exchange membrane
Surface or inside；Compound proton exchange membrane thickness is 5-150 μm, and orientation layer thickness is 0.05-10 μm.
The preparation method of high-barrier of the present invention, high tolerance compound proton exchange membrane, includes the following steps：
1) oriented layer pre-processes
Graphene oxide processing：Reducing agent is added in graphene oxide water solution, is filtered by molecular filter, vacuum is done
Redox graphene is obtained after dry or first passes through molecular filter suction filtration, then be put in reducing agent and reacted, be dried in vacuo
After obtain；
Single-walled carbon nanotube processing：Single-walled carbon nanotube is put into progress-COOH functional modifications in mixing concentrated acid, then pass through
Filtering, ultrasonic disperse and centrifugal process, obtain homogeneous high-dispersibility carbon nanotube suspension；
Montmorillonite is handled：Montmorillonite is dissolved in deionized water, after swelling, intercalator is added dropwise and is modified；
2) prepared by amberlite lipoprotein solution
Ion exchange resin is configured to the solution of solid content 10-40wt.%；
3) prepared by oriented layer
a：Redox graphene deposits film forming under conditions of induction is filtered, and redox graphene oriented layer is made；
b：Single-walled carbon nanotube suspension deposits film forming under conditions of electric field induction, and single-walled carbon nanotube orientation is made
Layer；
c：Modified montmorillonoid is mixed with amberlite lipoprotein solution；
4) prepared by compound proton exchange membrane
a：Amberlite lipoprotein solution by way of solution-cast, curtain coating or spraying with redox graphene oriented layer
Or single-walled carbon nanotube oriented layer composite membrane-forming；
b：After modified montmorillonoid is mixed with amberlite lipoprotein solution, the system by way of solution-cast, curtain coating or spraying
Into composite membrane.
In the step 1), reducing agent is hydrazine hydrate or hydroiodic acid, and reduction reaction temperature is 80-150 DEG C, and the reaction time is
1-2h；
In the step 1), mixing concentrated acid is the concentrated sulfuric acid and concentrated nitric acid mass ratio is 3:1 mixed acid；Single-walled carbon nanotube
Suspension concentration is 0.01-1.0wt.%.
Preferably, concentrated sulfuric acid mass fraction is 98%；Nitric acid mass fraction is 70%.
Single-walled carbon nanotube-COOH is modified, and is the function to the port of single-walled carbon nanotube and the progress of side wall defect sites
It is modified.In the step 3), for single-walled carbon nanotube when depositing film forming, the thin-film material for selecting printed on both sides silver inks electrode is lining
Bottom, and the excitation electrical field scanning range for adjusting electric field induction is 0-10V/cm, time duration scan ranging from 5-60min.
Electric field strength and the duration of electric field induction are adjusted, can obtain the carbon nanotube deposition film of different-thickness.
Substrate is microporous PVDF or PTFE material；
In the step 1), montmorillonite is sodium-based montmorillonite, and intercalator is cationic surface active agent, anionic table
One kind in face activating agent, zwitterionic surfactant or nonionic surfactant.
Preferably, the cationic surface active agent is tetradecyl dimethyl benzyl ammonium, cetyl three
One kind in methyl bromide ammonium or polyethers ammonium cation；Anionic surfactant is dodecyl sodium sulfate or dodecyl
Sodium sulphate；Zwitterionic surfactant is 3- sulfopropyl dodecyl dimethyl ammoniums or 3- sulfopropyl dodecyldimethylamine bases
Ammonium；Nonionic surfactant is brejs nonionic surfactant.
In the step 1), intercalator additive amount is 0.1-5 times of montmorillonite cation exchange capacity；Intercalation spacing is 1-
10nm。
In the step 4), graphene oxide and single-walled carbon nanotube and ion exchange resin are solution combined, composite solution
Mass fraction is 0.1-40%.
Compared with prior art, the present invention has the advantages that：
The orientation layer material of compound proton exchange membrane described in 1., redox graphene, single-walled carbon nanotube or modification
Montmorillonite all has excellent electricity, mechanics, thermal property so that compound proton exchange membrane is possessing efficient proton conducting power
While, show good barrier property and mechanical resistance；
2. compound proton exchange membrane hydrogen transmitance made from is less than 3.0 × 10-9mol/(cm2S), methanol permeability is low
In 8.7 × 10-7cm2·s-1；Hardness is higher than 1.5MPa, and in the case where not influencing proton conductivity, elasticity modulus is compared to relatively
Film material promotes more than 25%；
3. the preparation method provided, scientific and reasonable, easy to implement, of low cost, safety and environmental protection；
Before 4. compound proton exchange membrane described in has wide application in terms of Hydrogen Energy source battery, the methanol fuel cell
Scape.
