CN101794889A - Interpenetrating network ion exchange membrane based on polyurethane and preparation method thereof - Google Patents
Interpenetrating network ion exchange membrane based on polyurethane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an interpenetrating network ion exchange membrane based on polyurethane and preparation method thereof. Polar organic solvent is adopted to dissolve perfluorinated sulfonic acid resin and anhydrous poly isocyanate as well as anhydrous polyalcohol; tape casting is adopted to form a membrane on smooth solid surface; then heating is carried out and poly isocyanate and anhydrous polyalcohol take polymerization, and products of the polymerization and perfluorinated sulfonic acid molecule chain form ion exchange membrane in macromolecule interpenetrating network structure. The membrane preparation method can obtain ion exchange membrane material with favourable proton commutativity, overcomes the defect that the existing fusion mould pressing process can not prepare homogeneous cross linking ion exchange membrane and has the advantages of simple technological process and easy industrial scale-up.
Description
Technical field
The present invention relates to a kind of amberplex, particularly a kind of all-vanadium flow battery (VRB) uses interpenetrating network ion exchange membrane based on polyurethane and preparation method thereof to belong to high molecular functional membrane material field.
Background technology
As a kind of novel environmental protection energy-storage battery, vanadium redox battery is a kind of secondary cell of novel green, has advantages such as capacity and adjustable power, the harmless deep discharge of big electric current, long service life, easy to operate and maintenance.It has avoided the electrolyte cross-contamination issue of traditional lead acid batteries and Fe/Cr battery as a kind of large-scale energy-storage system of single metal ion, is being applied to have showed very big advantage aspect the fixedly energy storage device of the renewable energy resources.It not only can but also can make it be applied to enjoy people's attention aspect the vehicle power by the characteristic of exchange electrolyte mode machinery charging by power charge.Through the development in 20 years, just progressively move towards practicability.All-vanadium flow battery (VRB) not only can be used as solar energy, the supporting energy storage device of wind power generation process, can also be used for peak load regulation network, improves grid stability, ensures power grid security.
Compare with other storage batterys, all-vanadium flow battery (VRB) has plurality of advantages: the rated power and the rated energy of (1) vanadium cell are separate, watt level depends on the performance (as resistance of battery pile etc.) of battery pile, and the energy of vanadium cell depends on the concentration of the volume and the electrolyte of electrolyte.Therefore, can be by concentration that increases electrolyte and the capacity that volume increases battery.(2) during charge and discharge, liquid phase reactor only takes place in vanadium oxide reduction flow battery, and electrode does not participate in chemical reaction.(3) vanadium cell is long storage life, and storage life is unlimited in theory.Because electrolyte can recycle, this greatly reduces battery cost.(4) vanadium cell can be realized 100% deep discharge and not damage battery.(5) cheap, replacing of simple in structure, the material price of vanadium cell and maintenance cost are cheap.(6) can realize that by the electrolyte of changing vanadium cell moment recharges.(7) vanadium cell is environmentally friendly, is novel environment-friendly battery.
Amberplex is the critical component of all-vanadium flow battery (VRB), plays the dual-use function of exchange ion, separation both positive and negative polarity active material (vanadium ion of different valence state).Its character produces significant impact to performance, life-span and the cost of all-vanadium flow battery (VRB).Widely used in the existing all-vanadium flow battery (VRB) is perfluorinated sulfonic acid type amberplex, it has advantages such as proton exchange rate height, mechanical stability and anti-oxidant degradability are good, but the production cost of the perfluorinate production process complexity of such film, procedure parameter control strictness, film is too high, has restricted the industrialization and the commercialization of all-vanadium flow battery (VRB) to a great extent.Compare with perfluorinated sulfonic acid type amberplex, hydro carbons sulfonic acid type ion exchange membrane has that preparation technology is simple, raw material is cheap and easy to get, production cost is far below advantages such as perfluorinated sulfonic acid type amberplexes, but it exists shortcomings such as poor chemical stability, anti-oxidant degradation capability be weak, when it is applied to the barrier film of all-vanadium flow battery (VRB), easily by the strong oxidizing property V in the anodal electrolyte solution
5+Institute's oxidative degradation causes the battery performance of all-vanadium flow battery (VRB) to descend, and shorten the useful life of battery.
