CN101851382A - Fiber and modified silica-doped fluorine-containing ion film and preparation method thereof - Google Patents

Fiber and modified silica-doped fluorine-containing ion film and preparation method thereof Download PDF

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CN101851382A
CN101851382A CN201010181581A CN201010181581A CN101851382A CN 101851382 A CN101851382 A CN 101851382A CN 201010181581 A CN201010181581 A CN 201010181581A CN 201010181581 A CN201010181581 A CN 201010181581A CN 101851382 A CN101851382 A CN 101851382A
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fiber
modified silica
fluorine
containing ion
sio
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CN101851382B (en
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张永明
徐涛
裴素朋
张恒
高自宏
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Shandong Dongyue Polymer Material Co Ltd
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Shandong Dongyue Polymer Material Co Ltd
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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
    • 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 invention relates to a fiber and modified silica-doped fluorine-containing ion film and a preparation method thereof and belongs to the technical field of polymer composite materials. The preparation method comprises the following steps of: performing surface modification on powder SiO2 by using fluorine-containing compounds; dissolving hydrogen fluorine-containing sulfonic acid resin and fluorine-containing sulfonic acid metal salt resin by using a polar solvent, and adding a reinforced fiber and powder SiO2 subjected to surface modification by the fluorine-containing compounds, and uniformly mixing the solution through ultrasound or stirring; and forming the film by the solution by adopting the pouring, casting, screen printing, spraying or impregnating technology, and preparing the fiber and modified silica-doped fluorine-containing ion film through stripping. The prepared fluorine-containing sulfonic acid film has the advantages of better water conservation, higher proton conductivity, and higher mechanical properties.

Description

A kind of fiber and modified silica-doped fluorine-containing ion film and preparation method thereof
Technical field
The present invention relates to a kind of fiber and modified silica-doped fluorine-containing ion film and preparation method thereof, belong to technical field of polymer composite materials.
Background technology
Fuel cell (Fuel Cell) be a kind of with chemical energy without overheated and be converted into the device of electric energy.It utilizes non-petroleum fuel such as hydrogen, Sweet natural gas, coal gas and methyl alcohol and pure oxygen or air at the two poles of the earth of battery oxidation-reduction reaction to take place respectively, continuously provides direct current to environment.Fuel cell is considered to be hopeful to provide in a large number the 4th kind of generation technology of electric power after firepower, waterpower and nuclear energy power generation.Fuel cell has multiple, and the difference between the various fuel cells is the ionogen difference used.Proton Exchange Membrane Fuel Cells (Proton Exchange Membrane Fuel Cell, i.e. PEMFC) is an ionogen with the proton exchange membrane, is characterized in noiselessness, and zero pollutes; Do not have corrosion, the life-span is long.Because its specific power is big, the energy efficiency height, working temperature is low, and toggle speed is fast, is particularly suitable for as power cell.
Though the sulfonic fluoropolymer proton exchange membrane is used for many years, but still have low, the poor dimensional stability of high temperature proton conductivity, the not high shortcoming of physical strength does not reach commercial requirement.Especially dimensional stability aspect, film are also different because of the different swelling ratios of water-intake rate under different humidity.In addition, when the sulfonic fluoropolymer exchange membrane is worked under comparatively high temps,, thereby the efficient of fuel cell is descended greatly because the rapid dehydration of film causes the proton-conducting of film sharply to descend.But high working temperature (being higher than 90 ℃) can improve the anti-carbon monoxide of fuel-cell catalyst greatly.In addition, existing sulfonic fluoropolymer film has certain hydrogen or methanol permeability, and especially in direct methanol fuel cell, methanol permeability is very big, becomes fatal problem.Therefore, how to improve sulfonic fluoropolymer proton exchange film strength, dimensional stability, the perviousness of reduction working medium etc. is the key subjects that fuel cell industries faces.
