CN101757860B - Ion exchange membrane with interpenetrating network structure and preparation method thereof - Google Patents
Ion exchange membrane with interpenetrating network structure and preparation method thereof Download PDFInfo
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- CN101757860B CN101757860B CN2009102300739A CN200910230073A CN101757860B CN 101757860 B CN101757860 B CN 101757860B CN 2009102300739 A CN2009102300739 A CN 2009102300739A CN 200910230073 A CN200910230073 A CN 200910230073A CN 101757860 B CN101757860 B CN 101757860B
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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 invention relates to an ion exchange membrane with an interpenetrating network structure and a preparation method thereof. The preparation method comprises the following steps: a perfluorinated sulfonic acid exchange resin and a polymerizable monomer containing proton exchange functional groups are dissolved by using a polar organic solvent; and casting film is formed on the smooth surface of a solid by using the tape casting method; and the polymerizable monomer containing the proton exchange functional groups is initiated to generate polymerization reaction, and the products of the polymerization reaction and perfluorinated sulfonic acid molecular chains form the ion exchange membrane with the interpenetrating network structure. The preparation method of the ion exchange membrane can obtain ion exchange membrane materials with very good proton exchange property, overcomes the defects that the homogeneous cross-linked ion exchange membrane can not be prepared in the existing melt molding process, and has the advantages of simple technological process, easy industrial scale-up and the like.
Description
Technical field
The present invention relates to a proton exchanging film fuel battery (PEMFC) and all-vanadium flow battery (VRB) is used ion-exchange membrane, particularly a kind of interpenetrating network ion exchange membrane and preparation method thereof belongs to high molecular functional mould material field.
Background technology
All-vanadium flow battery is a kind of novel electric power storage energy storage device, not only can be used as sun power, 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.In the existing energy storage technology, since all-vanadium flow battery (VRB) have have extended cycle life, energy efficiency height, operation and maintenance cost lack with cheap, environmental friendliness, time of response and deep discharge and to advantages such as battery do not work the mischief, make it can satisfy the demand in multiple field: it both can support the very strong renewable energy power generations of randomness such as sun power, wind energy, can be used as uninterrupted power supply (ups) Unity prevention supply of electric power interrupt event again, can also be used for electrical network peak load shifting, balanced load, the raising quality of power supply and power station operation stability.All-vanadium flow battery all has a good application prospect at aspects such as the power supply of large-scale power company, side area and medium-sized power consumer, the energy storage of ordinarily resident's user power utilization, the technical characterstic that it is efficient, energy-conservation has long-range influence for the exploitation of China's new forms of energy.
Proton Exchange Membrane Fuel Cells (PEMFC) is the quiet electrochemical generating unit of a kind of clean and effective, the perfluorinated sulfonic resin Proton Exchange Membrane Fuel Cells is low with its operating temperature, specific power is big, environmentally friendly, fuel handling safe ready and at movable electrical appliances, automobile and other industries has good application prospects.
, play exchange ion, separate the dual-use function of positive and negative electrode active substance (vanadium ion of different valence state) as one of critical material of Proton Exchange Membrane Fuel Cells (PEMFC) and all-vanadium flow battery (VRB) as the key part ion-exchange membrane of Proton Exchange Membrane Fuel Cells (PEMFC) and all-vanadium flow battery (VRB).Its character produces great effect to performance, life-span and the cost of PEMFC and VRB.Widely used in the existing all-vanadium flow battery (VRB) is perfluorinated sulfonic acid type ion-exchange membrane, it has advantages such as proton exchange rate height, mechanical stability and anti-oxidant degradation property are good, but the production cost of the perfluorination production process complexity of such film, process 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 ion-exchange membrane, 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 ion-exchange membranees, 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 work-ing life of battery.Therefore, the ion-exchange membrane 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.
