CN101030644A - Production of composite proton exchange-film of water-retaining component uniform dispersion - Google Patents

Production of composite proton exchange-film of water-retaining component uniform dispersion Download PDF

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CN101030644A
CN101030644A CNA2007100516778A CN200710051677A CN101030644A CN 101030644 A CN101030644 A CN 101030644A CN A2007100516778 A CNA2007100516778 A CN A2007100516778A CN 200710051677 A CN200710051677 A CN 200710051677A CN 101030644 A CN101030644 A CN 101030644A
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inorganic oxide
preparation
water
solution
proton exchange
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CN100479242C (en
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唐浩林
邬静杰
潘牧
宛朝辉
李跃卿
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Wuhan University of Science and Engineering WUSE
Wuhan University of Technology WUT
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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

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Abstract

The invention is concerned with the preparation method of the compounding proton exchanging film that the water reserving group separates equally. The characteristic is: compounds inorganic oxide colloid that decorates the ionic polymer; prepares the exchange film by the colloid liquid directly. The ionic polymer in the film is with the proton conducting capability, the inorganic oxide colloid is with the water reserving capability. The inorganic oxide water reserving group in the compounding proton exchanging film is with better decentrality, because ionic polymer is with better steric hindrance and the static effect in the decentralization system and the inorganic oxide nanometer grain prepares at the original position, in order that the proton exchange film is with better mechanism intensity and water reserving capability and with better capability at the low humidity condition.

Description

The preparation method of the homodisperse compound proton exchange membrane of a kind of water-retaining component
Technical field
The present invention relates to a kind of fuel cell homodisperse compound proton exchange membrane of water-retaining component and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) has high power density; high-energy conversion efficiency; advantages of environment protection; promise to be most the power source of zero disposal of pollutants electric automobile; make it in today that global energy crisis and environment go from bad to worse, become one of focus of international new and high technology competition.Proton exchange membrane is the core carrier of electrochemical reaction of fuel battery, plays a part to provide proton channel and isolates reacting gas.Desirable proton exchange membrane should have: high proton conductivity, low gas permeability, sufficiently high mechanical strength, good thermal stability and chemical stability, suitable cost performance.At present general proton exchange membrane material is the conductive polymer membrane that du pont company is produced, and the composite membrane that makes based on electrically conductive polymer resin of Canadian Gore company.There is the not enough problem of film water holding capacity in the both, especially in hot environment.And the conductivity of proton exchange membrane is almost linear with the water content of film.And the even aquation of whole proton exchange membrane, can prevent local dehydration of film and hot localised points, therefore can avoid because the battery performance that local dehydration of film and hot localised points cause descends and the membrane material degraded.That is to say that Proton Exchange Membrane Fuel Cells ground service behaviour relies on the water content of film to a great extent.Therefore in order to guarantee the Proton Exchange Membrane Fuel Cells normal power generation, just must carry out water management to fuel cell.Usual method is reacting gas to be carried out humidification prevent that film is dry, the especially anode-side of proton exchange membrane and not dehydration of entrance point, the water content of increase proton exchange membrane.Reacting gas humidifying equipment commonly used has bubbling humidifier, membrane humidifier, dew point humidifier, direct work of water sprinkling for better material moisture device etc.Yet these humidifying equipments make the whole generating system become complicated, have increased system cost, and have been unfavorable for portable use.Preparation at present is to add the supported catalyst that contains Pt in electrically conductive polymer resin solution from the method for moistened membrane, relies on from the O of yin, yang the two poles of the earth infiltration 2And H 2Pt catalyst surface generation chemical catalysis water generation reaction in proton exchange membrane is with the water humidifying proton exchange film of electrochemical cathode reaction generation.But because the adding of Pt makes the preparation cost of film improve, and the skewness of Pt, therefore dispersed relatively poor in film by the water that the Pt catalytic reaction generates, easily in film, generate focus and damage composite membrane.Mix hydrophilic SiO 2, TiO 2Can improve the water retention property of film etc. inorganic oxide nanoparticles, but the SiO that mixes 2, TiO 2There is the problem of interface compatibility with electrically conductive polymer resin solution, and preparation method routinely, SiO 2, TiO 2Disperse unevenly equally in electrically conductive polymer resin solution, make that water distribution is inhomogeneous in the film, influence water transporting continuously in film, equally easily generation focus and damage composite membrane in film.Therefore, research has the appropriateness price ratio, and the proton exchange membrane that water-retaining component is uniformly dispersed and water holding capacity is good is an important problem.