For solving the high temperature proton conduction behavior of sulfonic fluoropolymer film, the inorganic additive that much has the high-temp water-preserving ability is added in the sulfonic fluoropolymer exchange membrane.Choose the requirement of inorganic water conservation particle: (1) particle has water retention capacity preferably, and higher dehydration temperature is just arranged; (2) has intermiscibility preferably with proton exchange resins; (3) particle has certain proton conducting ability; (4) be easy to obtain nanometer particle; (5) particle structure stability; (6) help keeping or improving the mechanical strength or the physical size stability of proton exchange membrane; Usually the inorganic water conservation particle that adopts is SiO 2, TiO 2, ZrHPO 4, ZrO 2Particle, heteropolyacid or solid acid particle, zeolite family mineral particle, stratotype clay mineral such as montmorillonite and intercalation clay mineral thereof etc.
Chinese patent CN1862857, CN200810138704.X, CN200810107853.X and CN200810138186.1 etc. disclose and added SiO in perfluorinated sulfonic resins 2Can improve the high-temperature electric conduction performance of proton exchange membrane etc. inorganic water-holding agent, mix fiber to improve the mechanical property of film.But they are not recognized: because the inorganic particulate particle diameter is little, specific surface area is big, reunite easily in the machine-shaping process; And owing to inorganic particulate tends to be separated with the matrix fluoro-resin, thereby have a strong impact on work-ing life, dimensional stability and the high-temperature electric conduction of film.
The sulfonic fluoropolymer ionic membrane that is used for fuel cell need satisfy following requirement: high temperature low humidity water retention property, Gaoyou specific conductivity, high mechanical strength preferably.Generally speaking, when ion-exchange capacity raise, the equivalent value of fluoropolymer decline (equivalent value EW value reduces, loading capacity IEC=1000/EW) film strength simultaneously also reduced.Therefore, preparation has a macroion exchange capacity, can exempt to keep physical strength simultaneously, and the ionic membrane with good water retention property and high proton conductivity is very important.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of ion-exchange membrane and preparation method with better conductivity and physical strength is provided.The present invention is by carrying out modification to silicon-dioxide, improve the degree of scatter of silicon dioxide microparticle in perfluorinated sulfonic resin, strengthen the affinity of particle and matrix resin, and in resin, mix fortifying fibre, finally improved physical strength, water retention property and the proton conductivity of sulfonic fluoropolymer ionic membrane.
A kind of fiber and modified silica-doped fluorine-containing ion film, it is a matrix with Hydrogen sulfonic fluoropolymer resin and sulfonic fluoropolymer metal-salt resin, fortifying fibre and through the SiO of fluorochemicals surface modification 2Powder is dispersed in the matrix.
Described sulfonic fluoropolymer metal-salt resin is 0.01～10wt% with respect to the content of Hydrogen sulfonic fluoropolymer resin, and the repeating unit number is 10～6000, has following (I) structure:
Figure GSA00000136972500021
M?M′＝Ce?Mn?La?Zn?W?Ti?V?Cr?Fe?Co?Ni?Cu?Zr?Nb?Mo?Ru?Rh?Pd?Ta?Re?Ir?Pt?H?Na?K
N, m represent the metal valence state;
A, b are not less than 1 integer, c, d=0 or 1 and c+d ≠ 0; (a+b)/(a+b+c+d)=0.5-0.99; (c+d)/(a+b+c+d)=0.01-0.5.
Described Hydrogen sulfonic fluoropolymer resin is repeated to form by the structural unit shown in the following formula II, and the repeating unit number is 30～3000:
Figure GSA00000136972500031
Wherein, X=H or F, Y=H, F or Cl, n=3～15, m=2～5, p=1 or 2, q=2 or 3.
Described SiO through the fluorochemicals surface modification 2Powder makes as follows:
(1) by amino silicane coupling agent to SiO 2The powder surface hydroxyl carries out amination modified, forms amination SiO 2Powder;
(2) with amination SiO 2Powder and fluorine-containing carboxylic acid reaction dehydration and finally form the SiO of fluorochemicals surface modification 2Powder;
Described amination SiO 2The amination degree of powder surface hydroxyl is 10～50mol%;
The structural formula of described amino silicane coupling agent is as follows:
Figure GSA00000136972500032
R 1, R 2And R 3Can choose from alkane, preferred carbonatoms is 1～5; R 4Contain AZA (Cyclo) Alkanes, R for the hydrogeneous alkane of carbonatoms 1～10 or carbonatoms 1～10 4Preferred carbonatoms be 2～6; R 5Alkane or perfluoro alkane for hydrogen atom or carbonatoms 1～10 are preferably hydrogen atom.Most preferred, amino silicane coupling agent is selected from one of γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, phenylamino Union carbide A-162, phenylamino methyltrimethoxy silane, phenylamino methyltrimethoxy silane, aminoethyl aminoethyl aminopropyl trimethoxysilane.
