CN1416186A - Method for preparing complex film of proton exchange film for fuel cell - Google Patents
Method for preparing complex film of proton exchange film for fuel cell Download PDFInfo
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- CN1416186A CN1416186A CN01136845A CN01136845A CN1416186A CN 1416186 A CN1416186 A CN 1416186A CN 01136845 A CN01136845 A CN 01136845A CN 01136845 A CN01136845 A CN 01136845A CN 1416186 A CN1416186 A CN 1416186A
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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
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- 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 method includes following steps. The porous membrane of high polymer is dipped in ethanol solution in order to remove the organic matter on the surface. The organic solvent with high boiling point is added to the porous membrane, which is then put to the vacuum oven heating to obtain the composite proton exchange membrane of perfluorosulfuric acid. The thickness of the membrane is 10-100 micron m. The invention possessesthe advantages of easy to control the thickness of the composite membrane and the immersion quantity of the perfluoro resin, providing the membrane with the proporties of airtight and good intensity. It is safe to be used in the fuel cell.
Description
Technical field
The present invention relates to a kind of method for preparing complex film of proton exchange film for fuel cell, relate in particular to a kind of employing perfluorinated sulfonic resin and height.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) has high power density, high-energy conversion efficiency, and cold-starting, advantages of environment protection, it will be widely used in fields such as space flight, military affairs, the energy and traffic.The electrode of PEMFC is a porous gas diffusive electrode, makes eelctro-catalyst with pure Pt, Pt/C or Pt-Ru/C etc., and electrolyte is a solid polymer proton exchange membrane.Proton exchange membrane (PEM) is one of core building block of PEMFC, it with general chemical power source in the barrier film that uses a great difference is arranged, at first it is not a kind of diaphragm material, and it still is the substrate of electrolyte (transmission proton) and electrode active material (eelctro-catalyst); In addition, PEM still is a kind of selective permeation film of densification, and is different from common porous membrane.Desirable PEM should have the proton conductivity height, gas permeability is low, sufficiently high mechanical strength, thermal stability and chemical stability, suitable performance and price ratio.
At present, the key factor that hinders PEMFC commercialization process is the unsatisfactory of the price of proton exchange membrane and performance.The way of dealing with problems has two: the one, and the consumption of minimizing perfluorinated resin; The 2nd, develop non-fluorine proton exchange membrane material.But perfluorinated resin has the incomparable advantage of other material aspect chemical property and the chemical stability at present.Therefore the composite membrane of developing perfluorinated sulfonic resin and high molecular polymer is just very necessary.So not only can save material, reduce cost; Can also improve the character of original film, improve the mechanical strength and the dimensional stability of film.And adopt complex method to do film very thinly, and can reduce the internal resistance of cell, improve battery performance.
In preparing the three-in-one process of membrane electrode, the dry state film strength is very important.Because it also is very important that the variation of degree of hydration causes the size stability of polymer film.Yet, adopt film and EW (to refer to every mole of ion-exchange group (SO usually in order to improve fuel cell performance
3H
+) weight of contained dried resin) film that value is low, this just must cause the mechanical strength of film when dry state and the decline of the dimensional stability during hygrometric state.And if the material of bad mechanical strength is made proton exchange membrane, the problem of running into is exactly the film embrittlement of making, and intensity is not high, so just can't be applied in the fuel cell at all and go.
For improving the mechanical strength and the dimensional stability of proton exchange membrane, a kind of solution is utilized a backing material exactly, makes composite membrane.The method of making composite membrane is a lot, for example: make film and support membrane respectively, and then the two is assembled.Another kind of method commonly used is that polymer material solution is incorporated in the hole of porous support membrane, then composite membrane is dried, and the two is become one.A kind of method in back can make two kinds of materials contact more closely, therefore is better than other method.And the polymer of filming performance difference such as embrittlement, intensity difference during for film forming, can improve its filming performance.
Whether utilize perfluorinated sulfonic acid solution system composite membrane patent documentation more at present, be exactly how to reduce the surface tension of perforated membrane and can produce continuously with the subject matter of perfluor solution system polymer compound film in fact.Generally the method for Cai Yonging has the method for spraying, blade coating, brushing and dipping.