[US5766787] introduced a kind of compound from moistened membrane.With noble metal granules such as platinum, etc. nano level particle add in the electrically conductive polymer resin solution, rely on from the O of yin, yang the two poles of the earth infiltration 2And H 2Pt catalyst surface chemical catalysis water generation reaction in proton exchange membrane, with the water humidifying proton exchange film that the electrochemical cathode reaction generates, wherein oxidation particle plays the effect that keeps moisture in the film.This composite membrane has been compared water holding capacity preferably with the Nafion film, but its SiO 2, TiO 2Skewness in film, and the Pt distribution of particles is inhomogeneous in the composite membrane all can cause in the film water distribution inhomogeneous, generates focus, damages composite membrane.
Dalian Chemical Physics Research Institute adds perfluorinated sulfonic resin earlier in the mixed solvent of the organic alcohol and water of low boiling in patent [CN1464580], make perfluor sulfoacid resin solution after the high pressure heating for dissolving.Add supported catalyst and the high boiling organic solvent that contains Pt in perfluor sulfoacid resin solution, after mixing this mixed solution is dripped on the organic porous films surface, heating in vacuum makes self-humidifying composite proton exchange film.Though the preparation technology of this composite membrane is simpler, the skewness of its Pt easily generates focus and damages composite membrane.
[US20060096913] comprising SO 2X, PO 2In the polymeric matrix of X or COX (X=F, Cl, Br, I) group, add the TiO that hydrolysis generates 2, ZrO 2, SnO 2, SiO 2Form the organic/inorganic blended liquid etc. inorganic oxide nanoparticles, and prepare the organic/inorganic blend film with this organic/inorganic blended liquid.The blend film of preparation has machinery and thermal stability preferably, has demonstrated certain water holding capacity during in T＞80 ℃.But hydrolysis does not add protective agent when generating inorganic oxide nanoparticles, inorganic oxide nanoparticles easily reunite and polymeric matrix in disperse inhomogeneous.
[US20050227135] directly adds the porous TiO of particle diameter 100nm～50 μ m in Nafion solution 2, ZrO 2, GeO 2, SnO 2, SiO 2Or Zr 3(PO 4) 4Preparation of granules Nafion/ inorganic matter composite membrane.Nafion/ inorganic matter composite membrane is compared with the Nafion film, and battery performance is superior under no humidified condition.But inorganic oxide nanoparticles is a machinery to add, and unavoidably causes inorganic oxide nanoparticles skewness in Nafion solution, makes water at Nafion/ inorganic matter composite membrane skewness, influences film and gets proton conductivity.
In [EP0926754], the nanometer SiO that Arico Antonino and Antonucci Vincenzo then will synthesize in advance 2Particle dopedly pass to blend film forming in the resin solution to proton.Nanometer SiO in this film 2Decentralization is better, can also keep higher conductivity in the time of 145 ℃, but nanometer SiO 2Particle is easy to reunite in phase transition behavior takes place, and its particle diameter is difficult to control, and the mechanical strength of film also waits to improve.People such as Masahiro Watenabe (J.Electrochem.Soc, 1996,143,3847-3852) colloid that contains titanium oxide and Nafion resin solution double teeming film forming have been made Nafion/SiO 2Composite membrane, but TiO in the composite membrane 2Particle diameter and decentralization be difficult to control.
Summary of the invention:
The purpose of this invention is to provide the homodisperse proton exchange membrane of a kind of water-retaining component, thereby reduce the dependence of Proton Exchange Membrane Fuel Cells humidification system.
