CN100412116C - Proton conducting membrane and production - Google Patents
Proton conducting membrane and production Download PDFInfo
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- CN100412116C CN100412116C CNB2005100077112A CN200510007711A CN100412116C CN 100412116 C CN100412116 C CN 100412116C CN B2005100077112 A CNB2005100077112 A CN B2005100077112A CN 200510007711 A CN200510007711 A CN 200510007711A CN 100412116 C CN100412116 C CN 100412116C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to a proton conducting membrane with a low methanol penetrating rate and a method for preparing the proton conducting membrane. Styrene monomers containing fluorine are grafted on polymeric membrane material, and after the polymeric membrane material on which fluorine containing styrene is grafted forms a membrane, the membrane is acidified to make cationic exchange groups combined on benzene rings of fluorine containing styryls through displacement. The proton conductive membrane has a lower penetrating degree than the existing membrane and can be used for direct methanol feeding type fuel batteries or traditional hydrogen-oxygen fuel batteries to reduce the penetrating phenomenon of fuel and improve the battery performance.
Description
Technical field
The invention relates to a kind of proton-conductive films and method for making thereof, particularly about a kind of the polymer proton-conductive films and the method for making thereof that are the proton conduction base with fluorine-containing cationic exchange base.
Background technology
Direct methanol feeding type fuel cell (Direct Methanol Fuel Cell, DMFC) be to use the fuel (fuel) of methanol-water solution as battery, produce electronics and proton via the anode catalyst reaction, electronics enters external circuit, proton is then via proton-conductive films (proton exchangemembrane, PEM) be sent to negative electrode, the electronics that reaches from external circuit with oxygen combines, again via the catalyst water generation reaction.
At present, the greatest problem that is present in the proton-conductive films of direct methanol feeding type fuel cell is that methyl alcohol is and water highly compatible and easy and proton formation misfit thing.Hydrogen ion (proton) is gymnoplasm that does not contain electricity, because it lacks the nuclear electric charge of shielding, proton can produce strong interaction with its surrounding environment and form covalent linkage.Therefore, the methanol fuel that DMFC uses combines with proton at galvanic anode easily, pass PEM through conduction, cause the loss of anode fuel, methanol fuel by PEM can be at cathode consumption catalyst and oxygen, the Poisoning cathode catalyst, and then reduce electrode activity, this phenomenon generally is to be called methanol crossover (Methanol Crossover), and this is one of unfavorable major reason of usefulness that causes DMFC.
Generally speaking, PEM is if need possess high proton conductivity, and its chemical structure can form intensive wetting ability (Hydrophilic) environment, and hydrophilic environments also is that methyl alcohol is easy to the environment that reacts with water, makes the methanol crossover phenomenon can be obvious all the more.Therefore, one of solution is to reduce the wetting ability of structure, or reduces the volume of the high hydrophilic cluster of PEM radical ion (cluster).Yet existing document shows, when the wetting ability of PEM structure reduces, can follow the conductance of proton to descend.Therefore, an ideal proton-conductive films must possess high efficiency proton conductivity simultaneously, and small molecules methyl alcohol is had highly selective.But with regard to chemical structure, reducing the methanol crossover phenomenon is conflicting with improving the proton conductive degree, and existing single-material can't satisfy the requirement of the proton-conductive films that is applicable to direct methanol feeding type fuel cell.
The Nafion (r) (perfluorinated sulfonic acid polymer) that develops with company of Du Pont (Du Pont) in the commercial goods is present proton-exchange material than the tool practicality at present.It is by the nanometer microfacies space that the polymer parent/hydrophobic phase separation structure forms, and the sulfonate radical in this space is assembled the cluster structure that forms and formed water passage by absorbing moisture, drives proton by included water molecules and conducts.Though this macromolecular structure brings breakthrough development for fuel-cell electrolyte research, finding in the application of direct methanol feeding type fuel cell has fuel to permeate loss (MethanolCrossover) in a large number.And the ($800-1000/m that costs an arm and a leg of Nafion (r)
2), even make methanol feeding type fuel cell mass production also can't effectively reduce manufacturing cost.Therefore, the utmost point need be developed and be applicable to direct methanol feeding type battery system, possesses low methanol crossover and high proton transmissibility simultaneously, and can be with a large amount of proton-conductive films of making of low cost.