At United States Patent 5,834, in 523, Ballard company is the α of sulfonation, β, β-trifluorostyrene sulfonic acid and m-trifluoromethyl-α, β, methyl alcohol/propyl alcohol (3: 1) solution impregnation of β-trifluorostyrene copolymer is dried under 50 ℃ of conditions in the hole of the porous PTFE film of swelling then, obtains a composite membrane.Adopt the polymer of low EW value better fuel battery performance to be arranged than the composite membrane that adopts high EW value polymer to make.But need repeat polymer fully is filled in the hole of PTFE perforated membrane.
At US Patent 5,547, adopt 5% perfluor sulfoacid resin solution in 551 and add the wetability that a certain amount of non-ionic surface active agent (Triton X-100, octylphenol polyethylene ethoxy ethanol) strengthens solution, promote the immersion of perfluorinated resin fenestra in the PTFE perforated membrane.Mixed solution is brushed on the thick polytetrafluoroethylene expansion system of 20 μ m with brush, after 140 ℃ of processing, composite membrane is immersed in the Triton X-100 that removes in the isopropyl alcohol in the striping.This composite membrane is transparent, Nafion in the film
(R)Resin is blocked the micropore among the PTFE fully.But this method operation is too complicated, operates too loaded down with trivial details.
In WO Patent 98/51733, prepare Nafion
(R)The process of/PTFE composite membrane is more loaded down with trivial details.At first the Nafion of the thick sulfuryl fluoride type of 25 μ m
(R)The PTFE film of the GORE company that film and 23-25 μ m are thick by hot pressing under 310 ℃ of vacuum states together.Then film hydrolysis in the KOH solution of dimethyl sulfoxide (DMSO) (DMSO), make in the film-SO
2The F group changes into-SO
3 -At last be coated with three times 5% Nafion in the one side of porous PTFE film
(R)Solution makes film become as a whole in 150 ℃ of vacuum drying ovens.Obvious this method is too time-consuming, needs several cloth just can finish suddenly.
In US Patent 5,082,472, also introduced a kind of similar method.At first the Nafion of sulfuryl fluoride type
(R)Film and the hot pressing of PTFE perforated membrane are together; Perfluorinated sulfonic acid solution (2%wt) with low EW value is immersed in the PTFE fenestra then; At last film water is separated and transformed into H
+Ionic species.This method is not suitable for commercially producing.
In WO Patent 00/78850A1, introduced a kind of new method.Nafion 5%
(R)Add two 500cm in the solution
2Electrode applies 50V voltage on the electrode, allow then the aperture be the PTFE perforated membrane of 1.5 μ m by between two plate electrodes, the perfluorinated sulfonic resin in the solution will move under effect of electric field, and the fenestra of PTFE is blocked.As long as the PTFE perforated membrane passes through electrode with certain speed, will produce composite membrane continuously like this.But this method is difficult to make the good composite membrane of compactness.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of fuel cell with the perfluorinated sulfonic acid compound proton exchange membrane, this method is simple to operate, and one step of composite membrane finishes, the composite membrane of making is airtight, intensity is good, and cost is low, goes in the fuel cell that can use safely.
For achieving the above object, the technical solution used in the present invention comprises the steps:
A. adopt the high molecular polymer perforated membrane, as the expander of polytetrafluoroethylene, have the microporous barrier of space network, its aperture is 0.1-0.8 μ m, be preferably 0.2-0.5 μ m; Thickness is 5-100 μ m, is preferably 5-50 μ m, and porosity should be soaked in ethanolic solution greater than 70%, removes the organic substance on surface;
B. then perforated membrane is layered on the glass plate, drip high boiling organic solvent such as N in the above, dinethylformamide (DMF), N, the perfluorinated sulfonic acid solution of N-dimethylacetylamide (DMAC) or dimethyl sulfoxide (DMSO) (DMSO), be put on the 40-50 ℃ of hot platform, make solvent evaporates;
C. glass plate is taken off from hot platform, be put in the vacuum drying oven, heating-up temperature is a 120-200 ℃ of scope, takes out after 10-16 hour, promptly makes the perfluorinated sulfonic acid compound proton exchange membrane, and the thickness that makes is 10-100 μ m.