Therefore, the amberplex of developing cheap, excellent performance, good in oxidation resistance is one of key that promotes all-vanadium flow battery (VRB) development, and the preparation of novel proton exchange membranes has caused whole world scientific research personnel's concern.In order to overcome these difficulties, the various countries researcher has carried out a large amount of work.Yu Jingrong (phys.Chem.Chem.Phys., 2003,5 (3): 611-615) wait the method that adopts hot pressing, prepared the PSSA-Nafion composite membrane, and be used for Proton Exchange Membrane Fuel Cells (PEMFC); (Electrochemistry Communications 2004, (6): 231-236) adopt pressure sintering to prepare the Nafion/SPEEK/Nafion composite membrane, and be used for direct methanol fuel cell (DMFC) such as Bo Yang; Ren Suzhen (J.Membr.Sci., 2005, (247): 59-63) wait the repeatedly method of immersion/drying of employing, prepared the SPEEK/Nafion composite membrane, and be applied to direct methanol fuel cell (DMFC).More than Zhi Bei fluorine/hydrocarbon composite ion exchange film does not have chemical bond crosslinked owing between the two membranes, and its associativity is relatively poor, and lamination takes place in application process easily, thereby causes the resistance of fluorine/hydrocarbon composite ion exchange film to increase.Patent (publication number CN101383404) has proposed a kind of all-vanadium flow battery (VRB) that is applicable to, has fluorine/hydrocarbon composite ion exchange film of good combination and preparation method thereof between perfluorinated sulfonic acid type amberplex and the hydro carbons sulfonic acid type ion exchange membrane.Yet this kind is compound and crosslinkedly also only carry out on two-layer contact-making surface, is difficult to guarantee the mechanics of whole composite membrane and the stable homogeneous of mechanical performance.Document (J Membr Sci, 1995,98C1-2): the 77-87.) film behind use crosslinking agent divinylbenzene processing ion exchange resin Amberlite CG400 and the AmberliteCG120 dipping, improve the blocking effect to vanadium ion.Yet when increasing the degree of cross linking, may reduce the conductivity of ion exchange resin.
Although above-mentioned research improves the proton exchange film properties to a certain extent, ubiquity two aspect problems.1) the membrane material recombination process is difficult to control, and higher and use sulfonating agent of cost causes environmental pollution easily; 2) processing procedure usually comprises a plurality of steps, is difficult to be applicable to large-scale batch production.
Summary of the invention
At the deficiencies in the prior art, the object of the present invention is to provide a kind of be applicable to all-vanadium flow battery (VRB) based on interpenetrating network ion exchange membrane of polyurethane and preparation method thereof.
Technical scheme of the present invention is as follows:
A kind of interpenetrating network ion exchange membrane based on polyurethane of the present invention is formed inierpeneirating network structure by perfluorinated sulfonic acid ion exchange resin molecule and a kind of urethane crosslinks polymer.Its inierpeneirating network structure schematic diagram is referring to accompanying drawing 1.
The interpenetrating polymer networks structure is IPN (interpenetrating Polymer Network), it is two or more polymer blend, strand runs through mutually, and the network configuration that forms with the mode interlinkage of chemical bond of at least a polymer molecular chain.
Interpenetrating polymer networks (IPN) is a kind of novel high polymer material that grows up the seventies in 20th century, because the polymer network in the IPN material more than 2 kinds or 2 kinds tangles mutually, IPN and do not lose the intrinsic characteristic of original copolymer, thus the incomparable special performance of other polymer obtained.
The chemical constitution of described perfluorinated sulfonic acid type ion exchange resin is shown in structural formula 1:
Structural formula 1
Wherein x, y, z are respectively 1～10000 integer; And x/ (x+y+z)=40%～85%, y/ (x+y+z)=10%～50%, z/ (x+y+z)=0.01%～10% is mol ratio; Wherein, m is 0,1 or 2, and n is the integer of 1-6; Rf is-F ,-CF
3,-CF
2CF
3,-CF
2CF
2CF
3Or-CF (CF
3)
2According to the difference of monomer ratio in m, n value and the structure, formed perfluorinated sulfonic acid ion exchange resin exchange capacity is at 0.8-2.6mmol/g.X is H
+Or Na
+
Described perfluorinated sulfonic acid ion exchange resin is dried resin, and number-average molecular weight is 60,000 to 300,000.