SiO 2There is great amount of hydroxy group in particle surface, can and slough small molecular alcohol with organoalkoxysilane reaction, utilizes this reaction can be easily at SiO 2The surface of powder is introduced amino; Amino can further be sloughed a part water with the perfluorocarboxylic acid reaction again, finally at SiO 2Fluorine-containing molecular chain is introduced on the surface.SiO 2The amination degree of powder surface hydroxyl should be controlled at 10～50mol% usually, the too high then SiO of amination degree 2Lose moisture retention.
Perfluorocarboxylic acid be the perfluorocarboxylic acid of carbonatoms 1～10 or carbonatoms 1～100 contain the oxygen perfluorocarboxylic acid, as Perfluorocaprylic Acid, perfluoro propene oxid homopolymer carboxylic acid (synthetic method of perfluoro propene oxid homopolymer can with reference to U.S. Pat 3412148).
The SiO of described fluorochemicals surface modification 2The mass ratio of powder and perfluorinated sulfonic resin is 0.5～100: 100, and preferred, mass ratio is 0.5～50: 100; SiO 2Particle diameter be 0.05～30 μ m.
Described fortifying fibre is selected from: one or more of glass fibre, fluorocarbon polymer fiber, ceramic fiber, silica fiber, mineral fibre or silicon carbide fiber preferably, are selected from one or both of silica fiber or fluorocarbon polymer fiber; The fortifying fibre diameter is 0.005～50 μ m, and length is 0.05～200 μ m, and preferred length is 0.05～80 μ m, and reinforced fiber content is 0.01～35% of a gross weight.
Described glass fibre is selected from alkali resistant glass fibre or alkali free glass fibre.
Described fluorocarbon polymer fiber is selected from polytetrafluoroethylene fiber, poly-perfluoro propyl vinyl fiber, perfluoroethylene-propylene fiber.
The preparation method of a kind of fiber and modified silica-doped fluorine-containing ion film, step is as follows:
Sulfonic fluoropolymer metal-salt resin and Hydrogen sulfonic fluoropolymer resin shown in the logical formula I are dissolved with polar solvent, obtain perfluor sulfoacid resin solution; The SiO that in perfluor sulfoacid resin solution, adds dispersion agent, fortifying fibre, fluorochemicals surface modification then 2Powder, and even by stirring and ultra-sonic dispersion; With the technology film forming of finely dispersed solution by solution-cast, solution casting, silk-screen printing technique, spraying or dipping, and, make fiber and modified silica-doped fluorine-containing ion film through peeling off with film thermal treatment 0.02～800 minute under 30～250 ℃ temperature.
Dispersion agent is selected from: sodium polyphosphate, Rapisol or ammonium polyphosphate, add-on are 0.01～10% of gross weight.Polar solvent is selected from one or more in dimethyl formamide, N,N-DIMETHYLACETAMIDE, methylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, water, ethanol, methyl alcohol, propyl alcohol, the Virahol.The adding of dispersion agent is for improving the degree of scatter of fiber in resin.
Fiber of the present invention and modified silica-doped fluorine-containing ion film can also be kept high mechanical strength when having the macroion exchange capacity, and have better water retention performance and high proton transmissibility.
Embodiment:
The present invention will be further described below by embodiment, but institute of the present invention protection domain is not limited only to this.