The homodisperse proton exchange membrane of water-retaining component provided by the present invention, the inorganic oxide nanoparticles colloidal solution of being modified by ionomer prepares.Water retaining function is provided by the inorganic oxide of possess hydrophilic property, and the proton conduction function is provided by the ionomer sulfonate radical side chain of modifying in the inorganic oxide outside.Ionomer and inorganic oxide nanoparticles adjustable ratio make that the compound proton exchange membrane water retaining function of preparation is adjustable.
The preparation process of the homodisperse proton exchange membrane of water-retaining component of the present invention is:
1), preparation inorganic oxide precursor liquid solution: earlier ionomer solution is regulated pH value to 6.5～7.5 with NaOH, be transferred in the anhydrous organic solvent then, make ionomer content in anhydrous organic solvent reach 1-10wt.%, then distill this solution 4-6 hour to remove moisture in the solution;
2), the preparation of colloid precursor solution: according to inorganic oxide precursor body and ionomer weight ratio 0.05: 1～0.3: 1, the inorganic oxide precursor body is joined in the inorganic oxide precursor liquid solution of step 1) preparation, stirred 20～30 minutes, and made the colloid precursor solution;
3), the preparation of the inorganic oxide nanoparticles colloidal solution that ionomer is modified: according to required 1: 1～10: 1 the ratio of the water yield of inorganic oxide precursor body hydrolysis, with HCl content is 37wt.%, water content is that the concentrated hydrochloric acid of 63wt% joins step 2) preparation the colloid precursor solution in, fully mix (6～8 hours), obtain the inorganic oxide nanoparticles colloidal solution that ionomer is modified, evenly wrapped up by ionomer around the inorganic oxide nanoparticles, because ionomer has good steric effect and electrostatic effect in dispersion, the inorganic oxide nanoparticles good dispersion in colloidal solution that makes the ionomer modification;
4), the homodisperse compound proton exchange membrane preparation of water-retaining component: the colloidal solution of step 3) preparation is placed culture dish, regulate pH value to 6.5～7.5 with NaOH, stir and be placed in the vacuum drying chamber after 20～30 minutes, be incubated 3～5 hours down at 110～140 ℃, and then be incubated 1～3 hour down at 180～200 ℃, make the homodisperse compound proton exchange membrane of water-retaining component after the solvent evaporates;
Wherein, described inorganic oxide is SiO 2Or TiO 2Any, select SiO for use 2The time, then the inorganic oxide precursor body be tetraethoxysilane, tetramethoxy-silicane any one; Select TiO for use 2The time, then the inorganic oxide precursor body be metatitanic acid second fat, metatitanic acid isopropyl ester and metatitanic acid fourth fat any one.
Described ionomer, selecting the sulfonic acid type anionic polymer of the side chain that has sulfonate group, this polymer for use is any in the hydrocarbon alkyl resin of perfluorinated sulfonic resin, sulfonation trifluorostyrene, sulfonated polyether-ether-ketone and sulfonation.
Described anhydrous organic solvent is selected N-methyl pyrrolidone, fourth-two eyeball, acetate, glycol-ether or ethylene glycol-methyl ether, or the mixed solution of above-mentioned any two kinds of solvents.
Proton exchange membrane of the present invention is the inorganic oxide nanoparticles colloidal solution preparation of being modified by ionomer.Water retaining function is provided by the inorganic oxide of possess hydrophilic property, and the proton conduction function is provided by the ionomer sulfonate radical side chain of modifying in the inorganic oxide outside.Ionomer and inorganic oxide nanoparticles adjustable ratio make that the compound proton exchange membrane water retaining function of preparation is adjustable.Ionomer has good steric effect and electrostatic effect in dispersion, and inorganic oxide nanoparticles is that in-situ preparing forms, there are interface compatibility preferably in ionomer and inorganic oxide nanoparticles, inorganic oxide water-retaining component particle diameter is even in the compound proton exchange membrane of finally preparing, good dispersion, thereby make proton exchange membrane have good mechanical strength and water holding capacity, have good battery performance under the low humidity condition, this water holding capacity also makes this proton exchange membrane have under 100～120 ℃ of hot conditionss to have good ability to work.