Except the above,, still there is multiple different scheme to propose at present at the improvement of PEM among the DMFC.One of them is the reduction that is conceived to PEM intermediate ion base concentration.The concentration of PEM intermediate ion base (Ion Exchange Capacity) is the important factor of decision PEM proton conductive degree.Yet the PEM of macroion base concentration also forms hydrophilic cluster (hydrophilic cluster) easily in its structure, causes the phenomenon of methanol crossover PEM.Therefore have and utilize the PEM of different ions base concentration to make lamination structure, or utilize the polymer that contains phenyl ring in addition sulfonated, the technology that the concentration of Controlling System intermediate ion base reduces methanol crossover PEM proposes.For example, the heterocycle that utilizes imidazolium compounds of announcement such as United States Patent (USP) No. 5525436, No. 5716727, No. 6025085, No. 6099988, No. 6124060 and No. 5599639 provides proton-conducting; No. 6444343 United States Patent (USP) etc. disclose (PolystyreneSulfonic Acid is PSSA) with poly-difluoroethylene (polyvinylidene fluoride with poly-sulfonic acid vinylbenzene; PVDF) crosslinking reaction forms film; What United States Patent (USP) waited announcement No. 6365294 again is the PEM of base material with polyphosphonitrile (polyphosphazene).Though the technology of above-mentioned United States Patent (USP) is with the radical ion concentration that reduces the PEM material or select other PEM equivalent material for use, the methanol crossover rate of the PEM of formation is reduced, but the enforcement of above-mentioned technology need be operated under high temperature or anhydrous environment mostly and just have preferable proton conductive degree, and its proton conductive degree can reduce along with the reduction of methanol crossover rate.
Part is to be conceived to improve the full water-based that PEM uses at high temperature at the patent of PEM material upgrading, or reduces the penetration phenomenon of oxyhydrogen.The simple building-up reactions of research and utilization is filled in inorganic, metal oxide in the cluster (cluster) of PEM material, or direct and the blending of PEM material, and expectation strengthens the conductive stability of PEM proton in hot environment whereby or reduces the penetration coefficient of fuel.For example, No. 5849428 grade of United States Patent (USP) discloses at tetrafluoroethylene (Polyterafluoroethylene; PTFE) with in the porous-film of zirconium white phosphorus (ZrOP) add the technology of inorganic oxide; United States Patent (USP) waits the method that deposits ZrOP in PEM that discloses for No. 5849428; United States Patent (USP) waits the method that adds the inorganic proton conductor in PEM that discloses for No. 5919583; Announcements such as United States Patent (USP) No. 6059943, No. 6387230 with sol-gel process PEM is at high temperature combined with ZrOP, improve its conductance; No. the 5795496th, United States Patent (USP) wait disclose with polyether-ether-ketone (poly (ether ether ketone); S-PEEK), polyethersulfone (poly (ether sulfone); S-PES) with zeolite (H-zeolite), utilize the sulfonated of high performance engineering plastics, make macromolecule membrane have the proton conductive degree, and add zeolite reduction methanol crossover rate.Though yet aforesaid method can reduce the volume of the hydrophilic cluster (cluster) of conventional P EM material, part reduces the methanol crossover rate of PEM, but usually and fail effectively to improve, and because reduce the volume of hydrophilic cluster in the PEM material, also can reduce the conducting path of proton simultaneously, cause the decline of conductance.