Embodiment 1
Under 100 ℃ of normal pressures, be 200nm SiO with particle diameter 2Powder and γ-An Bingjisanjiayangjiguiwan obtain amination SiO reflux in toluene 3 hours 2Powder, amination SiO 2The amination degree of powder surface hydroxyl is 10mol%, adds and the equimolar Perfluorocaprylic Acid of γ-An Bingjisanjiayangjiguiwan then, reclaims solvent at 120 ℃ of following decompression vacuum pumpings after keeping refluxing 3 hours, obtains the SiO of fluorochemicals surface modification 2Powder (content is 10%); To have logical formula I a=1, b=1, c=0, d=1, the sulfonic fluoropolymer metal-salt resin of M=M '=Ce structure and have a logical formula II n=9, p=2, X=F, Y=F, the Hydrogen sulfonic fluoropolymer resin dissolves of q=2 is (the perfluorinated sulfonic resin total concn is 40%) in dimethyl formamide, sulfonic fluoropolymer cerium salt resin is 0.3wt% with respect to the content of Hydrogen sulfonic fluoropolymer resin, obtains perfluor sulfoacid resin solution, adds the SiO of fluorochemicals surface modification under the state of the stirring that keeps 200r/min successively 2Powder, sodium polyphosphate (account for total mass 5%), diameter are the silica fiber (silica fiber quality account for total mass 5%) of 0.02 μ m length, 0.05 μ m, the method of utilizing spraying coating process is prepared fiber and modified silica-doped fluorine-containing ion film that thickness is 50 μ m 190 ℃ of following thermal treatments 45 minutes.Tensile strength is: 27MPa, electricity lead and are 125mS/cm.
Embodiment 2
Under 100 ℃ of normal pressures, be 5 μ m SiO with particle diameter 2Powder and N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan obtain amination SiO reflux in toluene 3 hours 2Powder, amination SiO 2The amination degree of powder surface hydroxyl is 16.5mol%, add and N-β (the aminoethyl)-equimolar perfluoro propene oxid homopolymer of γ-An Bingjisanjiayangjiguiwan carboxylic acid (mean polymerisation degree is 6) then, reclaim solvent at 120 ℃ of following decompression vacuum pumpings after keeping refluxing 3 hours, obtain the SiO of fluorochemicals surface modification 2Powder (content is 16.5%); To have logical formula I a=1, b=2, c=1, d=1, M=Mn, the sulfonic fluoropolymer metal-salt resin of M '=Zn structure and have a logical formula II n=14, p=2, X=F, Y=Cl, the Hydrogen sulfonic fluoropolymer resin dissolves of q=3 is (the perfluorinated sulfonic resin total concn is 40%) in N,N-DIMETHYLACETAMIDE, sulfonic fluoropolymer metal-salt resin is 0.25wt% with respect to the content of Hydrogen sulfonic fluoropolymer resin, obtain perfluor sulfoacid resin solution, under the state of the stirring that keeps 178r/min, add the SiO of fluorochemicals surface modification successively 2Powder, ammonium polyphosphate (account for total mass 7.6%), diameter are the polytetrafluoroethylene fiber (content that fiber quality accounts for total mass is 10%) of 40 μ m length, 150 μ m, the method of utilizing silk-screen printing technique is prepared fiber and modified silica-doped fluorine-containing ion film that thickness is 30 μ m 170 ℃ of following thermal treatments 15 minutes.Tensile strength is: 33MPa, electricity lead and are 105mS/cm.
Embodiment 3
Under 100 ℃ of normal pressures, be 5 μ m SiO with particle diameter 2Powder and N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan obtain amination SiO reflux in toluene 3 hours 2Powder, amination SiO 2The amination degree of powder surface hydroxyl is 21.5mol%, add and N-β (the aminoethyl)-equimolar perfluoro propene oxid homopolymer of γ-An Bingjisanjiayangjiguiwan carboxylic acid (mean polymerisation degree is 10) then, reclaim solvent at 120 ℃ of following decompression vacuum pumpings after keeping refluxing 3 hours, obtain the SiO of fluorochemicals surface modification 2Powder; To have logical formula I a=2, b=1, c=0.1, d=0.1, M=Mn, the sulfonic fluoropolymer metal-salt resin of M '=Zn structure and have logical formula II n=5, p=1, an X=F, Y=Cl, the Hydrogen sulfonic fluoropolymer resin dissolves of q=2 is (the perfluorinated sulfonic resin total concn is 40%) in ethanol, and sulfonic fluoropolymer metal-salt resin is 0.3wt% with respect to the content of Hydrogen sulfonic fluoropolymer resin, adds the SiO of fluorochemicals surface modification under the state that keeps high-speed stirring successively 2Powder (content is 25%), Rapisol (account for total mass 6%), diameter are the polytetrafluoroethylene fiber (fiber quality content is 6%) of 10 μ m length, 50 μ m, the method of utilizing casting is prepared fiber and modified silica-doped fluorine-containing ion film that thickness is 80 μ m 150 ℃ of following thermal treatments 40 minutes.Tensile strength is: 30MPa, electricity lead and are 135mS/cm.

