CN101728549A - High-temperature proton exchange compound film - Google Patents
High-temperature proton exchange compound film Download PDFInfo
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- CN101728549A CN101728549A CN200910231121A CN200910231121A CN101728549A CN 101728549 A CN101728549 A CN 101728549A CN 200910231121 A CN200910231121 A CN 200910231121A CN 200910231121 A CN200910231121 A CN 200910231121A CN 101728549 A CN101728549 A CN 101728549A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a high-temperature proton exchange compound film. The film is formed by using a fluorine-containing thin polymer film having a cellular structure as a carrier, filling a perfluor resin having a function of ion exchange into the micro-pores of a micro-porous film and covering the surface of the micro-porous film, wherein the compound film is 5 to 15 microns thick. The fluorine-containing thin polymer film having a cellular structure is a polyfluortetraethylene porous film, a polyvinylidene fluoride porous film, a polytrifluorochloroethylene porous film or a polyfluortetraethylene ethylene porous film. The perfluor resin having a function of ion exchange is a perfluor sulfo resin, a perfluor carboxylic resin or a perfluor phosphoric resin. The compound film of the invention is thin and can be applied to a fuel cell having a decreased internal resistance in order to promote the output power of the cell.
Description
Technical field
The present invention relates to a kind of high temperature proton exchange film, particularly by the composite membrane of fluoride ion polymer and perforated membrane.
Background technology
Proton Exchange Membrane Fuel Cells is a kind ofly directly chemical energy to be converted into the Blast Furnace Top Gas Recovery Turbine Unit (TRT) of electric energy by electrochemical means, is considered to the cleaning of 21 century first-selection, generation technology efficiently.(proton exchange membrane PEM) is Proton Exchange Membrane Fuel Cells (proton exchange membrane fuel cell, critical material PEMFC) to proton exchange membrane.
Now the perfluorinated sulfonic acid proton exchange membrane of using have good proton-conducting and chemical stability under (80 ℃) and the higher humidity at a lower temperature.But they also have a lot of deficiencies such as poor dimensional stability, and mechanical strength is not high, poor chemical stability etc.Film water absorption rate and size of causing because of suction under different humidity expand different, and when film during at different operating mode down conversion, the size of film also will so change.The mechanical damage that so finally causes proton exchange membrane repeatedly.In addition, the reaction of the positive pole of fuel cell usually produces the material that a large amount of hydroxyl free radicals and hydrogen peroxide etc. have strong oxidizing property, and non-fluorin radical on these materials meeting attack film-forming resin molecules causes the chemical degradation and damaged, the foaming of film.At last, when the working temperature of perfluorinated sulfonic acid exchange membrane is higher than 90 ℃,, 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 can improve the anti-carbon monoxide of fuel-cell catalyst greatly.Be exactly that existing perfluoro sulfonic acid membrane all has certain hydrogen or methanol permeability in addition, especially in direct methanol fuel cell, methanol permeability is very big, becomes fatal problem.Therefore, how to improve the proton conduction efficient under perfluorinated sulfonic acid proton exchange film strength, dimensional stability and the high temperature, the permeability of reduction working media etc. is the key subjects that fuel cell industries faces.
People have proposed certain methods and have solved these problems at present.Adopt perfluorinated sulfonic resin to flood the porous media that polytetrafluoroethylene (PTFE) makes as Japan Patent JP-B-5-75835 and strengthen film strength.Yet the porous media of this PTFE is because the PTFE material is softer relatively, and humidification is insufficient, still fails to address the above problem.The Gore-Select series composite membrane liquid of W.L.Gore company exploitation adopts the porous teflon to fill the method (US5547551 of Nafion ionic conductivity liquid, US5635041, US5599614), this film has high proton conductive and bigger dimensional stability, but teflon creep at high temperature is very big, causes decreased performance.Japan Patent JP-B-7-68377 also proposed a kind of method, the porous media made from the proton exchange resins filled polyolefin, but its chemical durability deficiency, thereby long-time stability aspect existing problems.And, make the proton conduction path reduce the proton exchange ability drop of film owing to do not possess the adding of the porous media of proton conductive ability.