It is the mixed solution of low boiling organic alcohols and water that the present invention prepares the perfluorinated sulfonic acid solution that composite membrane uses, and adds the solution of higher boiling point polar organic solvent as the preparation composite membrane therein.The organic alcohols solvent can improve the affinity of perfluorinated sulfonic resin and perforated membrane, perfluorinated resin is immersed in the hole become easier; High boiling solvent can make the composite membrane of making, and embrittlement, existing compliance do not have certain mechanical strength again.Drip a certain amount of perfluorinated resin solution on the surface of perforated membrane, rely on the effect of gravity that perfluorinated resin is immersed in the fenestra.Adopt the surface tension of the way reduction perfluorinated sulfonic acid solution of heating simultaneously, the immersion of perfluorinated resin is more prone to, the immersion amount of the thickness of composite membrane and perfluorinated resin is controlled easily.The film of making is airtight, and intensity is good, and cost is low, can be applied in the fuel cell safely.
It can be polytetrafluoroethylene, tetrafluoroethene, polypropylene, polyethylene, polyimides or polysulfones etc. partially that the present invention is used to prepare perforated membrane that the perfluor compound proton exchange membrane adopts, consider heat, the chemical degradation of non-fluorine film in the fuel cell operation process, optimum should be poly-tetrafluoro hole alkene expansion perforated membrane, its aperture is preferably between the 0.2-0.5 μ m between 0.1-0.8 μ m; Thickness is preferably between the 5-50 μ m between 5-100 μ m, and porosity should be greater than 70%.
For perfluor sulfoacid resin solution is immersed in the perforated membrane easily, just must reduce the surface tension of perfluorinated sulfonic acid solution.The surface tension of porous film material is very little, if the surface tension of perfluorinated sulfonic acid solution greater than the surface tension of perforated membrane, then the immersion of perfluor sulfoacid resin solution will become very difficult.Near the temperature (reaching boiling point) that improves perfluor sulfoacid resin solution can make its temperature immerse and become molten easy, will produce bubble in solution but temperature is too high, make to produce defective in the composite membrane, so the temperature of perfluor sulfoacid resin solution should be at 40-50 ℃.
To the heat treatment of composite membrane is a committed step in the film-forming process.In perfluorinated sulfonic resin, its similar polytetrafluoroethylene fluorine carbon backbone chain forms certain crystalline phase hydrophobic region; Form phase separation structure with the side chain of hydrophilic sulfonate radical.During aquation, the elastic force between the fluorine carbon backbone chain weakens under being higher than room temperature, forms inverted structure.When heat treatment, merge again between the fluorine carbon backbone chain, form certain intensity, insoluble structure.Obtain the good film of performance, must be with high boiling solvent such as DMSO, DMF, DMAC and NMP etc. Nafion
(R)Low boiling point solvents such as water in the solution and low fat alcohol cement out, again the high-temperature process film forming.Therefore, the film-forming temperature of perfluorinated sulfonic acid/high molecular polymer compound proton exchange membrane (120-200 ℃) between its glass transformation temperature and melt temperature.
The method of being introduced in the present invention and the background technology relatively has following advantage:
1. the present invention can perfluoro sulfonic acid membrane carries out recycling and prepares perfluorinated sulfonic resin/PTFE composite membrane.Compare with US Patent 5,834,523 and US Patent 5,547,551, it is simple to operate that the present invention prepares the perfluor composite membrane, and one step of composite membrane finishes, and need not repeatedly repetitive operation.The thickness of the composite membrane that adds the amount of perfluorinated sulfonic resin and make is controlled easily.
2. compare with WO Patent 00/78850A1, the perfluorinated sulfonic acid composite membrane compactness of this method preparation is good, can be applied in the fuel cell as proton exchange membrane.
3. the perfluorinated sulfonic acid compound film battery performance that adopts the present invention to prepare thickness 25 μ m is better than the business-like Nafion of company with Du Pont
(R)The battery performance (see figure 5) of 115 films assembling.
For further understanding flesh and blood of the present invention, provide embodiment below and also in conjunction with the accompanying drawings the present invention is described in detail.