Another improvement scheme is to change the mode of proton conduction.Changing the mode of proton conduction, is with the mode of proton from originally conducting with the radical ion form among PEM, changes the proton jump mechanism (Hopping Mechanism) of utilizing the solid-state acidic group of inorganics into and conducts.For example, during in gas phase, the reacting of propositions such as No. the 4594297th, United States Patent (USP), change the proton transfer mode with polyvinyl alcohol (PVA) and heteropolyacid (Heteropolyacid); Using in gas phase of No. 4380575 prompting of United States Patent (USP) with the heteropolyacid solid electrolyte; No. 9852243 patents of WO etc. are pointed out out fully with zeolite as ionogen.Yet, for fear of organic materials difficulty possess this characteristic, and inorganic materials has its congenital restriction on the film forming processibility, simultaneously, it is limited and mostly be water-soluble to have the inorganic materials of high proton conductance under the room temperature, so this method is applied in the improvement of PEM, there is no breakthrough progress at present.
Summary of the invention
For overcoming the shortcoming of above-mentioned prior art, main purpose of the present invention is to provide the proton-conductive films and the method for making thereof of the low methanol crossover that is applicable to direct methanol feeding fuel cell.
For reaching above-mentioned and other purpose, the method for making of proton-conductive films provided by the invention is earlier fluorine-containing styrene monomer to be grafted on the polymeric membrane material, to be grafted with the polymeric membrane material film forming of fluorine-containing styryl more, with this film of acid solution acidifying of cation exchange group, this cationic exchange base is replaced on this fluorine-containing cinnamic phenyl ring then.The present invention also provides a kind of usefulness proton-conductive films that above-mentioned method for making is made.
Particularly, the method for making of proton-conductive films of the present invention is that the inclined to one side fluorine that the fluorine-containing styrene monomer with different grafting position is grafted on as poly-difluoroethylene resin (PVDF) is on the polymeric membrane material, again after acidifying, the cationic exchange base is replaced on the phenyl ring of fluorine-containing styryl makes proton-conductive films of the present invention.
In preferred embodiment, the present invention is to be the main composition of proton-conductive films with the sulfonic fluoropolymer polystyrene graft to poly-difluoroethylene resin (PVDF-g-PS-F).
The present invention is the manufacturing of polymeric membrane material with the inclined to one side fluorine that fluorine-containing styrene monomer is grafted on as poly-difluoroethylene resin, only otherwise the carrying out of influence reaction can be adopted any existing physics or chemical process.Preferably carry out with following two kinds of methods: the first is earlier with the polymeric membrane material of irradiation such as X-ray, electron beam, gamma-rays or electricity slurry as poly-difluoroethylene resin, then with fluorine-containing vinylbenzene (fluoro-styrene) monomer-grafted be to make the poly-difluoroethylene resin of fluorophenethyl thiazolinyl grafted on the polymeric membrane material to activated alkene; Another kind method is with radical polymerization fluorine-containing styrene monomer to be directly grafted to as on the polymeric membrane material that gathers the difluoroethylene resin, makes fluorine-containing styryl grafted polymeric membrane material.
In above-mentioned irradiation, control irradiation dose and monomeric usage quantity can change graft(ing) degree, suitable graft(ing) degree can make resin keep original mechanical property, and has suitable solvent solubility, this solvability to help the manufacturing of film or the carrying out of follow-up upgrading process.The polymerizing condition of knowing in then can kind, addition, monomeric usage quantity and this technical field of initiator in radical polymerization waits controls graft(ing) degree.
No matter which kind of method preparing the inclined to one side fluorine that is grafted with fluorine-containing styryl with is the polymeric membrane material, the graft(ing) degree of fluorine-containing styryl is advisable with 10 to 100wt% ((gross weight after the grafting-original polymeric membrane material weight)/original polymeric membrane material weight), at graft product that obtains under this graft(ing) degree and the ionic polymer after the acidifying preferable mechanical properties is arranged.
Fluorine atom on the fluorine-containing styrene monomer of the present invention can be grafted on the optional position on the phenyl ring, wherein to graft on contraposition (para) or a position (meta) for good.For example, of the present invention is that polymeric membrane material preferred embodiments is the poly-difluoroethylene resin (PVDF-g-PS-m-F or PVDF-g-PS-3-F) of the poly-difluoroethylene resin (PVDF-g-PS-p-F or PVDF-g-PS-4-F) of the polystyrene-based grafted of contraposition-fluoro-or a position-fluoro-polystyrene graft with fluorine-containing styrene monomer grafted as the inclined to one side fluorine that gathers the difluoroethylene resin.