The present invention compares with prior art, has following advantage:
(1) the compound proton exchange membrane water-retaining component of the present invention's preparation evenly disperses, and can make the even aquation of film, prevents local dehydration of film and hot localised points, can avoid because the battery performance that local dehydration of film and hot localised points cause descends and the membrane material degraded.
(2) the compound proton exchange membrane water holding capacity of the present invention preparation is superior, utilizes the battery of this film assembling, low-humidification or fully not under the humidification condition battery performance be better than the battery of pure film assembling greatly.
(3) compound proton exchange membrane of the present invention's preparation can be realized stable operation, and preparation technology is simple, and production cost is relatively low, makes things convenient for large-scale production.
Description of drawings
Fig. 1 is the SiO that the perfluorinated sulfonic resin (Nafion DE 520 solution) produced of the embodiment of the invention 1 is modified 2Nano particle high power transmission electron microscope picture.
Fig. 2 a, Fig. 2 b are respectively SiO in the proton exchange membrane SEM stereoscan photograph produced of the embodiment of the invention 1 and the film 2The EDAX spectrogram.
Fig. 3 is the proton exchange membrane different humidity that the embodiment of the invention 1 is produced, 600mAcm -2Discharge curve under the constant current.
Fig. 4 is Nafion 212 film different humidity, 600mAcm -2Discharge curve under the constant current.
Embodiment
In order to understand the present invention better, further illustrate the present invention ground content below in conjunction with example.
Embodiment 1:
Water-retaining component is SiO 2The homodisperse compound proton exchange membrane preparation of nano particle
Preparation process is:
(1) measure 500 milliliters of perfluorinated sulfonic resins (Nafion DE 520 solution), regulate pH value to 7.5 with NaOH, be transferred to then in 500 milliliters of N-methyl pyrrolidones, electromagnetic agitation 30 minutes fully is dissolved in the N-methyl pyrrolidone perfluorinated sulfonic resin.Distill this solution, reach 203 ℃ to solution temperature, finish;
(2) measure 20 milliliters of tetraethoxysilanes, be dissolved in 80 milliliters of perfluorinated sulfonic resins (Nafion DE 520 solution)/N-methyl pyrrolidone solution electromagnetic agitation 30 minutes.Add the hydrochloric acid (HCl mass content 37wt.%) that is in excess in 4 times of hydrolysis, electromagnetic agitation 8 hours obtains the SiO that perfluorinated sulfonic resin (Nafion DE 520 solution) is modified 2Nanoparticulate dispersion;
(3) SiO of the perfluorinated sulfonic resin that step (2) is made (Nafion DE 520 solution) modification 2Nanoparticulate dispersion places surface plate, dilute by excessive 5 times perfluorinated sulfonic resin (Nafion DE 520 solution), regulate pH value to 7.5 with NaOH, then this resin solution is put into vacuum furnace, 130 ℃ are incubated 5 hours down, and then 200 ℃ are incubated 3 hours down, make proton exchange membrane after the solvent evaporates.The protonated processing of proton exchange membrane is under 80 ℃, earlier at 5wt%H 2O 2The middle infiltration 30 minutes then soaked into 30 minutes at deionized water, used the protonated processing of 0.5 mol dilution heat of sulfuric acid 30 minutes then, embathed 30 minutes promptly with deionized water once more.
The film of producing by this method, water-retaining component is uniformly dispersed, and water retention property is very excellent (sees Fig. 1, Fig. 2).Under 90 ℃ not outside humidification, conductivity can be stabilized in 0.8S/cm.With this film fuel battery assembled, 75RH% and 100RH% battery performance basically identical are under the no humidification condition, the battery performance rate of decay is 0.29 millivolt/minute, and under the Nafion 212 film 50RH% humidification conditions, the battery performance rate of decay is 0.83 millivolt/minute and (sees Fig. 3, Fig. 4).