Description of drawings
Fig. 1 is the microphoto of polytetrafluoroethylporous porous membrane under scanning electron microscopy that embodiment 1 adopts;
Fig. 2 is the battery polarization curve chart of embodiment 1;
Fig. 3 is the microphoto of polytetrafluoroethylporous porous membrane under scanning electron microscopy that embodiment 2, embodiment 3 and embodiment 4 adopt;
Fig. 4 is the battery polarization curve chart of embodiment 2;
Fig. 5 is the battery polarization curve chart of embodiment 3;
Fig. 6 is embodiment 4 and known Nafion
(R)The performance comparison diagram of 115 film assembled batteries;
The battery life curve figure of Fig. 7 for adopting exchange membrane of the present invention to make.
Embodiment
Embodiment 1: cut a slice 10 * 11cm
2The polytetrafluoroethylene (PTFE) perforated membrane of thick 30 μ m (the SEM electron scanning micrograph is seen accompanying drawing 1) is placed in the ethanolic solution and soaks, and removes the organic substance on surface.Then the PTFE perforated membrane is layered on the plate glass Nafion
(R)Solution and DMSO drip 17.6g at porous film surface by the mixed solution of 1: 8 (volume).Be put on 50 ℃ of hot platforms, temperature is brought up to 75 ℃ after 1 hour, and temperature is brought up to 120 ℃ after 1 hour.Take off from hot platform, be put into 100 ℃ of vacuum drying ovens interior 12 hours, cool to room temperature takes out, and promptly makes Nafion
(R)/ PTFE composite membrane (film thickness 45 μ m).Put in the redistilled water film is taken out, in deionized water, preserve standby.
Adopt carbon paper, polytetrafluoroethylene (PTFE) emulsion, XC-72 carbon dust and 20%Pt/C Preparation of Catalyst porous gas diffusive electrode, catalyst loading is 0.30mg Ptcm in the electrode
-2Electrode sprays a certain amount of 5%Nafion to Catalytic Layer before use
(R)Solution (U.S. Du Pont company) carries out three-dimensional and handles to increase the phase reaction area of electrode, with Nafion (R) solution dilution 2-4 doubly, be sprayed on the electrode catalyst laminar surface equably, in the room temperature airing, in about 80 ℃, dry by the fire 40min down, promptly finish electrode three-dimensional step.
For guaranteeing that electrode and the effective of proton exchange membrane contact, reduce the contact resistance between electrode and the proton exchange membrane, adopt hot-pressing technique that electrode and proton exchange membrane are bonded together.The preparation method places two gas-diffusion electrodes respectively to cast Nafion again
(R)The film both sides, the Catalytic Layer one side is towards proton exchange membrane.In 130 ℃ of hot pressing, earlier little exerting pressure after water drains in the film, improved pressure again to 2MPa in forcing press, and hot pressing 2min takes out rapidly and cools off for little pressurization, and it is three-in-one promptly to make membrane electrode.
With the three-in-one PEMFC that is assembled into of membrane electrode of preparation, test battery performance on the monocell evaluating apparatus.The test battery polarization curve is seen accompanying drawing 2.The operating condition of battery is as follows: battery temperature is 80 ℃, and Hydrogen Vapor Pressure is 0.20MPa, and oxygen pressure is 0.20MPa, and hydrogen and oxygen is the outer humidifier humidification by 80 ℃ all.
Embodiment 2: adopt example 1 method to prepare perfluorinated sulfonic acid Nafion
(R)/ PTFE composite membrane and membrane electrode are three-in-one, and the PTFE perforated membrane adopts 15 μ m thick film (10 * 11cm
2), its SEM electromicroscopic photograph is seen accompanying drawing 3.At Nafion
(R)Add DMF by 1: 8 (volume ratio) in the solution.Drip the 28g mixed solution at porous film surface.The composite membrane that makes is put in 150 ℃ of vacuum drying ovens and spends the night.Preparation Nafion
(R)/ PTFE composite membrane thickness is 70 μ m, and it is three-in-one to adopt this film hot pressing to prepare membrane electrode.With the PEMFC of assembling, test battery performance on the monocell evaluating apparatus.The test battery polarization curve is seen accompanying drawing 4.The operating condition of battery is with embodiment 1.