Described a kind of urethane crosslinks polymer is meant by multicomponent isocyanate and polyalcohol polymerization and the cross-linked polyurethane polymer that generates.Anhydrous multicomponent isocyanate reacts in the organic solvent that contains perfluorinated sulfonic acid type ion exchange resin with no water-polyol, when forming the urethane crosslinks polymer, forms inierpeneirating network structure with perfluorinated sulfonic acid type ion exchange resin.
A kind of interpenetrating network ion exchange membrane based on polyurethane of the present invention, its preparation process comprises the following steps:
(1) dried perfluorinated sulfonic acid type ion exchange resin is dissolved in the organic solvent, under anhydrous condition, adds anhydrous multicomponent isocyanate and no water-polyol then, stir evenly solution for later use;
(2) use solution that The tape casting obtains step (1) under anhydrous condition, become film in level and level and smooth glass plate or Hastelloy surface of steel plate curtain coating;
(3) film that step (2) is obtained is heated to uniform temperature under anhydrous condition, peels off the perfluorinated sulfonic acid ion exchange membrane that obtains inierpeneirating network structure from planar surface after a period of time;
(4) amberplex that step (3) is obtained is fluoridized with fluorine gas and to be obtained ion exchange membrane of interpenetrating network structure of the present invention, and the nonessential step of this step can be omitted according to concrete condition.
Organic solvent described in the step (1) is N, dinethylformamide (DMF), N, the mixed solvent of one or more solvents in N-dimethylacetylamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO) or the N-N-methyl-2-2-pyrrolidone N-(NMP);
Perfluorinated sulfonic acid ion exchange resin described in the step (1) is dried resin, and number-average molecular weight is 60,000 to 300,000, is H
+Type or Na
+Type, exchange capacity is 0.8-2.60mmol/g, is 5%～50% when the concentration in solution is represented with percetage by weight, with multicomponent isocyanate described in the step (1) and polyalcohol total mass ratio be 1: 1～15: 1;
Multicomponent isocyanate described in the step (1), be selected from toluene di-isocyanate(TDI) (TDI, comprise Toluene-2,4-diisocyanate, 4-vulcabond and Toluene-2,4-diisocyanate, the 6-vulcabond), methyl diphenylene diisocyanate (MDI, comprise 4,4 '-, 2,4 '-, 2,2 '-, three kinds of isomers), one or more the mixture in the partially fluorinated and perfluoro-compound of triphenylmethane triisocyanate (TTI), hexamethylene diisocyanate (HDI), IPDI (IPDI), two (vulcabond methyl) cyclohexane (HXDI) or above-mentioned multicomponent isocyanate;
Polyalcohol described in the step (1) is selected from the mixture of one or several crosslinking agents in ethylene glycol, diglycol, glycerol, trimethylolpropane (TMP), pentaerythrite, triethanolamine, the polyvinyl alcohol, and described polyalcohol addition is 1: 0.8～1: 2 with the function number of functional groups of multicomponent isocyanate addition than (hydroxyl-OH number and cyanate ester based-NCO number);
Resulting film in the step (2), thickness is between 15～250 microns; Can peel off from described planar surface after the drying;
Heating-up temperature described in the step (3) is 50 ℃～180 ℃, and the length of heating time was at 10 minutes to 12 hours, and wherein temperature-rise period can comprise gradient increased temperature.
Compared with prior art, excellent results of the present invention is as follows:
Method of the present invention is avoided using loaded down with trivial details technical processs such as sulfonating agent, multistep processing in the existing method, and fusion method can't prepare the shortcoming of homogeneous phase or cross-linked proton exchange membrane.In casting solution, import sulfonic acid group in advance, use solution casting method to prepare the homogeneous phase proton exchange membrane with proton exchange function.Performance fluoro-containing macromolecule material electrochemical corrosion resistant is strong, the speciality of good toughness, the essential part of component film material.Use heating initiation mode to make the monomeric compound polymerization reaction take place, form the interpenetrating networks structure with the matrix macromolecule that contains fluorine element, therefore can use the perfluorinated sulfonic resin of high-exchange-capacity, the contained sulfonic acid group composition ion channel that is connected to each other effectively reduces membranous son exchange resistance.Described film-forming method is simple, realizes industrial amplification production easily.This proton exchange membrane is applicable to the barrier film as all-vanadium flow battery, also can be used as the occasions such as separation process that common cation-exchange membrane is used for electric field driven.Utilize the high characteristics of proton exchange membrane electrical conductance of the present invention, can effectively reduce the all-vanadium flow battery internal resistance, for the preparation of development novel proton exchange membranes provides the universality method, for further industrial production lays the foundation.