In addition, Japan Patent JP-A-6-231779 has proposed another kind of Enhancement Method, is to use fluororesin fiber.The amberplex that it adopts the fluorocarbon polymer reinforcing material of fibrillation form to strengthen.But this method must add a large amount of relatively reinforcing materials, and in this case, the processing of film is tending towards difficulty, and the film resistance increase takes place possibly.
And European patent EP 0875524B1 discloses, and utilizes the technology of the glass fibre membrane enhancing nafion film of glass fibre non-woven technology preparation, mentions oxides such as silicon dioxide in this patent simultaneously.But non-woven glass fibre cloth is the base material that must use in this patent, and this will limit the scope of application that strengthens greatly.
U.S. Pat 6692858 discloses, and polytetrafluoroethylene fibre strengthens the technology of perfluorinated sulfonic resin.In this technology, with perfluor sulfonyl fluororesin and polytetrafluoroethylene fibre mix, extrude, making the transition makes fibre-reinforced perfluorinated sulfonic resin.This method can not be produced continuously because transformation process is consuming time.
U.S. Pat RE37701 has described the invention that ionomer and expansion tetrafluoroethylene is combined into composite membrane, but their employed expansion tetrafluoroethene film thickness is greater than 20 microns, can't be thinner with the trend and the thickness of the development of modern fuels battery, intensity is higher to adapt.Thereby can not adapt to the service condition of high temperature proton exchange film fuel cell.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of high-temperature proton exchange compound film and preparation method thereof.
Technical scheme of the present invention is as follows:
A kind of proton exchange composite membrane is carrier, is filled in the micropore of microporous barrier with the perfluorinated resin with ion exchanging function and is overlying on the micropore face composite membrane thickness 5-15 micron with the fluoro-containing copolymer film with microcellular structure.
Described fluoro-containing copolymer film with microcellular structure is the polytetrafluoroethylene (PTFE) perforated membrane, polyvinylidene fluoride porous film (PVDF), polytrifluorochloroethylene perforated membrane, polytetrafluoroethylene-ethene (ETFE) perforated membrane.
Described thickness 1-20 micron with fluoro-containing copolymer film of microcellular structure, voidage is 60～97%, 0.2～5 micron in aperture.
The described preferred thickness of fluoro-containing copolymer film carrier with microcellular structure is 5～20 microns, and preferred thickness is 5～15 microns, and most preferred thickness is 8～12 microns; Preferred voidage 80～95%; 0.5～4 micron in preferred aperture, more preferred aperture is 1～3 micron.
Preferably, described fluoro-containing copolymer film carrier thickness with microcellular structure is 5～15 microns, voidage 80～95%, 1～3 micron in aperture.
Described fluoro-containing copolymer film with microcellular structure can be the simple tension film, also biaxial stretching film.
The above perfluorinated resin with ion exchanging function is selected from one of following or combination: perfluorinated sulfonic resin, perfluorinated carboxylic acid resin or perfluor phosphoric acid resin.Wherein,
Described perfluorinated sulfonic resin has following general formula:
In the formula, x=3～15, n=0～2, p=2～5, ion exchange capacity is 0.90～1.60mmol/g.Molecular weight is 10-60 ten thousand, and preferred molecular weight is 15-30 ten thousand.
Described perfluorinated carboxylic acid resin has following construction unit:
In the formula (II), c=0 or 1, d=1～5, a=3～11,, b=1～3, ion exchange capacity is 0.85～1.50mmol/g.Molecular weight is 10-60 ten thousand, and preferred molecular weight is 15-30 ten thousand.
Described perfluor phosphoric acid resin has following construction unit:
In the formula (III), e=3～20, f=1, ion exchange capacity is 0.80～2.5mmol/g.Molecular weight is 10-60 ten thousand, and preferred molecular weight is 15-30 ten thousand.
Perfluorinated sulfonic resin, perfluorinated carboxylic acid resin or perfluor phosphoric acid resin all adopt the known method preparation.
The preparation method of above-mentioned proton exchange composite membrane of the present invention comprises the steps:
(1) have the perfluorinated resin of ion exchanging function or their precursor by extrude, hot pressing, solution-cast, curtain coating, silk screen printing, spraying or impregnation technology and have the fluoro-containing copolymer film composite membrane-forming of microcellular structure;
(2) film that step (1) is made obtains high-temperature proton exchange compound film in 30～250 ℃ of heat treatments.