Embodiment 3: with mixed solvent heating for dissolving perfluorinated sulfonic acid Nafion in closed reactor of low mass molecule alcohol class and water
(R)The corner material of film is made Nafion
(R)Solution.Use this solution, adopt example 1 method to prepare the perfluorinated sulfonic acid composite membrane and membrane electrode three-in-one, the PTFE perforated membrane adopts 15 μ m thick film (10 * 11cm
2), its SEM electromicroscopic photograph is seen accompanying drawing 3.At Nafion
(R)Add DMAC by 1: 8 (volume ratio) in the solution.Drip the 14.6g mixed solution at porous film surface.The composite membrane that makes is put in 200 ℃ of vacuum drying ovens and spends the night.Preparation Nafion
(R)/ PTFE composite membrane thickness is 25 μ m, and it is three-in-one to adopt this film hot pressing to prepare membrane electrode.With the PEMFC of assembling, test battery performance on the monocell evaluating apparatus.The test battery polarization curve is seen accompanying drawing 5.The operating condition of battery is with embodiment 1.
Embodiment 4: adopt example 1 method to prepare perfluorinated sulfonic acid Nafion
(R)/ PTFE composite membrane and membrane electrode are three-in-one, and the PTFE perforated membrane adopts 15 μ m thick films, and its SEM electromicroscopic photograph is seen accompanying drawing 3.Preparation Nafion
(R)/ PTFE composite membrane thickness is 25 μ m, and it is three-in-one to adopt this film hot pressing to prepare membrane electrode.With the PEMFC of assembling, test battery performance on the monocell evaluating apparatus.Test battery polarization curve and Nafion
(R)The performance of 115 film assembled batteries is relatively seen accompanying drawing 6.Battery life curve is seen accompanying drawing 7.The operating condition of battery is with embodiment 1.
Claims (7)
1, a kind of method for preparing complex film of proton exchange film for fuel cell, the high molecular polymer perforated membrane is placed in the ethanolic solution soaks, remove the organic substance on surface, it is characterized in that, on perforated membrane, drip the mixed solution of perfluorinated sulfonic acid solution and high boiling organic solvent, and heat and make solvent evaporates; In vacuum drying oven, heat, take out in the cooling back.
2, method for preparing complex film of proton exchange film for fuel cell as claimed in claim 1, it is characterized in that used high molecular polymer perforated membrane is the expander of polytetrafluoroethylene, have the microporous barrier of space network, its aperture is 0.1-0.8 μ m, and thickness is 5-100 μ m.
3, fuel cell as claimed in claim 2 proton exchange composite membrane preparation method is characterized in that, its aperture is preferably 0.2-0.5 μ m, and thickness is preferably 5-50 μ m.
4, method for preparing complex film of proton exchange film for fuel cell as claimed in claim 1 is characterized in that, described high boiling organic solvent is N, dinethylformamide, N, N-dimethylacetylamide or dimethyl sulfoxide (DMSO).
5, method for preparing complex film of proton exchange film for fuel cell as claimed in claim 1 is characterized in that, the mixed solution ratio of described perfluorinated sulfonic acid solution and high boiling organic solvent is 1: 8 (volume ratio).
6, method for preparing complex film of proton exchange film for fuel cell as claimed in claim 1 is characterized in that, the temperature of described solvent flashing is 40-50 ℃.