Problems such as the ionic membrane that uses exists life-span weak point, later stage bad mechanical strength at present, specific conductivity is on the low side.In order to overcome these difficulties, the various countries investigator has carried out a large amount of work.Yu Jingrong (phys.Chem.Chem.Phys., 2003,5 (3): 611-615) wait the hot pressed method of employing, 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 repeatedly immersion/exsiccant method 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 demixing phenomenon 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 ion-exchange membrane 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 surface, is difficult to guarantee the mechanics of whole composite membrane and the stable homogeneous of mechanical property.Document (J Membr Sci, 1995,98C1-2): the 77-87.) film behind use linking agent Vinylstyrene processing ion exchange resin Amberlite CG400 and the Amberlite CG120 dipping, improve the blocking effect to vanadium ion.Yet when increasing degree of crosslinking, may reduce the specific 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 mould material recombination process is difficult to control, and higher and use sulphonating agent of cost causes environmental pollution easily; 2) treating processes 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 ion exchange membrane of interpenetrating network structure that is applicable to Proton Exchange Membrane Fuel Cells (PEMFC) and all-vanadium flow battery (VRB) usefulness and preparation method thereof.
Technical scheme of the present invention is as follows:
A kind of ion exchange membrane of interpenetrating network structure of the present invention is that the IPN corsslinking molecular is formed inierpeneirating network structure by perfluorinated sulfonic acid ion exchange resin molecule with the another kind of macromole that contains ion-exchange group, and the network structure of this ion exchange membrane of interpenetrating network structure structural formula 1 as shown in Figure 1;
The interpenetrating polymer networks structure is IPN (interpenetrating Polymer Network), it is two or more polymer blend, molecular chain runs through mutually, and the network structure 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 original copolymer inherent characteristic, thus the incomparable special performance of other polymkeric substance obtained.
The chemical structure of described perfluorinated sulfonic acid type ion exchange resin is shown in structural formula 2:
Structural formula 2
Wherein x, y, z are respectively 1～10000 integer; And x/ (x+y+z)=45%～85%, y/ (x+y+z)=10%～45%, 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-CF
3,-CF
2CF
3,-CF
2CF
2CF
3Or-CF (CF
3)
2
Described perfluorinated sulfonic acid type ion exchange resin is dried resin, and number-average molecular weight is 60,000 to 300,000, and exchange capacity is 0.75-1.50mmol/g, H
+Type or Na
+Type.
Described a kind of macromole that contains ion-exchange group is that the IPN corsslinking molecular is meant the polymerisable monomer that contains the proton exchange functional group, is selected from one or several the monomeric mixtures in sodium allylsulfonate, methylpropene sodium sulfonate, vinylbenzenesulfonic acid sodium, perfluoro propylene sodium sulfonate or the perfluoro-methyl sodium allylsulfonate.
A kind of ion exchange membrane of interpenetrating network structure of the present invention, its preparation process comprises the following steps:
(1) perfluorinated sulfonic acid type ion exchange resin is dissolved in the organic solvent, adds the linking agent that contains polymerisable monomer, the initiator of proton exchange functional group and contain at least 2 polymerizable groups then, stir evenly solution for later use;
(2) use casting method that the solution that step (1) obtains is become film in level and level and smooth sheet glass or Hastelloy surface of steel plate curtain coating;
(3) film that step (2) is obtained is heated to certain temperature, peels off the perfluorinated sulfonic acid ion exchange membrane that obtains inierpeneirating network structure from planar surface after for some time;
(4) ion-exchange membrane 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.
Organic solvent described in the step (1) is N, the mixed solvent of one or more solvents in dinethylformamide (DMF), N,N-dimethylacetamide (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 0.75-1.50mmol/g, is 5%～50% when the concentration in solution is represented with weight percentage;
The polymerisable monomer that contains the proton exchange functional group described in the step (1) is the molecule that contains a sulfonic acid group and a carbon-to-carbon double bond at least, be selected from one or several the monomeric mixtures in sodium allylsulfonate, methylpropene sodium sulfonate, vinylbenzenesulfonic acid sodium, perfluoro propylene sodium sulfonate or the perfluoro-methyl sodium allylsulfonate, the concentration of described monomer in solution is 10%～25% when representing with weight percentage;
Initiator described in the step (1) is selected from benzoyl peroxide (BPO), Diisopropyl azodicarboxylate (AIBN), and described amount of initiator is for adding the 0.2wt%～2wt% of amount of monomer;
Linking agent described in the step (1) is selected from Vinylstyrene (DVB), Ethylene glycol dimethacrylate (EGDMA), diacrylate-1, the mixture of one or several linking agents in 4-fourth diester or the trimethylolpropane trimethacrylate (TMPTA), the mass ratio of described linking agent add-on and monomer add-on is 1: 6～1: 2;
Resulting film in the step (2), thickness is between 25～300 microns; Can peel off from described planar surface after the drying.