The fluorine-containing polystyrene monomers grafted of above-mentioned usefulness polymeric membrane material is to handle with the acid solution of suitable cationic reagent or cation exchange group subsequently, makes the fluorine-containing styrene-grafted polymeric membrane material with cationic exchange base.Being applicable to that cation radical of the present invention can be sulfonic group, carboxyl, phosphate, inferior amide group, the inferior amide group of sulphur or sulfoamido etc., is good (PVDF-g-SPS-4-F) with liberation degree and the preferable sulfonate group of acidity wherein.The selection of this cationic reagent can suitably be selected according to reaction is required, is example with sulfonate group reagent, the spendable for example vitriol oil, chlorsulfonic acid, sulphur trioxide, oleum, the acetyl sulfonate etc. of comprising.And formed fluorine-containing styrene-grafted inclined to one side fluorine with cationic exchange base is in the polymeric membrane material, and the cationic exchange equivalent is at least 0.1mmol/g, is preferably 0.1 to 10mmol/g, especially with 0.1 to 2.5mmol/g for better.
In order further to promote chemical resistance, thermotolerance and the mechanical properties of film, also can add other resinous principle in the proton-conductive films of the present invention or form composite membrane in conjunction with other electronic conduction film.This other resinous principle can be fluorine resin or fluorine resin not.Fluorine resin can be single polymers or multipolymer, for example poly(vinylidene fluoride), poly(vinylidene fluoride)/R 1216 co-polymer, a poly(vinylidene fluoride)/chlorotrifluoroethylene co-polymer, poly(vinylidene fluoride)/R 1216/tetrafluoroethylene terpolymer or polymonochlorotrifluoroethylene etc.Hydrocarbon resinoid can for example be the hydrocarbon resin that polyacrylic ester (polyacrylate), polyester (polyester), polyether-ether-ketone (polyether ether ketone), polysulfonates (polysulfonate), polyethers (polyether), polymeric amide (polyamide), polyphenylene oxide (polyphenylene oxide) and polyethylene oxide tradition such as (polyethylene oxide) are known.That the weight that the addition of above-mentioned other resinous principle is the polymeric membrane material with the fluorine-containing styrene-grafted inclined to one side fluorine of tool cationic exchange base is calculated as is preferable between 0 to 50 weight % (weight of adding resin divided by the fluorine-containing styrene-grafted inclined to one side fluorine of the tool cationic exchange base weight that is polymeric membrane material and resin with).
The solvent that uses in the manufacturing of film can be an aprotic solvent, as dimethyl formamide (Dimethylformamide), 1-Methyl-2-Pyrrolidone (1-Methyl-2-pyrrolidone) or methyl-sulphoxide (Dimethylsulfoxide) etc., also can add a spot of protic solvent, as alcoholic solvent etc.After the mixture dissolving that is compositions such as polymeric membrane material and other additive of fluorine-containing styrene-grafted inclined to one side fluorine, can be with scraper coating method film forming.Desolventize outside the method, the mode that the mode of system film also can any tradition be known is as pressure sintering, roll to wait around membrane process, method of spin coating or extrusion process and make.
Also can add processibility and other performance of improving film as compositions such as tensio-active agent, plasticizer, film smoothing agent, antioxidants in the composition of film.This composite membrane has good thermotolerance, resistance to acids and bases, mechanicalness and flexibility, and this film does not have decomposing phenomenon during standing storage yet in pH value 1 to 14 scope.
The proton-conductive films that makes according to the present invention, its proton conductive degree is at least 1 * 10
-3To 1 * 10
-1S/cm, and its methanol crossover rate is 1 * 10
-8To 2 * 10
-6Cm
2/ sec.
Description of drawings
Fig. 1 (a) is the chemical structural drawing of the proton-conductive films (PVDF-g-SPS-p-F) of the embodiment of the invention 1;
Fig. 1 (b) is the IR analytical results figure of the proton-conductive films (PVDF-g-SPS-p-F) of the embodiment of the invention 1;
Fig. 2 is the chemical structural drawing of the proton-conductive films (PVDF-g-SPS-p-F) of the embodiment of the invention 2.