Extruding in the above-mentioned steps (1), hot pressing, solution-cast, curtain coating, silk screen printing, spraying or impregnation technology can be by the state of the art.Wherein,
Use solution-cast, earlier perfluorinated resin is dissolved in when curtain coating, silk screen printing, spraying or impregnation technology and is made into perfluorinated resin solution in the solvent, employed solvent is selected from one of following or combination: one or more in dimethyl formamide, dimethylacetylamide, methylformamide, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, hempa acid amide, acetone, water, ethanol, methyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol or the glycerol.The preferred alcohol-water solution of employed solvent, alcohol gets final product the volume ratio of preferred alcohols of the present invention and water 1: 1 with the ratio of water by conventional selection the in this area.
Solid content in the above-mentioned perfluorinated resin solution is 1～80%, weight ratio, viscosity between 1～4000cP, preferred 20cP～2000cP.
Preferably, the heat treatment time of film is 10～600 minutes in the step (2), preferred 20～120min.
Proton exchange composite membrane after the above-mentioned heat treatment, according to the material form of film forming and the solvent species of film forming solution, also need to carry out reprocessing, post-processing approach all is a state of the art, for example 1. in 5% sulfuric acid, boiled 30-60 minute, 2. boil in distilled water and made the film swelling in 30 minutes, 3. hydrolysis 6-8h in 10%KOH solution earlier places 5%H again
2SO
4Middle 1h.
Even more important detailed preparation method will be illustrated in an embodiment, the present invention do not limit especially all by prior art.
Excellent results of the present invention is as follows:
The present invention with 1～20 micron fluoropolymer perforated membrane and the compound film thickness that obtains of perfluorinated ion polymer less than 20 microns, because the thickness of ionic membrane is very little, thereby electric conductivity is better than the big composite membrane of thickness, influence is beat all and this is to fuel cell performance, make the internal resistance of battery reduce greatly because of thickness reduces, thereby improved the power output of battery.Especially surprisingly so thin composite membrane is at high temperature＞95 degree, and low humidity (30%RH) battery performance is unexpectedly greater than the similar film more than 20 microns.Possible reason is when film becomes extremely thin, generate the water of water at anode oxygen and the hydrogen ion reaction just utmost point, back migration easily is to other one-level, thereby in the process of back migration, also just film has been carried out humidification, thereby the conductance of film and the output performance of battery have been improved virtually.
Description of drawings
Fig. 1 be embodiment 3 and Comparative Examples monocell output performance (95 degree, 30%RH) curve, ordinate are voltage, abscissa is the hydrogen permeate electric current, reaching the standard grade is 10 microns composite membranes, rolls off the production line to be 25 microns composite membranes of Comparative Examples.
Embodiment
The present invention will be further described below in conjunction with embodiment, Comparative Examples.The concentration of all perfluorinated resin solution is mass percent among the embodiment.
The poly tetrafluoroethylene (porosity 80%, 0.5～3 micron in aperture) of getting 5 microns floods in 5% perfluorinated sulfonic resin propyl alcohol-aqueous solution, and wherein the structural formula of perfluorinated sulfonic resin is
N=1, p=2, ion exchange capacity 0.97mmol/g, molecular weight 190,000.
Then, with the wet film sample in baking oven in 140 ℃ of dried 30 seconds.For the film inner pore is entirely shut, this processing step can repeat more than 2 times.Composite membrane was handled 30 fens at 190 ℃ the most at last, obtained the composite membrane of 8 microns of thickness, boiled under the normal pressure then promptly to get 5 microns composite membranes in 30 minutes in 5% sulfuric acid.
Embodiment 2
Get the biaxial tension poly tetrafluoroethylene (porosity 89%, 0.2～2 micron in aperture) of 10 micron thickness, be fixed on the flat board.With 15% perfluorinated sulfonic resin isopropyl alcohol-aqueous solution, be coated in above-mentioned poly tetrafluoroethylene one side, perfluor sulfoacid resin solution is filled up the pore volume in the film fully, make all holes entirely shut.Wherein the structural formula of perfluorinated sulfonic resin is
N=1, p=2, ion exchange capacity 1.05mmol/g molecular weight 210,000.