Description of the drawings
Fig. 1 is high-barrier, the part-structure schematic diagram of high tolerance compound proton exchange membrane；
Fig. 2 is that redox graphene oriented layer projects electron microscope in embodiment 2；
Fig. 3 is modified montmorillonoid transmission electron microscope picture in embodiment 6；
In figure, 1- oriented layer；2- ion exchange resin.
Specific embodiment
With reference to embodiment, the present invention is described further.
Embodiment 1
By the graphene oxide water solution concentration dilution purchased to 0.5mg/mL, graphene oxide water solution after 2L dilutions is taken
It adds in three-necked flask, is separately added into 2mL hydrazine hydrates thereto by constant pressure funnel, be put into after stirring evenly in 95 DEG C of oil baths anti-
1h is answered, the redox graphene solution of black uniform made from reaction is filtered by molecular filter, then vacuum is done at 50 DEG C
It is dry to obtain oriented layer that there is metallic luster, that thickness is 2 μm.
Orientation obtained is placed on basal lamina material, the perfluorinated sulfonic resin water-alcohol solution (water of solid content 25wt.%:
Ethyl alcohol=1:1) feeding is coated with by solution-cast, after resin solution penetrates into redox graphene oriented layer, wet film enters
Oven drying 2h, temperature gradient are 45 DEG C, 80 DEG C, 120 DEG C, and the thickness of the proton exchange membrane is 20 μm.
Embodiment 2
By the graphene oxide water solution concentration dilution purchased to 0.5mg/mL, graphene oxide water solution after 2L dilutions is taken
It filters to obtain the graphene oxide film of 2 μ m-thicks by molecular filter, be then immersed in hydroiodic acid and in 100 DEG C of oil bath items
1h is reacted under part, then successively ethyl alcohol and acetone are cleaned, are dried in vacuo, and obtain the black reduction-oxidation graphite with metallic luster
Alkene oriented layer.
Solid content be 18wt.% sulfonated polyether-ether-ketone resin DMF solution by die head cast coat feeding, by above-mentioned system
The oriented layer obtained is overlying on resin liquid film, again by die head cast coat feeding, treats that resin solution penetrates into reduction-oxidation graphite
After alkene oriented layer, wet film enters oven drying 4h, and temperature gradient is 90 DEG C, 170 DEG C, and the thickness of the proton exchange membrane is 50 μm.
Embodiment 3
By the graphene oxide water solution concentration dilution purchased to 0.5mg/mL, graphene oxide water solution after 6L dilutions is taken
It filters to obtain the graphene oxide film of two 3 μ m-thicks by molecular filter, be dipped in hydroiodic acid and in 100 DEG C of oil bath items
2h is reacted under part, then successively ethyl alcohol and acetone are cleaned, are dried in vacuo, and obtain the black reduction-oxidation graphite with metallic luster
Alkene oriented layer.
Perfluorinated sulfonic resin water-alcohol solution (the water of solid content 19wt%:Isopropanol=4:6) by die head cast coat
Expect, on basal lamina material, then a wherein oriented layer obtained above to be overlying on resin liquid film, treat that resin solution penetrates into also
Die head cast coat feeding after former graphene oxide oriented layer；Second oriented layer obtained is overlying on resin liquid film, waits to set
Lipoprotein solution is penetrated into after lamella again by die head cast coat feeding, and wet film enters oven drying 2h, and temperature gradient is 45 DEG C, 80
DEG C, 130 DEG C, the thickness of the proton exchange membrane is 15 μm.
Embodiment 4
The nitric acid of sulfuric acid and 100mL70wt% that 1g single pipe powders are added to 300ml98wt% is mixed dense
In acid, it is put in 110 DEG C of oil baths and stirs 1h.It cools down after reaction, solution is diluted to 2L by addition deionized water, uses film mistake
Filter cleaning carbon nano-tube solution until cleaning solution PH higher than 5, by the carbon nanotube of carboxyl modified again with 1L deionized waters, auxiliary
Supersound process is helped to be disperseed, the single-walled carbon nanotube suspension of homogeneous polymolecularity is made.