Heating temperature described in the step (3) is 50 ℃～180 ℃, and the length of heat-up time was at 15 minutes to 12 hours, and wherein temperature-rise period can comprise gradient increased temperature;
Weak point at above-mentioned proton exchange membrane prepare and modification technology, the present invention proposes following thinking: with the stable perfluorinated sulfonic resin of chemical property is matrix material, with itself and polymerization reaction monomer compound with sulfonic acid group, as sodium vinyl sulfonate, in non-proton intensive polar solvent, dissolve, make uniform solution after the mixing, by curtain coating legal system film.This film is heat-treated at a certain temperature, and trigger monomer polymerization reaction take place and matrix polymer form the proton exchange membrane of inierpeneirating network structure (IPN, interpenetrating Polymer Network).The maximum characteristics of IPN structure are the thermodynamics incompatible polymers can be mixed mutually and form the material of alloy property that at least can be stable on kinetics, the various polymkeric substance itself that constitute the polymer alloy state material of IPN structure are external phase, IPN and do not lose original copolymer inherent characteristic, thus the incomparable special performance of other polymkeric substance obtained.Body material wherein must possess good resistance to chemical attack characteristic and snappiness, and sulfonic acid group has the proton exchange ability, and the ionic channel of exchange hydrogen proton is provided.This proton exchange membrane preparation method is simple, be easy to industrialization amplifies, and preparation process avoids using the severe corrosive sulphonating agent, significantly improves the process environments condition.The barrier film that both can be used for all-vanadium flow battery also can be used as the occasions such as sepn process (as PEMFC) that cationic exchange membrane is used for electric field driven.
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 technological processs such as sulphonating agent, multistep processing in the existing method, and scorification can't prepare the shortcoming of homogeneous phase proton exchange membrane.In film-casting liquid, 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 adds the matrix polymer that the thermal initiation mode makes the monomeric compound polymerization reaction take place and contain fluorine element and forms the interpenetrating(polymer)networks structure, and the contained sulfonic acid group composition ionic 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 sepn process that common cationic exchange membrane is used for electric field driven.Utilize the high characteristics of proton exchange membrane electric conductivity 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 the network structure of interpenetrating network ion exchange membrane structural formula 1.
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 0.95mmol/g, Na
+Type) is dissolved in 880g N, in the dinethylformamide (DMF), obtain sulfonic acid solutions (film-casting liquid), add vinylbenzenesulfonic acid sodium monomer 110g, initiator Diisopropyl azodicarboxylate 0.5g, and linking agent Vinylstyrene (DVB) 50g, after dissolving, stirring, glass surface hydrostomia in smooth and level, 70 ℃ of following evaporating solvent 10h film forming obtain ion-exchange membrane after on glass peeling off, fluoridize the ion-exchange membrane 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 0.8mmol/g, H
+Type) is dissolved in the 880g dimethyl sulfoxide (DMSO) (DMSO), obtain sulfonic acid solutions (film-casting liquid), add sodium allylsulfonate monomer 100g, initiator Diisopropyl azodicarboxylate 0.5g, and linking agent Ethylene glycol dimethacrylate (EGDMA) 30g, after dissolving, stirring, Hastelloy planar surface hydrostomia in smooth and level, be warmed up to 150 ℃ of evaporating solvent 1h film forming, after on glass peeling off, obtain ion-exchange membrane, fluoridize the ion-exchange membrane of the inierpeneirating network structure that obtains 30 microns of thickness with fluorine gas.