With the membrane sample after applying in drying oven in 100 ℃ of following dried 15 minutes.For the film inner pore is entirely shut, coating and drying process can repeat more than 2 times.Baking temperature is risen to 210 ℃ then, dry 5 minutes.In 5% sulfuric acid, boil under the normal pressure then and promptly got 12 microns composite membranes in 60 minutes.
Embodiment 3
The biaxial tension polyvinylidene fluoride film (porosity 75%, 5 microns in aperture) of getting 8 micron thickness is fixed on the flat board.24% perfluorinated sulfonic resin isopropyl alcohol-propyl alcohol-aqueous solution is coated on the both sides of polyvinylidene fluoride film by the mode of silk screen printing, and wherein the structural formula of perfluorinated sulfonic resin is
N=0, p=2, ion exchange capacity 1.35mmol/g, molecular weight 240,000.
Then film is placed 160 ℃ baking oven inner drying to handle 40 minutes.Then, the dry film after the dried is taken out to boil in distilled water made the film swelling obtain 10 microns composite membranes in 30 minutes.
Embodiment 4
The poly-poly tetrafluoroethylene (porosity 85%, 0.2～3 micron in aperture) of biaxial tension of getting 12 micron thickness is fixed on the flat board.The perfluorinated sulfonic resin precursor is compound by the mode and the polyvinylidene fluoride film of hot pressing, with composite membrane hydrolysis 8h in 10%KOH solution, place 5%H then
2SO
4Middle 1h obtains 12 microns composite membranes.Wherein the structural formula of perfluorinated sulfonic resin prerequisite is:
N=0, p=2, ion exchange capacity 1.50mmol/g, molecular weight 260,000.
Embodiment 5
The biaxial tension polyvinylidene fluoride film (porosity 75%, 5 microns in aperture) of getting 12 micron thickness is fixed on the flat board.The mode of 24% perfluorinated sulfonic resin ethanol-water solution by spraying is coated on the both sides of polyvinylidene fluoride film, and wherein the structural formula of perfluorinated sulfonic resin is
N=0, p=4, ion exchange capacity 1.20mmol/g, molecular weight 170,000.Then film is placed 160 ℃ baking oven inner drying to handle 1 minute.Then, the dry film after the dried is taken out to boil in distilled water obtained 12 microns composite membranes in 30 minutes.
Embodiment 6
The simple tension ETFE film (porosity 60%, 1 micron in aperture) of getting 20 micron thickness is fixed on the flat board.The mode of 36% perfluorinated sulfonic resin DMF solution by curtain coating is coated on the ETFE film, and wherein the structural formula of perfluorinated sulfonic resin is
N=1, p=3, ion exchange capacity 1.10mmol/g, molecular weight 210,000.Then film is placed 250 ℃ baking oven inner drying to handle 30 minutes.Then, the dry film after the dried is taken out to boil in distilled water obtained 20 micron membranes in 30 minutes.
Embodiment 7
The simple tension pvdf membrane (porosity 85%, 2 microns in aperture) of getting 15 micron thickness is fixed on the flat board.The mode of 10% perfluorinated carboxylic acid resin's ethanolic solution by curtain coating is coated on the pvdf membrane, and wherein perfluorinated carboxylic acid resin's structural formula is
C=1, d=2, ion exchange capacity 1.00mmol/g, molecular weight 220,000.Then film is placed 120 ℃ of baking oven inner dryings to handle 10 minutes.Then, the dry film after the dried is taken out to boil in distilled water obtained 16 microns composite membrane in 30 minutes.
Embodiment 8
The biaxial tension poly tetrafluoroethylene (porosity 85%, 3 microns in aperture) of getting 15 micron thickness is fixed on the flat board.The mode of 5% perfluorinated carboxylic acid resin NMP (N-methyl pyrrolidone) alcoholic solution by curtain coating is coated on the biaxial tension poly tetrafluoroethylene, and wherein perfluorinated carboxylic acid resin's structural formula is
C=1, d=3, ion exchange capacity 1.15mmol/g, molecular weight 180,000.Then film is placed 100 ℃ of baking oven inner dryings to handle 5 minutes.Then, the dry film after the dried is taken out to boil in distilled water obtained 15 microns composite membrane in 30 minutes.