Choose substrate material of the microporous PTFE film for electric field induction and deposition single-walled carbon nanotube that two sides is printed on silver inks electrode
Material, is put in the carboxylic carbon nano-tube solution of above-mentioned a concentration of 1g/L, adjusts cathode-anode plate spacing as 3.0cm, excitation electrical field
Intensity is set as 2V/cm, induction time 30min, and material is taken out naturally dry from functionalization solution, and it is 5 μm to obtain thickness
Single-walled carbon nanotube oriented layer.
Perfluorinated sulfonic resin water-alcohol solution (the water of solid content 20wt%:Ethyl alcohol=1:1) by spraying the two sides to film
Feeding, wet film enter oven drying 2h, and temperature gradient is 50 DEG C, 95 DEG C, 150 DEG C, and the thickness of the proton exchange membrane is 20 μm.
Embodiment 5
0.5g singles pipe powder is added in the sulfuric acid of 150ml98wt% and the nitric acid mixing concentrated acid of 50mL70wt%
In, it is put in 110 DEG C of oil baths and stirs 1h, cool down after reaction, solution is diluted to 1L by addition deionized water, uses membrane filtration
Device cleaning carbon nano-tube solution until cleaning solution PH higher than 5, by the carbon nanotube of carboxyl modified again with 500mL deionized waters,
Assisting ultrasonic processing is disperseed, and the single-walled carbon nanotube suspension of homogeneous polymolecularity is made.
Choose substrate material of the microporous PVDF membrane for electric field induction and deposition single-walled carbon nanotube that two sides is printed on silver inks electrode
Material, is put in the carboxylic carbon nano-tube solution of above-mentioned a concentration of 0.5g/L, and it is 2.5cm to adjust cathode-anode plate spacing, and excitation is electric
Field intensity is set as 1V/cm, induction time 20min, and material is taken out naturally dry from functionalization solution, obtains thickness as 8 μ
The single-walled carbon nanotube oriented layer of m.
The sulfonated polyether sulphone ketone DMF solution that solid content is 16wt% is by spraying the single side feeding to oriented layer, wet film
Into oven drying 4h, temperature gradient is 90 DEG C, 120 DEG C, and the thickness of the proton exchange membrane is 30 μm.
Embodiment 6
The addition of 1.0g sodium-based montmorillonites is filled in the round-bottomed flask of 20mL deionized waters, is stirred under 60 DEG C of water bath conditions
It is stood after 1h for 24 hours, until its complete swelling, by the cetyl trimethyl bromination of 0.40g (1.29eq montmorillonites exchange capacity)
Ammonium is dissolved in 10mL deionized waters, is gradually added dropwise in round-bottomed flask by constant pressure funnel, and standing collects white sink after reacting 6h
It forms sediment, deionized water filtering and washing to filtrate is detected with silver nitrate solution and is precipitated without pale yellow precipitate, and white precipitate obtained is in 100
At DEG C modified montmorillonoid powder is obtained after the sieving of dry and fine gtinding.
Modified montmorillonoid powder obtained above is added to progress ultrasonic disperse in NMP and obtains the suspended of homogeneous polymolecularity
Liquid is mixed with the nmp solution for the sulfonated aryl sulfoether ketone that 100mL solid contents are 12wt% and is stirred at room temperature for 24 hours, waits to react
After, for preparation liquid by solution-cast on basal lamina material, wet film enters predrying 1h at 80 DEG C of baking oven, then 300mL is consolidated
The sulfonated aryl sulfoether ketone nmp solution that content is 12wt% carries out secondary feeding by the method for solution-cast, and wet film enters baking
Case is dried in vacuo 6h, and temperature gradient is 80 DEG C, 100 DEG C, and the thickness of the proton exchange membrane is 125 μm.
Comparative example 1
Perfluorinated sulfonic resin (being purchased from Shandong Dongyue Polymer Material Co., Ltd.) water-alcohol solution that solid content is 20wt%
(water:Ethyl alcohol=1:1) by die head cast coat feeding on basal lamina material, wet film enters oven drying 2h, and temperature gradient is
50 DEG C, 90 DEG C, 130 DEG C, the thickness of the proton exchange membrane is 20 μm.
Comparative example 2
The Nafion115 proton exchange membrane of Dupont companies of the U.S..
At 85 DEG C, under conditions of 50DH%, embodiment 1-6 and comparative example 1-2 are tested for the property, test result such as table
Shown in 1.