Description of drawings
Fig. 1 is based on the interpenetrating network ion exchange membrane schematic network structure of polyurethane; Wherein solid line is represented perfluorinated sulfonic acid ion exchange resin molecule, and dotted line is represented the urethane crosslinks polymer.
Embodiment
By the following examples the present invention is further specified, but the present invention is not limited only to following examples.
Embodiment 1:
With the dried sulfonate resin of 120g (number-average molecular weight 80,000, exchange capacity 1.25mmol/g, H
+Type) under anhydrous condition, is dissolved in 880g N, in the dinethylformamide (DMF), obtain sulfonic acid solutions (casting solution), add dry toluene-2,4-vulcabond 4.5g, anhydrous trimethylolpropane (TMP) 3.5g (both hydroxyls-OH number is 1: 1 with the ratio of cyanate ester based-NCO number), fully dissolving, after stirring, under anhydrous condition at the glass surface hydrostomia of smooth and level, 75 ℃ of following evaporating solvent 10h film forming, after on glass peeling off, obtain amberplex, fluoridize the amberplex of the inierpeneirating network structure that obtains 50 microns of thickness with fluorine gas.
Embodiment 2:
With the dried sulfonate resin of 45g (number-average molecular weight 150,000, exchange capacity 2.55mmol/g, Na
+Type) under anhydrous condition, is dissolved in the 880g N-N-methyl-2-2-pyrrolidone N-(NMP), obtain sulfonic acid solutions (casting solution), add anhydrous 4, the anhydrous pentaerythrite of 4 '-methyl diphenylene diisocyanate (MDI) is 44g (both hydroxyls-OH number is 1: 0.8 with the ratio of cyanate ester based-NCO number) altogether, after fully dissolving, stirring, under anhydrous condition at the Hastelloy planar surface hydrostomia of smooth and level, be warmed up to 150 ℃ of evaporating solvent 1h film forming, peel off from glass, obtain the amberplex of the inierpeneirating network structure of 20 microns of thickness.
Embodiment 3:
With the dried sulfonate resin of 420g (number-average molecular weight 250,000, exchange capacity 1.05mmol/g, Na
+Type) under anhydrous condition, is dissolved in 880g N, in the N-dimethylacetylamide (DMAc), obtain sulfonic acid solutions (casting solution), add anhydrous triphenylmethane triisocyanate (TTI), anhydrous diglycol is 210g (both hydroxyls-OH number is 1: 1.5 with the ratio of cyanate ester based-NCO number) altogether, fully dissolving, after stirring, under anhydrous condition at the glass surface hydrostomia of smooth and level, 100 ℃ of following evaporating solvent 2h film forming, after on glass peeling off, obtain amberplex, fluoridize the amberplex of the inierpeneirating network structure that obtains 150 microns of thickness with fluorine gas.
Embodiment 4:
With the dried sulfonate resin of 800g (number-average molecular weight 200,000, exchange capacity 2.25mmol/g, Na
+Type) under anhydrous condition, is dissolved in the 880g dimethyl sulfoxide (DMSO) (DMSO), obtain sulfonic acid solutions (casting solution), add IPDI (IPDI) 444g, polyvinyl alcohol 88g (both hydroxyls-OH number is 1: 2 with the ratio of cyanate ester based-NCO number), after dissolving, stirring, glass surface hydrostomia in smooth and level, 20 minutes film forming of 160 ℃ of following evaporating solvents, after on glass peeling off, obtain amberplex, fluoridize the amberplex of the inierpeneirating network structure that obtains 250 microns of thickness with fluorine gas.