Embodiment 9
The biaxial tension poly tetrafluoroethylene (porosity 75%, 0.4 micron in aperture) of getting 14 micron thickness is fixed on the flat board.The precursor of perfluor phosphoric acid resin is compound by the mode and the biaxial tension poly tetrafluoroethylene of hot pressing, then film is placed 10% sulfuric acid to handle 5h, obtain the composite membrane of 14 microns of acid types.Wherein the structural formula of perfluor phosphoric acid resin precursor is
Ion exchange capacity 1.70mmol/g, molecular weight 250,000.
Comparative Examples:
The biaxial tension polyvinylidene fluoride film (porosity 75%, 5 microns in aperture) of getting 25 micron thickness is fixed on the flat board.24% perfluorinated sulfonic resin isopropyl alcohol-propyl alcohol-aqueous solution is coated on the both sides of polyvinylidene fluoride film by the mode of silk screen printing, and wherein the structural formula of perfluorinated sulfonic resin is
N=0, p=2, ion exchange capacity 1.35mmol/g, molecular weight 230,000.
Then film is placed 160 ℃ baking oven inner drying to handle 20 minutes.Then, the dry film after the dried is taken out to boil in distilled water made the film swelling obtain 25 microns composite membranes in 30 minutes.
The mensuration of monocell performance:
Being prepared as follows of membrane electrode assembly:
(1) preparation of gas diffusion layers:, it is made hydrophobic handle with the PTFE emulsion that carbon paper immerses 25wt%.The carbon paper that will soak PTFE again places 340 ℃ Muffle furnace roasting, and the surfactant that is immersed in the carbon paper is removed, thereby reaches good hydrophobic effect.A certain amount of carbon dust, PTFE and an amount of isopropanol water solution are mixed, use supersonic oscillations 15min, be applied on the carbon paper with brushing technology then, the carbon paper that coats is toasted 30min down at 340 ℃ respectively, can make gas diffusion layers.
(2) preparation of membrane electrode MEA: the Pt carrying capacity is 0.3mg/cm in the catalyst layer
2, a certain amount of 40%Pt/C (JM company) eelctro-catalyst, deionized water, isopropyl alcohol are mixed sonic oscillation 15min; Add a certain amount of 5%Nafion solution (Dupont company) again, continue sonic oscillation 15min, behind ultrasonic one-tenth ink shape, be sprayed on equably on the composite membrane of the present invention again, obtain membrane electrode MEA.
Two gaseous diffusion are placed on the MEA both sides under 3MPa pressure, obtain monocell, utilize this monocell on battery operated station equipment, to test.
By above method the performance of various films is measured, be the results are shown in Table 1.As can be seen from Table 1, performances such as 95 of composite membrane of the present invention ℃ of conductivity, hot strength, hydrogen permeate electric current all are better than or suitable general thickness composite ionic membrane.But 95 ℃ of monocell output performances are better than thickness greater than 20 microns similar composite membrane.
The various film properties of table 1
Claims (10)
1. proton exchange composite membrane is characterized in that being carrier, being filled in the micropore of microporous barrier with the perfluorinated resin with ion exchanging function and being overlying on the micropore face composite membrane thickness 5-15 micron with the fluoro-containing copolymer film with microcellular structure;
Described fluoro-containing copolymer film with microcellular structure is the polytetrafluoroethylene (PTFE) perforated membrane, polyvinylidene fluoride porous film (PVDF), polytrifluorochloroethylene perforated membrane, polytetrafluoroethylene-ethene (ETFE) perforated membrane;
Described perfluorinated resin with ion exchanging function is selected from one of following or combination: perfluorinated sulfonic resin, perfluorinated carboxylic acid resin or perfluor phosphoric acid resin.
2. proton exchange composite membrane as claimed in claim 1 is characterized in that described thickness 1-20 micron with fluoro-containing copolymer film of microcellular structure, and voidage is 60～97%, 0.2～5 micron in aperture.
3. proton exchange composite membrane as claimed in claim 1 is characterized in that described fluoro-containing copolymer film carrier thickness with microcellular structure is 5～15 microns, voidage 80～95%, 1～3 micron in aperture.