Embodiment 3:
With the dried sulfonate resin of 420g (number-average molecular weight 250,000, exchange capacity 1.05mmol/g, Na
+Type) is dissolved in 880g N, in the N-N,N-DIMETHYLACETAMIDE (DMAc), obtain sulfonic acid solutions (film-casting liquid), add vinylbenzenesulfonic acid sodium monomer 300g, initiator benzoyl peroxide (BPO) 3g, and linking agent Vinylstyrene (DVB) 50g, after dissolving, stirring, glass surface hydrostomia in smooth and level, 100 ℃ of following evaporating solvent 2h film forming obtain ion-exchange membrane after on glass peeling off, fluoridize the ion-exchange membrane 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 120,000, exchange capacity 1.45mmol/g, Na
+Type) is dissolved in the 880g N-N-methyl-2-2-pyrrolidone N-(NMP), obtain sulfonic acid solutions (film-casting liquid), add perfluoro-methyl sodium allylsulfonate monomer 200g, initiator Diisopropyl azodicarboxylate 1g, and linking agent trimethylolpropane trimethacrylate (TMPTA) 60g, 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 ion-exchange membrane, fluoridize the ion-exchange membrane 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 film-casting liquid, 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 film-casting liquid.
Embodiment 7:
With embodiment 1, different is that initiator amount is 1.6g in the film-casting liquid.
Embodiment 8:
With embodiment 1, different is that dosage of crosslinking agent is 17g in the film-casting liquid.
Embodiment 9:
With embodiment 2, different is film-casting liquid is warmed up to 55 ℃ of evaporating solvents after 10 minutes behind the planar surface hydrostomia, be warmed up to 175 degree again, and 15 minutes, film forming.
Embodiment 10:
With embodiment 2, different is film-casting liquid is warmed up to 75 ℃ of evaporating solvents after 5 minutes behind the planar surface hydrostomia, be warmed up to 175 degree again, and 15 minutes, film forming.
Embodiment 11:
Embodiment 3, and different is that solvent is N-N-methyl-2-2-pyrrolidone N-(NMP).
Embodiment 12:
With embodiment 3, that different is dried sulfonate resin (number-average molecular weight 280,000, exchange capacity 1.05mmol/g, H
+Type).
Embodiment 13:
Embodiment 3, and different is that linking agent is the mixture (mass ratio 1: 1) of Ethylene glycol dimethacrylate (EGDMA) and trimethylolpropane trimethacrylate (TMPTA).
Embodiment 14:
With embodiment 3, different is that monomer is the mixture (mass ratio 1: 1) of sodium allylsulfonate and methylpropene sodium sulfonate.
Embodiment 15:
With embodiment 4, different is that monomer is the mixture (mass ratio 1: 1) of perfluoro propylene sodium sulfonate and perfluoro-methyl sodium allylsulfonate.
Embodiment 16:
With embodiment 4, different is that monomer is the mixture (mass ratio 3: 1) of perfluoro propylene sodium sulfonate and perfluoro-methyl sodium allylsulfonate.
Claims (9)
1. the ion-exchange membrane of an inierpeneirating network structure is characterized in that: is that the IPN corsslinking molecular is formed inierpeneirating network structure by perfluorinated sulfonic acid ion exchange resin molecule with the another kind of macromole that contains ion-exchange group;
The chemical structure of described perfluorinated sulfonic acid type ion exchange resin has following structural formula:
Wherein x, y, z are respectively 1～10000 integer; And x/ (x+y+z)=45%～85%, y/ (x+y+z)=10%～45%, 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-CF
3,-CF
2CF
3,-CF
2CF
2CF
3Or-CF (CF
3)
2
Described perfluorinated sulfonic acid type ion exchange resin dried resin, number-average molecular weight is 60,000 to 300,000, exchange capacity is 0.75-1.50mmol/g, H
+Type or Na
+Type.
2. the method for the ion-exchange membrane of the described a kind of inierpeneirating network structure of preparation claim 1 comprises the steps:
(1) perfluorinated sulfonic acid type ion exchange resin is dissolved in the organic solvent, adds the linking agent that contains polymerisable monomer, the initiator of proton exchange functional group and contain at least 2 polymerizable groups then, stir evenly solution for later use;
(2) use casting method that the solution that step (1) obtains is become film in level and level and smooth sheet glass or Hastelloy surface of steel plate curtain coating;
(3) film that step (2) is obtained is heated to certain temperature, peels off the perfluorinated sulfonic acid ion exchange membrane that obtains inierpeneirating network structure from planar surface after for some time;
(4) ion-exchange membrane that step (3) is obtained is fluoridized with fluorine gas and to be obtained ion exchange membrane of interpenetrating network structure.