Performance parameter Mechanical strength/MPa Conductance/Scm -2 Gas permeability/cm 3cm·cm -2·sec -1·cm Hg -1 600mAcm -2Voltage attenuation speed/mV/min under 25% humidity
Performance index 26 0.92 1.2×10 -8 0.18
Embodiment 2:
Water-retaining component is TiO 2The homodisperse compound proton exchange membrane preparation of nano particle
Preparation process is:
(1) measure 500 milliliters of sulfonation trifluorostyrene, regulate pH value to 6.5 with NaOH, be transferred to then in 500 milliliters of glycol-ethers, electromagnetic agitation 30 minutes fully is dissolved in the glycol-ether sulfonation trifluorostyrene.Distill this solution, reach 203 ℃ to solution temperature, finish;
(2) measure 40 milliliters of metatitanic acid second fat, be dissolved in 100 milliliters of sulfonation trifluorostyrene/glycol-ether solution electromagnetic agitation 30 minutes.Add the hydrochloric acid (HCl mass content 37%) that is in excess in 5 times of hydrolysis, electromagnetic agitation 6 hours obtains the TiO that the sulfonation trifluorostyrene is modified 2Nanoparticulate dispersion;
(3) TiO that the sulfonation trifluorostyrene that step (2) is made is modified 2Nanoparticulate dispersion places surface plate, sulfonation trifluorostyrene dilution by 5 times of excessive metatitanic acid second fat hydrolysis, regulate pH value to 6.5 with NaOH, then this resin solution is put into vacuum furnace, 130 ℃ are incubated 6 hours down, and then 200 ℃ are incubated 4 hours down, make proton exchange membrane after the solvent evaporates.The protonated processing of proton exchange membrane is under 80 ℃, earlier at 5wt%H 2O 2The middle infiltration 30 minutes then soaked into 30 minutes at deionized water, used the protonated processing of 0.5 mol dilution heat of sulfuric acid 30 minutes then, embathed 30 minutes promptly with deionized water once more.
Performance parameter Mechanical strength/MPa Conductance/Scm -2 Gas permeability/cm 3cm·cm -2·sec -1·cm Hg -1 600mAcm -2Voltage attenuation speed/millivolt under 25% humidity/minute
Performance index 14.2 0.63 1.5×10 -8 0.23
Embodiment 3:
Water-retaining component is SiO 2The homodisperse compound proton exchange membrane preparation of nano particle
Preparation process is:
(1) measure 500 milliliters of sulfonated polyether-ether-ketones, regulate pH value to 7 with NaOH, be transferred to then in 500 milliliters of ethylene glycol-methyl ethers, electromagnetic agitation 30 minutes fully is dissolved in ethylene glycol-methyl ether sulfonated polyether-ether-ketone.Distill this solution, reach 203 ℃ to solution temperature, finish;
(2) measure 50 milliliters of tetramethoxy-silicanes, be dissolved in 80 milliliters of sulfonated polyether-ether-ketone/ethylene glycol-methyl ether solution electromagnetic agitation 30 minutes.Add the hydrochloric acid (HCl mass content 37%) that is in excess in 4 times of hydrolysis, electromagnetic agitation 6 hours obtains the SiO that sulfonated polyether-ether-ketone is modified 2Nanoparticulate dispersion;
(3) SiO that the sulfonated polyether-ether-ketone that step (2) is made is modified 2Nanoparticulate dispersion places surface plate, sulfonated polyether-ether-ketone dilution by 5 times of excessive tetramethoxy-silicane hydrolysis, regulate pH value to 7 with NaOH, then this dispersion liquid is put into vacuum furnace, 130 ℃ are incubated 6 hours down, and then 200 ℃ are incubated 4 hours down, make proton exchange membrane after the solvent evaporates.The protonated processing of proton exchange membrane is under 80 ℃, earlier at 5wt%H 2O 2The middle infiltration 30 minutes then soaked into 30 minutes at deionized water, used the protonated processing of 0.5 mol dilution heat of sulfuric acid 30 minutes then, embathed 30 minutes promptly with deionized water once more.