Embodiment
Embodiment 1
20g contraposition-fluorobenzene ethene (p-fluoro-styrene) monomer (purity 99.8%) is added in the poly-difluoroethylene resin (PVDF) of 40g, after stirring, carry out radiation irradiation with Co-60 and carry out graft reaction, irradiation dose is to be controlled at 25gGy.The PVDF-g-PS-p-F crude product of gained carries out soxhlet extraction (Soxhlet extraction) with ethyl acetate, removes unreacted monomer and vinylbenzene homopolymer.Product obtains the PVDF-g-PS product of white under room temperature or heat drying, graft weight per-cent is 38.5 weight %.PVDF-g-PS-p-F is added (solids content 3 is to 50wt%) among the 1-Methyl-2-Pyrrolidone 20ml with the plain tensio-active agent FC-430 of 10mg fluorine, then with scraper coating method (120 ℃) film forming under heating.Afterwards, this film carries out sulfonated reaction with chlorsulfonic acid under 25 ℃, and the reaction times is 8 hours.Film after sulfonated successively cleans with tetrahydrofuran (THF) and water, then 80 ℃ under vacuum condition dry 6 hours, promptly make proton-conductive films of the present invention.The chemical structure of the proton-conductive films that makes is seen Fig. 1 (a), and its IR analytical results is seen Fig. 1 (b).The proton conductive degree of testing this proton-conductive films with AC alternating-current impedance method is 1.3 * 10
-2S/cm.
Embodiment 2
Position-fluorobenzene ethene (m-fluoro-styrene) monomer (purity 99.8%) between 20g is added in the poly-difluoroethylene resin (PVDF) of 40g, after stirring, carry out radiation irradiation to produce graft reaction with Co-60, irradiation dose is to be controlled at 25gGy.The PVDF-g-PS-m-F crude product of gained carries out soxhlet extraction (Soxhlet extraction) with ethyl acetate, removes unreacted monomer and vinylbenzene homopolymer.Product obtains the PVDF-g-PS product of white under room temperature or heat drying, graft weight per-cent is 32.5 weight %.PVDF-g-PS-3-F is added (solids content 3 is to 50wt%) among the 1-Methyl-2-Pyrrolidone 20ml with the plain tensio-active agent FC-430 of 10mg fluorine, then with scraper coating method (130 ℃) film forming under heating.Afterwards, this film carries out sulfonated reaction with chlorsulfonic acid under 25 ℃, and the reaction times is 8 hours.Film after sulfonated successively cleans with tetrahydrofuran (THF) and water, then under 80 ℃ of vacuum conditions dry 6 hours, promptly makes proton-conductive films of the present invention.The chemical structure of the proton-conductive films that makes is seen Fig. 2.The proton conductive degree of testing this proton-conductive films with AC alternating-current impedance method is 3.5 * 10
-3S/cm.
Water-intake rate is analyzed
Exsiccant is had proton-conductive films that the poly-difluoroethylene resin of sulfonic polystyrene graft makes boils 30 minutes in boiling water (or methyl alcohol) after, with its taking-up and with lens paper the water droplet on film surface is dried, with the proton-conductive films weighing that is about to dry, the weight of water that film absorbs is made the weight of dry film divided by the poly-difluoroethylene resin with sulfonic polystyrene graft, promptly obtain the water-intake rate of film.
Comparison test
The proton-conductive films that makes with the commercially available Nafion117 and the embodiment of the invention 1 carries out the comparison test of conductance, methanol crossover (methanol crossover), water-intake rate and methyl alcohol specific absorption, and it the results are shown in Table 1.