4. proton exchange composite membrane as claimed in claim 1 is characterized in that describedly having the fluoro-containing copolymer film of microcellular structure to be simple tension film or biaxial stretching film.
5. proton exchange composite membrane as claimed in claim 1 is characterized in that described perfluorinated sulfonic resin has following general formula:
In the formula, x=3～15, n=0～2, p=2～5, ion exchange capacity is 0.90～1.60mmol/g, molecular weight is 10-60 ten thousand.
6. proton exchange composite membrane as claimed in claim 1 is characterized in that described perfluorinated carboxylic acid resin has following construction unit:
In the formula (II), c=0 or 1, d=1～5, a=3～11,, b=1～3, ion exchange capacity is 0.85～1.50mmol/g, molecular weight is 10-60 ten thousand.
7. proton exchange composite membrane as claimed in claim 1 is characterized in that described perfluor phosphoric acid resin has following construction unit:
In the formula (III), e=3～20, f=1, ion exchange capacity is 0.80～2.5mmol/g, molecular weight is 10-60 ten thousand.
8. the preparation method of the described proton exchange composite membrane of claim 1 comprises the steps:
(1) have the perfluorinated resin of ion exchanging function or their precursor by extrude, hot pressing, solution-cast, curtain coating, silk screen printing, spraying or impregnation technology and have the fluoro-containing copolymer film composite membrane-forming of microcellular structure;
(2) film that step (1) is made obtains high-temperature proton exchange compound film in 30～250 ℃ of heat treatments.
9. the preparation method of proton exchange composite membrane as claimed in claim 1, it is characterized in that using in the step (1) solution-cast, earlier perfluorinated resin is dissolved in when curtain coating, silk screen printing, spraying or impregnation technology and is made into perfluorinated resin solution in the solvent, employed solvent is selected from one of following or combination: one or more in dimethyl formamide, dimethylacetylamide, methylformamide, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, hempa acid amide, acetone, water, ethanol, methyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol or the glycerol.
10. the preparation method of proton exchange composite membrane as claimed in claim 9 is characterized in that the solid content in the described perfluorinated resin solution is 1～80%, weight ratio, and viscosity is between 1～4000cP.
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| CN102010555A (en) * | 2010-06-18 | 2011-04-13 | 山东东岳神舟新材料有限公司 | Fluorine-containing ionomer composite with ion exchange function as well as preparation method and application thereof |
| CN102649315A (en) * | 2011-02-23 | 2012-08-29 | 北京化工大学 | Polyvinylidene fluoride microporous film prepared through gelatin extrusion tape casting method |
| CN102658645A (en) * | 2012-05-14 | 2012-09-12 | 华北电力大学 | Method for preparing perfluorinated sulfonic acid proton exchange membrane with specifically-oriented structure |
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| US5834523A (en) * | 1993-09-21 | 1998-11-10 | Ballard Power Systems, Inc. | Substituted α,β,β-trifluorostyrene-based composite membranes |
| CN101320818B (en) * | 2008-07-15 | 2010-06-09 | 山东东岳神舟新材料有限公司 | Fibre reinforced multi-layer fluorine-contained ionic exchange film |
| CN100580987C (en) * | 2008-07-22 | 2010-01-13 | 山东东岳神舟新材料有限公司 | Microporous-film-reinforced fluorine-containing cross-linking ion-exchange membrane and preparation method thereof |
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| CN102010555B (en) * | 2010-06-18 | 2013-07-31 | 山东华夏神舟新材料有限公司 | Fluorine-containing ionomer composite with ion exchange function as well as preparation method and application thereof |
| CN102649315A (en) * | 2011-02-23 | 2012-08-29 | 北京化工大学 | Polyvinylidene fluoride microporous film prepared through gelatin extrusion tape casting method |
| CN102658645A (en) * | 2012-05-14 | 2012-09-12 | 华北电力大学 | Method for preparing perfluorinated sulfonic acid proton exchange membrane with specifically-oriented structure |
| CN102658645B (en) * | 2012-05-14 | 2014-06-25 | 华北电力大学 | Method for preparing perfluorinated sulfonic acid proton exchange membrane with specifically-oriented structure |
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