7, method for preparing complex film of proton exchange film for fuel cell as claimed in claim 1 is characterized in that, being heated into film temperature in the described vacuum is 120-200 ℃, and be 10-14 hour heating time.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312788C (en) * | 2005-09-30 | 2007-04-25 | 清华大学 | Proton exchange composite membrane for all vanadium redox flow battery and its preparing method |
| CN100342574C (en) * | 2004-06-30 | 2007-10-10 | 三星Sdi株式会社 | Polymer electrolyte membrane for fuel cell and method for preparing the same |
| CN100344351C (en) * | 2005-06-14 | 2007-10-24 | 武汉理工大学 | Process for preparing composite proton exchange film by alkali metal ion type perfluoro sulfonate resin |
| CN100355132C (en) * | 2005-04-08 | 2007-12-12 | 中国科学院大连化学物理研究所 | Composite proton exchange membrane synthesizing method for fuel cell |
| CN101041721B (en) * | 2006-03-24 | 2011-05-18 | 比亚迪股份有限公司 | Vacuum flow-casting film forming machine and method for preparing composite proton interchange membrane |
| CN102104156A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院大连化学物理研究所 | Composite anion exchange membrane for fuel cell and preparation method thereof |
| CN1837268B (en) * | 2005-03-17 | 2011-07-13 | 索尔维索莱克西斯公司 | Ionomeric membrane |
| WO2011156936A1 (en) * | 2010-06-18 | 2011-12-22 | 山东东岳神舟新材料有限公司 | Proton exchange membrane and preparation method and use thereof |
| CN102304234A (en) * | 2011-07-15 | 2012-01-04 | 华南理工大学 | Preparation method of compact and composite proton exchange membrane |
| CN101029140B (en) * | 2006-02-23 | 2013-04-24 | 三星Sdi株式会社 | Polymer membrane, method of preparing the same and fuel cell employing the same |
| CN103326043A (en) * | 2013-06-14 | 2013-09-25 | 江苏中靖新能源科技有限公司 | Composite ion exchange membrane and preparation method thereof |
| CN104037431A (en) * | 2014-04-11 | 2014-09-10 | 成都赢创科技有限公司 | Ion exchange membrane for flow battery |
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| CN100342574C (en) * | 2004-06-30 | 2007-10-10 | 三星Sdi株式会社 | Polymer electrolyte membrane for fuel cell and method for preparing the same |
| CN1837268B (en) * | 2005-03-17 | 2011-07-13 | 索尔维索莱克西斯公司 | Ionomeric membrane |
| CN100355132C (en) * | 2005-04-08 | 2007-12-12 | 中国科学院大连化学物理研究所 | Composite proton exchange membrane synthesizing method for fuel cell |
| CN100344351C (en) * | 2005-06-14 | 2007-10-24 | 武汉理工大学 | Process for preparing composite proton exchange film by alkali metal ion type perfluoro sulfonate resin |
| CN1312788C (en) * | 2005-09-30 | 2007-04-25 | 清华大学 | Proton exchange composite membrane for all vanadium redox flow battery and its preparing method |
| CN101029140B (en) * | 2006-02-23 | 2013-04-24 | 三星Sdi株式会社 | Polymer membrane, method of preparing the same and fuel cell employing the same |
| CN101041721B (en) * | 2006-03-24 | 2011-05-18 | 比亚迪股份有限公司 | Vacuum flow-casting film forming machine and method for preparing composite proton interchange membrane |
| CN102104156B (en) * | 2009-12-18 | 2013-03-27 | 中国科学院大连化学物理研究所 | Composite anion exchange membrane for fuel cell and preparation method thereof |
| CN102104156A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院大连化学物理研究所 | Composite anion exchange membrane for fuel cell and preparation method thereof |
| WO2011156936A1 (en) * | 2010-06-18 | 2011-12-22 | 山东东岳神舟新材料有限公司 | Proton exchange membrane and preparation method and use thereof |
| CN102304234A (en) * | 2011-07-15 | 2012-01-04 | 华南理工大学 | Preparation method of compact and composite proton exchange membrane |
| CN102304234B (en) * | 2011-07-15 | 2013-03-20 | 华南理工大学 | Preparation method of compact and composite proton exchange membrane |
| CN103326043A (en) * | 2013-06-14 | 2013-09-25 | 江苏中靖新能源科技有限公司 | Composite ion exchange membrane and preparation method thereof |
| CN104037431B (en) * | 2014-04-11 | 2017-12-12 | 广东玖美新材料有限公司 | Flow battery amberplex |
| CN104037431A (en) * | 2014-04-11 | 2014-09-10 | 成都赢创科技有限公司 | Ion exchange membrane for flow battery |
| CN110010942A (en) * | 2019-03-15 | 2019-07-12 | 浙江吉利汽车研究院有限公司 | A kind of compoiste proton exchange film and preparation method thereof |
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