Claims (12)

1. fiber and modified silica-doped fluorine-containing ion film, it is characterized in that: it is a matrix with Hydrogen sulfonic fluoropolymer resin and sulfonic fluoropolymer metal-salt resin, fortifying fibre and through the SiO of fluorochemicals surface modification 2Powder is dispersed in the matrix.
2. fiber as claimed in claim 1 and modified silica-doped fluorine-containing ion film is characterized in that: repeated to form by structural unit as follows, the repeating unit number is 30～3000:
Figure FSA00000136972400011
Wherein, X=H or F, Y=H, F or Cl, n=3～15, m=2～5, p=1 or 2, q=2 or 3.
3. fiber as claimed in claim 1 and modified silica-doped fluorine-containing ion film is characterized in that: the content with respect to Hydrogen sulfonic fluoropolymer resin is 0.01～10wt%, and the repeating unit number is 10～6000, has following structure:
M?M＝Ce?Mn?La?Zn?W?Ti?V?Cr?Fe?Co?Ni?Cu?Zr?Nb?Mo?Ru?Rh?Pd?Ta?Re?Ir?Pt H?Na?K
N, m represent the metal valence state;
A, b are not less than 1 integer, c, d=0 or 1 and c+d ≠ 0; (a+b)/(a+b+c+d)=0.5-0.99; (c+d)/(a+b+c+d)=0.01-0.5.
4. fiber as claimed in claim 1 and modified silica-doped fluorine-containing ion film is characterized in that: described SiO through the fluorochemicals surface modification 2Powder makes as follows:
(1) by amino silicane coupling agent to SiO 2The powder surface hydroxyl carries out amination modified, forms amination SiO 2Powder;
(2) with amination SiO 2Powder and fluorine-containing carboxylic acid reaction dehydration and finally form the SiO of fluorochemicals surface modification 2Powder.
5. fiber as claimed in claim 4 and modified silica-doped fluorine-containing ion film is characterized in that: described amination SiO 2The amination degree of powder surface hydroxyl is 10～50mol%.
6. fiber as claimed in claim 4 and modified silica-doped fluorine-containing ion film is characterized in that: the structural formula of described amino silicane coupling agent is as follows:
Figure FSA00000136972400021
R 1, R 2And R 3Can choose from alkane, preferred carbonatoms is 1～5; R 4Contain AZA (Cyclo) Alkanes, R for the hydrogeneous alkane of carbonatoms 1～10 or carbonatoms 1～10 4Preferred carbonatoms be 2～6; R 5Alkane or perfluoro alkane for hydrogen atom or carbonatoms 1～10 are preferably hydrogen atom.Most preferred, amino silicane coupling agent is selected from one of γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, phenylamino Union carbide A-162, phenylamino methyltrimethoxy silane, phenylamino methyltrimethoxy silane, aminoethyl aminoethyl aminopropyl trimethoxysilane.
7. fiber as claimed in claim 4 and modified silica-doped fluorine-containing ion film is characterized in that: described perfluorocarboxylic acid be the perfluorocarboxylic acid of carbonatoms 1～10 or carbonatoms 1～100 contain the oxygen perfluorocarboxylic acid.
8. fiber as claimed in claim 1 and modified silica-doped fluorine-containing ion film is characterized in that: the SiO of described fluorochemicals surface modification 2The mass ratio of powder and perfluorinated sulfonic resin is 0.5～100: 100, and preferred, mass ratio is 0.5～50: 100; SiO 2Particle diameter be 0.05～30 μ m.