1 embodiment 1-6 of table and comparative example 1-2 performance test comparison results
Claims (10)
1. a kind of high-barrier, high tolerance compound proton exchange membrane, it is characterised in that：By the ion exchange resin of 95-99.5wt.%
It is formed with the oriented layer of 0.5-5wt.%；
Wherein, ion exchange resin is perfluorinated sulfonic resin, sulfonated polyether, sulfonated poly aryl ether ketone, sulfonated poly thioether ketone or sulphur
Change one kind in poly (aryl ether sulfone ketone)；
Orientation layer component is one kind in redox graphene, single-walled carbon nanotube or modified montmorillonoid.
2. high-barrier according to claim 1, high tolerance compound proton exchange membrane, it is characterised in that：Comprising individual layer or more
Layer oriented layer, oriented layer are located at the surface or inside of compound proton exchange membrane；Compound proton exchange membrane thickness is 5-150 μm, is taken
It it is 0.05-10 μm to layer thickness.
3. a kind of preparation method of high-barrier described in claim 1, high tolerance compound proton exchange membrane, it is characterised in that：Packet
Include following steps：
1) orientation layer component pretreatment
Graphene oxide processing：Reducing agent is added in graphene oxide water solution, after being filtered, being dried in vacuo by molecular filter
Obtain redox graphene or first pass through molecular filter suction filtration, then be put in reducing agent and reacted, be dried in vacuo after
It arrives；
Single-walled carbon nanotube processing：Single-walled carbon nanotube is put into and mixes progress-COOH functional modifications in concentrated acid, filtered,
Ultrasonic disperse and centrifugal process obtain homogeneous high-dispersibility carbon nanotube suspension；
Montmorillonite is handled：Montmorillonite is dissolved in deionized water, after swelling, intercalator is added dropwise and is modified；
2) prepared by amberlite lipoprotein solution
Ion exchange resin is configured to the solution of solid content 10-40wt.%；
3) prepared by oriented layer
a：Redox graphene deposits film forming under conditions of induction is filtered, and redox graphene oriented layer is made；
b：Single-walled carbon nanotube suspension deposits film forming under conditions of electric field induction, and single-walled carbon nanotube oriented layer is made；
c：Modified montmorillonoid is mixed with amberlite lipoprotein solution；
4) prepared by compound proton exchange membrane
a：Amberlite lipoprotein solution by way of solution-cast, curtain coating or spraying with redox graphene oriented layer or list
Wall carbon nano tube oriented layer composite membrane-forming；
b：After modified montmorillonoid is mixed with amberlite lipoprotein solution, it is made by way of solution-cast, curtain coating or spraying multiple
Close film.
4. the preparation method of high-barrier according to claim 3, high tolerance compound proton exchange membrane, it is characterised in that：Institute
It states in step 1), reducing agent is hydrazine hydrate or hydroiodic acid, and reduction reaction temperature is 80-150 DEG C, reaction time 1-2h.
5. the preparation method of high-barrier according to claim 3, high tolerance compound proton exchange membrane, it is characterised in that：Institute
It states in step 1), mixing concentrated acid is the concentrated sulfuric acid and concentrated nitric acid mass ratio is 3:1 mixed acid；Single-walled carbon nanotube suspension concentration
For 0.01-1.0wt.%.
6. the preparation method of high-barrier according to claim 3, high tolerance compound proton exchange membrane, it is characterised in that：Institute
It states in step 3), for single-walled carbon nanotube when depositing film forming, the thin-film material for selecting printed on both sides silver inks electrode is substrate, and adjust
The excitation electrical field scanning range that field induces of economizing on electricity is 0-10V/cm, time duration scan ranging from 5-60min.
7. the preparation method of high-barrier according to claim 6, high tolerance compound proton exchange membrane, it is characterised in that：Lining
Bottom is microporous PVDF or PTFE material.
8. the preparation method of high-barrier according to claim 3, high tolerance compound proton exchange membrane, it is characterised in that：Institute
State in step 1), montmorillonite is sodium-based montmorillonite, intercalator is cationic surface active agent, anionic surfactant,
One kind in zwitterionic surfactant or nonionic surfactant.
9. the preparation method of high-barrier according to claim 3, high tolerance compound proton exchange membrane, it is characterised in that：Institute
It states in step 1), intercalator additive amount is 0.1-5 times of montmorillonite cation exchange capacity；Intercalation spacing is 1-10nm.