Performance parameter Mechanical strength/MPa Conductance/Scm -2 Gas permeability/cm 3cm·cm -2·sec -1·cm Hg -1 600mAcm -2Voltage attenuation speed/millivolt under 25% humidity/minute
Performance index 18.3 0.58 1.3×10 -8 0.24

Claims (4)

1, the preparation method of the homodisperse compound proton exchange membrane of a kind of water-retaining component.It is characterized in that preparation process is undertaken by following process:
1), preparation inorganic oxide precursor liquid solution:: earlier ionomer solution is regulated pH value to 6.5～7.5 with NaOH, be transferred in the anhydrous organic solvent then, make ionomer content in anhydrous organic solvent reach 1-10wt.%, then distill this solution 4-6 hour to remove moisture in the solution;
2), the preparation of colloid precursor solution: according to inorganic oxide precursor body and ionomer weight ratio 0.05: 1～0.3: 1, the inorganic oxide precursor body is joined in the inorganic oxide precursor liquid solution of step 1) preparation and stirred 20～30 minutes, make the colloid precursor solution;
3), the preparation of the inorganic oxide nanoparticles colloidal solution of ionomer modification: according to required 1: 1～10: 1 the ratio of the water yield of inorganic oxide precursor body hydrolysis, with HCl content is 37wt.%, water content is that the concentrated hydrochloric acid of 63wt% joins step 2) preparation the colloid precursor solution in, fully mix, obtain the inorganic oxide nanoparticles colloidal solution that ionomer is modified;
4), the homodisperse compound proton exchange membrane preparation of water-retaining component: the colloidal solution of step 3) preparation is placed culture dish, regulate pH value to 6.5～7.5 with NaOH, stir and be placed in the vacuum drying chamber after 20～30 minutes, be incubated 3～5 hours down at 110～140 ℃, and then be incubated 1～3 hour down at 180～200 ℃, make compound proton exchange membrane after the solvent evaporates;
Wherein, described inorganic oxide is SiO 2Or TiO 2Any, select SiO for use 2The time, then the inorganic oxide precursor body be tetraethoxysilane, tetramethoxy-silicane any one; Select TiO for use 2The time, then the inorganic oxide precursor body be metatitanic acid second fat, metatitanic acid isopropyl ester and metatitanic acid fourth fat any one.
2, the preparation method of the homodisperse compound proton exchange membrane of water-retaining component as claimed in claim 1 is characterized in that: described ionomer, select the side chain sulfonic acid type anionic polymer that has sulfonate group for use.
3, the preparation method of the homodisperse compound proton exchange membrane of water-retaining component as claimed in claim 2, it is characterized in that: the described side chain sulfonic acid type anionic polymer that has sulfonate group, any in the hydrocarbon alkyl resin of perfluorinated sulfonic resin, sulfonation trifluorostyrene, sulfonated polyether-ether-ketone and sulfonation.
4, the preparation method of the homodisperse compound proton exchange membrane of water-retaining component as claimed in claim 1, it is characterized in that: the anhydrous organic solvent described in the step 1) is selected the N-methyl pyrrolidone, fourth-two eyeball, acetate, glycol-ether or ethylene glycol-methyl ether, or the mixed solution of above-mentioned any two kinds of solvents.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102945972A (en) * 2012-09-07 2013-02-27 四川大学 Preparation method of composite proton exchange membrane for all vanadium redox flow battery
CN104835932A (en) * 2015-04-28 2015-08-12 大连理工大学 Preparation of organic-inorganic composite membrane and application thereof in alkaline fuel cell
CN114122470A (en) * 2021-11-24 2022-03-01 中汽创智科技有限公司 Proton exchange membrane and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102945972A (en) * 2012-09-07 2013-02-27 四川大学 Preparation method of composite proton exchange membrane for all vanadium redox flow battery
CN104835932A (en) * 2015-04-28 2015-08-12 大连理工大学 Preparation of organic-inorganic composite membrane and application thereof in alkaline fuel cell
CN114122470A (en) * 2021-11-24 2022-03-01 中汽创智科技有限公司 Proton exchange membrane and preparation method and application thereof
CN114122470B (en) * 2021-11-24 2023-12-29 中汽创智科技有限公司 Proton exchange membrane and preparation method and application thereof

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