9. fiber as claimed in claim 1 and modified silica-doped fluorine-containing ion film, it is characterized in that: described fortifying fibre is selected from: one or more of glass fibre, fluorocarbon polymer fiber, ceramic fiber, silica fiber, mineral fibre or silicon carbide fiber, preferably, be selected from one or both of silica fiber or fluorocarbon polymer fiber; The fortifying fibre diameter is 0.005～50 μ m, and length is 0.05～200 μ m, and preferred length is 0.05～80 μ m, and reinforced fiber content is 0.01～35% of a gross weight.
10. fiber as claimed in claim 9 and modified silica-doped fluorine-containing ion film is characterized in that: described glass fibre is selected from alkali resistant glass fibre or alkali free glass fibre; Described fluorocarbon polymer fiber is selected from polytetrafluoroethylene fiber, poly-perfluoro propyl vinyl fiber, perfluoroethylene-propylene fiber.
11. the preparation method of fiber as claimed in claim 1 and modified silica-doped fluorine-containing ion film, step is as follows:
(1) sulfonic fluoropolymer metal-salt resin shown in the general formula (I) and Hydrogen sulfonic fluoropolymer resin are dissolved with polar solvent, obtain perfluor sulfoacid resin solution;
(2) in the perfluor sulfoacid resin solution that step (1) makes, add the SiO of dispersion agent, fortifying fibre, fluorochemicals surface modification 2Powder, and even by stirring and ultra-sonic dispersion;
(3) the finely dispersed solution that step (2) is made is by the technology film forming of solution-cast, solution casting, silk-screen printing technique, spraying or dipping, and, make fiber and modified silica-doped fluorine-containing ion film through peeling off with film thermal treatment 0.02～800 minute under 30～250 ℃ temperature.
12. the preparation method of fiber as claimed in claim 11 and modified silica-doped fluorine-containing ion film is characterized in that: described dispersion agent is selected from: sodium polyphosphate, Rapisol or ammonium polyphosphate, add-on are 0.01～10% of gross weight; Described polar solvent is selected from one or more in dimethyl formamide, N,N-DIMETHYLACETAMIDE, methylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, water, ethanol, methyl alcohol, propyl alcohol, the Virahol.
CN2010101815815A 2010-05-25 2010-05-25 Fiber and modified silica-doped fluorine-containing ion film and preparation method thereof Active CN101851382B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105820481A (en) * 2016-05-04 2016-08-03 江苏富仕德科技发展有限公司 Fluorinated silicate fiber electronic felt and preparation method thereof
US9725568B2 (en) 2011-12-19 2017-08-08 National Research Council Of Canada Co-extruded ultra thin films
CN111129559A (en) * 2019-12-26 2020-05-08 佛山市金辉高科光电材料股份有限公司 Proton exchange membrane for fuel cell and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN101237055A (en) * 2008-02-03 2008-08-06 山东东岳神舟新材料有限公司 A fiber enhanced inorganic adulterated full fluorin proton exchange film
CN101348574A (en) * 2008-07-22 2009-01-21 山东东岳神舟新材料有限公司 Fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101237055A (en) * 2008-02-03 2008-08-06 山东东岳神舟新材料有限公司 A fiber enhanced inorganic adulterated full fluorin proton exchange film
CN101290996A (en) * 2008-02-03 2008-10-22 山东东岳神舟新材料有限公司 Fiber reinforced inorganic doped proton exchange film containing fluorine
CN101348574A (en) * 2008-07-22 2009-01-21 山东东岳神舟新材料有限公司 Fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9725568B2 (en) 2011-12-19 2017-08-08 National Research Council Of Canada Co-extruded ultra thin films
CN105820481A (en) * 2016-05-04 2016-08-03 江苏富仕德科技发展有限公司 Fluorinated silicate fiber electronic felt and preparation method thereof
CN111129559A (en) * 2019-12-26 2020-05-08 佛山市金辉高科光电材料股份有限公司 Proton exchange membrane for fuel cell and preparation method thereof
CN111129559B (en) * 2019-12-26 2021-06-15 佛山市金辉高科光电材料股份有限公司 Proton exchange membrane for fuel cell and preparation method thereof

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