10. the preparation method of high-barrier according to claim 3, high tolerance compound proton exchange membrane, it is characterised in that：Institute
It states in step 4), graphene oxide and single-walled carbon nanotube and ion exchange resin are solution combined, and composite solution mass fraction is
0.1-40%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109326810A (en) * | 2018-10-10 | 2019-02-12 | 东北大学 | A method of high temperature proton exchange film is prepared based on modified carbon nano-tube |
| CN113113651A (en) * | 2021-03-12 | 2021-07-13 | 嘉寓氢能源科技(辽宁)有限公司 | Preparation method of proton exchange membrane material for hydrogen fuel cell |
| CN113471496A (en) * | 2021-06-29 | 2021-10-01 | 上海化工研究院有限公司 | High-proton conductivity high-strength perfluorosulfonic acid composite proton exchange membrane and preparation method thereof |
| CN114171764A (en) * | 2021-11-25 | 2022-03-11 | 湖北工业大学 | Proton exchange membrane and preparation method thereof |
| CN114864978A (en) * | 2022-06-16 | 2022-08-05 | 电子科技大学 | Hollow fiber membrane material of humidifier of high-humidity hydrogen fuel cell and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1677732A (en) * | 2005-01-04 | 2005-10-05 | 华南理工大学 | Organic-inorganic compoiste proton exchange film and preparing method |
| CN101319051A (en) * | 2008-07-15 | 2008-12-10 | 山东东岳神舟新材料有限公司 | Fibre reinforcement inorganics doped multi-layer fluorine ion exchange containing film |
| CN103367773A (en) * | 2013-06-24 | 2013-10-23 | 天津大学 | Alcohol-rejection proton conducting composite film and preparation method thereof |
| CN105355930A (en) * | 2015-11-30 | 2016-02-24 | 湖北工程学院 | Sulfonated aromatic polymer-modified carbon nanotube composite proton exchange membrane and preparation method thereof |
| CN105529485A (en) * | 2015-12-28 | 2016-04-27 | 湖北工程学院 | Preparation method of carbon nanotube-loaded heteropolyacid-sulfonated polyether ether ketone proton exchange membrane |
-
2017
- 2017-12-29 CN CN201711485481.XA patent/CN108232262A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1677732A (en) * | 2005-01-04 | 2005-10-05 | 华南理工大学 | Organic-inorganic compoiste proton exchange film and preparing method |
| CN101319051A (en) * | 2008-07-15 | 2008-12-10 | 山东东岳神舟新材料有限公司 | Fibre reinforcement inorganics doped multi-layer fluorine ion exchange containing film |
| CN103367773A (en) * | 2013-06-24 | 2013-10-23 | 天津大学 | Alcohol-rejection proton conducting composite film and preparation method thereof |
| CN105355930A (en) * | 2015-11-30 | 2016-02-24 | 湖北工程学院 | Sulfonated aromatic polymer-modified carbon nanotube composite proton exchange membrane and preparation method thereof |
| CN105529485A (en) * | 2015-12-28 | 2016-04-27 | 湖北工程学院 | Preparation method of carbon nanotube-loaded heteropolyacid-sulfonated polyether ether ketone proton exchange membrane |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109326810A (en) * | 2018-10-10 | 2019-02-12 | 东北大学 | A method of high temperature proton exchange film is prepared based on modified carbon nano-tube |
| CN109326810B (en) * | 2018-10-10 | 2021-03-19 | 东北大学 | Method for preparing high-temperature proton exchange membrane based on modified carbon nano tube |
| CN113113651A (en) * | 2021-03-12 | 2021-07-13 | 嘉寓氢能源科技(辽宁)有限公司 | Preparation method of proton exchange membrane material for hydrogen fuel cell |
| CN113471496A (en) * | 2021-06-29 | 2021-10-01 | 上海化工研究院有限公司 | High-proton conductivity high-strength perfluorosulfonic acid composite proton exchange membrane and preparation method thereof |
| CN114171764A (en) * | 2021-11-25 | 2022-03-11 | 湖北工业大学 | Proton exchange membrane and preparation method thereof |
| CN114171764B (en) * | 2021-11-25 | 2024-02-23 | 湖北工业大学 | Proton exchange membrane and preparation method thereof |
| CN114864978A (en) * | 2022-06-16 | 2022-08-05 | 电子科技大学 | Hollow fiber membrane material of humidifier of high-humidity hydrogen fuel cell and preparation method and application thereof |
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