3. preparation method as claimed in claim 2, it is characterized in that: the organic solvent described in the step (1) is N, the mixed solvent of one or more solvents in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or the N-N-methyl-2-2-pyrrolidone N-.
4. preparation method as claimed in claim 2 is characterized in that: the perfluorinated sulfonic acid ion exchange resin described in the step (1) is for being dried resin, and number-average molecular weight is 60,000 to 300,000, and exchange capacity is 0.75-1.50mmol/g, H
+Type or Na
+Type is 5%～50% when the concentration in solution is represented with weight percentage.
5. preparation method as claimed in claim 2, it is characterized in that: the polymerisable monomer that contains the proton exchange functional group described in the step (1) is the molecule that contains a sulfonic acid group and a carbon-to-carbon double bond at least, be selected from one or several the monomeric mixtures in sodium allylsulfonate, methylpropene sodium sulfonate, vinylbenzenesulfonic acid sodium, perfluoro propylene sodium sulfonate or the perfluoro-methyl sodium allylsulfonate, the concentration of described monomer in solution is 10%～25% when representing with weight percentage.
6. preparation method as claimed in claim 2 is characterized in that: the initiator described in the step (1) is selected from benzoyl peroxide, Diisopropyl azodicarboxylate, and described amount of initiator is for adding the 0.2wt%～2wt% of amount of monomer.
7. preparation method as claimed in claim 2, it is characterized in that: the linking agent described in the step (1) is selected from Vinylstyrene, Ethylene glycol dimethacrylate, diacrylate-1, the mixture of one or several linking agents in 4-fourth diester or the trimethylolpropane trimethacrylate, the mass ratio of described linking agent add-on and monomer add-on is 1: 6～1: 2.
8. preparation method as claimed in claim 2 is characterized in that: resulting film in the step (2), and thickness is between 25～300 microns; Peel off from described planar surface dry back.
9. preparation method as claimed in claim 2 is characterized in that: the Heating temperature described in the step (3) is 50 ℃～180 ℃, and heat-up time was at 15 minutes to 12 hours.
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| CN102008906B (en) * | 2010-09-14 | 2013-01-30 | 清华大学 | Method for preparing diester interpenetrating network membrane material for gasoline desulfurization |
| CN103201025A (en) * | 2010-10-04 | 2013-07-10 | 苏特沃克技术有限公司 | Resilient ion exchange membranes |
| CN103304945A (en) * | 2012-03-09 | 2013-09-18 | 陈铭 | Perfluorosulfonic acid ion exchange membrane and preparation method thereof |
| CN111085120B (en) * | 2019-12-30 | 2022-02-22 | 山东天维膜技术有限公司 | Preparation method of monovalent selective cation exchange membrane |
| EP3936558A1 (en) * | 2020-07-07 | 2022-01-12 | HurraH SarL | Composite ion-exchange membrane comprising pei and process for production thereof |
| EP3936557A1 (en) * | 2020-07-07 | 2022-01-12 | HurraH SarL | Composite ion-exchange membrane and process for production thereof |
| CN113690474A (en) * | 2021-08-30 | 2021-11-23 | 中北大学 | Ultrathin low-permeability hydrogen proton exchange membrane and preparation method thereof |
| CN114773517B (en) * | 2022-04-07 | 2023-04-07 | 国家电投集团氢能科技发展有限公司 | Fluorine-containing sulfonic acid resin and preparation method thereof |
| KR102593282B1 (en) * | 2023-05-25 | 2023-10-24 | 주식회사 넥스트이앤엠 | Method for manufacturing a multi-layered ion exchange membrane having rectifying properties and multi-layered ion exchange membrane manufactured thereby |
| KR102593274B1 (en) * | 2023-05-25 | 2023-10-24 | 주식회사 넥스트이앤엠 | Apparatus for manufacturing a multi-layered ion exchange membrane having rectifying properties |
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| CN101003588A (en) * | 2006-12-25 | 2007-07-25 | 山东东岳神舟新材料有限公司 | Polymer of containing fluorin, and application as material of ion exchange fiber |
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