Embodiment 5:
With embodiment 1, different is that solvent load is 480g in the casting solution, and used flat board is the Hastelloy plate.
Embodiment 6:
With embodiment 1, different is that solvent is the mixture (volume ratio 1: 1) of dimethyl sulfoxide (DMSO) (DMSO) and N-N-methyl-2-2-pyrrolidone N-(NMP) in the casting solution.
Embodiment 7:
With embodiment 1, different is dry toluene in the casting solution-2, and 4-vulcabond consumption is 8.5g.
Embodiment 8:
With embodiment 2, different is, and methyl diphenylene diisocyanate in the casting solution (MDI) is 4,4 '-and 2, the mixture of 4 '-methyl diphenylene diisocyanate (1: 1).
Embodiment 9:
With embodiment 2, different is that polyalcohol is the mixture (1: 1) of trimethylolpropane (TMP) and triethanolamine in the casting solution.
Embodiment 10:
With embodiment 2, different is casting solution is warmed up to 90 ℃ of evaporating solvents after 5 minutes behind the planar surface hydrostomia, be warmed up to 175 ℃ again, and 15 minutes, film forming.
Embodiment 11:
With embodiment 2, different is casting solution is warmed up to 80 ℃ of evaporating solvents after 10 minutes behind the planar surface hydrostomia, be warmed up to 180 ℃ again, and 15 minutes, film forming.
Embodiment 12:
With embodiment 3, different is that (number-average molecular weight is respectively 280,000,200,000 to two kinds of dried sulfonate resins, exchange capacity 1.05mmol/g and 2.35mmol/g, Na
+Type) mixture.
Embodiment 13:
Embodiment 3, and different is that polyalcohol is the mixture (mass ratio 2: 1) of ethylene glycol and diglycol.
Embodiment 14:
With embodiment 3, different is that multicomponent isocyanate is the mixture (mass ratio 1: 1: 1) of hexamethylene diisocyanate (HDI), IPDI (IPDI), two (vulcabond methyl) cyclohexane (HXDI).
Embodiment 15:
With embodiment 4, different is that isocyanate-monomer is perfluorinate hexamethylene diisocyanate (HDI).
Embodiment 16:
With embodiment 4, different is that isocyanate-monomer is partially fluorinated IPDI (IPDI).
Claims (9)
1. interpenetrating network ion exchange membrane based on polyurethane, it is characterized in that: form inierpeneirating network structure by perfluorinated sulfonic acid ion exchange resin molecule and a kind of urethane crosslinks polymer, the chemical constitution of described perfluorinated sulfonic acid type ion exchange resin is shown in structural formula 1:
Structural formula 1
Wherein x, y, z are respectively 1～10000 integer; And x/ (x+y+z)=40%～85%, y/ (x+y+z)=10%～50%, z/ (x+y+z)=0.01%～10% is mol ratio; Wherein, m is 0,1 or 2, and n is the integer of 1-6; Rf is-F ,-CF
3,-CF
2CF
3,-CF
2CF
2CF
3Or-CF (CF
3)
2According to the difference of monomer ratio in m, n value and the structure, formed perfluorinated sulfonic acid ion exchange resin exchange capacity is at 0.8-2.6mmol/g; X is H
+Or Na
+
Described perfluorinated sulfonic acid ion exchange resin is dried resin, and number-average molecular weight is 60,000 to 300,000;
Described a kind of urethane crosslinks polymer is meant by multicomponent isocyanate and polyalcohol polymerization and the cross-linked polyurethane polymer that generates.
2. the method for the described a kind of interpenetrating network ion exchange membrane based on polyurethane of preparation claim 1 comprises the steps:
(1) perfluorinated sulfonic acid type ion exchange resin is dissolved in the organic solvent, under anhydrous condition, adds anhydrous multicomponent isocyanate and no water-polyol then, stir well solution for later use;
(2) use The tape casting that the solution that step (1) obtains is become film in level and level and smooth glass plate or Hastelloy surface of steel plate curtain coating;
(3) film that step (2) is obtained is heated to uniform temperature, peels off the sulfonic acid ion exchange membrane that obtains inierpeneirating network structure from planar surface after a period of time;
3. the method for the described a kind of interpenetrating network ion exchange membrane based on polyurethane of preparation claim 2 is characterized in that adding following steps afterwards in step (3):
(4) amberplex that step (3) is obtained is fluoridized with fluorine gas and to be obtained ion exchange membrane of interpenetrating network structure of the present invention.
4. preparation method as claimed in claim 2, it is characterized in that: the organic solvent described in the step (1) is N, dinethylformamide (DMF), N, the mixed solvent of one or more solvents in N-dimethylacetylamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO) or the N-N-methyl-2-2-pyrrolidone N-(NMP).
5. preparation method as claimed in claim 2, it is characterized in that: the perfluorinated sulfonic acid ion exchange resin described in the step (1) is dried resin, number-average molecular weight is 60,000 to 300,000, be H+ type or Na+ type, exchange capacity is 0.8-2.60mmol/g, be 5%～50% when the concentration in solution is represented with percetage by weight, with multicomponent isocyanate described in the step (1) and polyalcohol total mass ratio be 1: 1～15: 1.
6. preparation method as claimed in claim 2, it is characterized in that: the multicomponent isocyanate described in the step (1), be selected from toluene di-isocyanate(TDI) (TDI, comprise Toluene-2,4-diisocyanate, 4-vulcabond and Toluene-2,4-diisocyanate, the 6-vulcabond), methyl diphenylene diisocyanate (MDI, comprise 4,4 '-, 2,4 '-, 2,2 '-, three kinds of isomers), triphenylmethane triisocyanate (TTI), hexamethylene diisocyanate (HDI), IPDI (IPDI), the mixture of one or more in the partially fluorinated and perfluoro-compound of two (vulcabond methyl) cyclohexanes (HXDI) or above-mentioned multicomponent isocyanate.
7. preparation method as claimed in claim 2, it is characterized in that: the polyalcohol described in the step (1) is selected from the mixture of one or several crosslinking agents in ethylene glycol, diglycol, glycerol, trimethylolpropane (TMP), pentaerythrite, triethanolamine, the polyvinyl alcohol, and the function number of functional groups of described polyalcohol addition and multicomponent isocyanate addition is 1: 0.8～1: 2 than the ratio of cyanate ester based-NCO number (hydroxyl-OH number with).
8. preparation method as claimed in claim 2 is characterized in that: resulting film in the step (2), and thickness is between 15～250 microns; Can peel off from described planar surface after the drying.
9. preparation method as claimed in claim 2 is characterized in that: the heating-up temperature described in the step (3) is 50 ℃～180 ℃, and the length of heating time was at 10 minutes to 12 hours, and wherein temperature-rise period comprises gradient increased temperature.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3082186A1 (en) * | 2015-04-14 | 2016-10-19 | Chemtura Corporation | Non-aqueous flow cell comprising a polyurethane separator |
| US10186716B2 (en) | 2014-11-10 | 2019-01-22 | Lanxess Solutions Us Inc. | Non-aqueous flow cell comprising a polyurethane separator |
| CN114725459A (en) * | 2022-04-27 | 2022-07-08 | 深圳市通用氢能科技有限公司 | Proton exchange membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100519594C (en) * | 2006-12-25 | 2009-07-29 | 山东东岳神舟新材料有限公司 | Polymer containing fluorin, and application as material of ion exchange fiber |
| CN101475699B (en) * | 2009-01-16 | 2011-05-11 | 清华大学 | Preparation of proton conduction membrane |
| CN101481443A (en) * | 2009-01-23 | 2009-07-15 | 华南理工大学 | Polyurethane-polyacrylacid ester interpenetrating network polymer, preparation and use thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10186716B2 (en) | 2014-11-10 | 2019-01-22 | Lanxess Solutions Us Inc. | Non-aqueous flow cell comprising a polyurethane separator |
| EP3082186A1 (en) * | 2015-04-14 | 2016-10-19 | Chemtura Corporation | Non-aqueous flow cell comprising a polyurethane separator |
| CN114725459A (en) * | 2022-04-27 | 2022-07-08 | 深圳市通用氢能科技有限公司 | Proton exchange membrane and preparation method thereof |
| CN114725459B (en) * | 2022-04-27 | 2024-02-13 | 深圳市通用氢能科技有限公司 | Proton exchange membrane and preparation method thereof |
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