Table 1
| Sample | Conductance (S/cm) | Methanol crossover rate (cm 2/s) | Water-intake rate (weight %) | Solvent absorbing rate (weight %) |
| Nafion117 | 6×10 -2 | 2.6×10 -6 | 23 | 100 |
| Embodiment 1 | 1×10 -2 | 2.2×10 -7 | 26 | 23 |
By table 1 result as can be known, proton-conductive films of the present invention is not subjected in conductance under the situation of materially affect, has the methanol crossover rate lower than the commercially available prod, lower water-intake rate and methyl alcohol specific absorption.Proton-conductive films just of the present invention is applied in the direct methanol feeding type fuel cell, can reduce the swelling in the methanol fuel cell of film material and obviously reduce penetrating of its methyl alcohol.
Claims (23)
1. proton-conductive films, being grafted on the polymeric membrane material by fluorine-containing styrene monomer forms, it is characterized in that this is grafted on the phenyl ring of the fluorine-containing styryl on the polymeric membrane material and is substituted with the cationic exchange base, and the contraposition of the fluorine substituted benzene ring of this fluorine-containing styryl or a position.
2. proton-conductive films as claimed in claim 1 is characterized in that the conductance of this proton-conductive films is 1 * 10
-3To 1 * 10
-1S/cm.
3. proton-conductive films as claimed in claim 1 is characterized in that, the methanol crossover rate of this proton-conductive films is 1 * 10
-8To 2 * 10
-6Cm
2/ sec.
4. proton-conductive films as claimed in claim 1 is characterized in that, this cationic exchange base is to be selected from by the inferior amide group of sulfonic group, carboxyl, phosphate, inferior amide group, sulphur to be become in the group one of them with sulfoamido.
5. proton-conductive films as claimed in claim 1 is characterized in that the equivalent of this cationic exchange base is at least 0.1mmol/g.
6. proton-conductive films as claimed in claim 5 is characterized in that, the equivalent of this cationic exchange base is 0.1 to 10mmol/g.
7. proton-conductive films as claimed in claim 6 is characterized in that, the equivalent of this cationic exchange base is 0.1 to 2.5mmol/g.
8. proton-conductive films as claimed in claim 1 is characterized in that, also comprises by interfacial agent, plasticizer, film smoothing agent and antioxidant being become in the group one of them.
9. proton-conductive films as claimed in claim 1 is characterized in that, the graft(ing) degree of this fluorine-containing phenylacetyl monomer and polymeric membrane material is 10 to 100 weight %, and wherein, graft(ing) degree calculates according to following formula:
(gross weight after the grafting-original polymeric membrane material weight)/original polymeric membrane material weight.
10. the method for making of a proton-conductive films is characterized in that, this method for making comprises the following steps:
Fluorine-containing styrene monomer is grafted on the polymeric membrane material contraposition of the fluorine substituted benzene ring of this fluorine-containing styryl or a position;
To be grafted with fluorine-containing cinnamic polymeric membrane material film forming; And
This is grafted with the film that fluorine-containing cinnamic polymeric membrane material is become with acid solution acidifying with cationic exchange base, makes the cationic exchange base replace the phenyl ring of this fluorine-containing styryl.
11. method for making as claimed in claim 10 is characterized in that, the conductance of this proton-conductive films is 1 * 10
-3To 1 * 10
-1S/cm.
12. method for making as claimed in claim 10 is characterized in that, the methanol crossover rate of this proton-conductive films is 1 * 10
-8To 2 * 10
-6Cm
2/ sec.
13. method for making as claimed in claim 10 is characterized in that, this cationic exchange base is to be selected from by the inferior amide group of sulfonic group, carboxyl, phosphate, inferior amide group, sulphur to be become in the group one of them with sulfoamido.
14. method for making as claimed in claim 10 is characterized in that, the equivalent of this cationic exchange base is at least 0.1mmol/g.
15. method for making as claimed in claim 14 is characterized in that, the equivalent of this cationic exchange base is 0.1 to 10mmol/g.
16. method for making as claimed in claim 15 is characterized in that, the equivalent of this cationic exchange base is 0.1 to 2.5mmol/g.
17. method for making as claimed in claim 10, it is characterized in that this polymeric membrane material is to be selected from by poly-difluoroethylene resin, poly-difluoroethylene/hexafluoropropylene copolymer, a poly-difluoroethylene/chlorotrifluoroethylcopolymer copolymer, poly-difluoroethylene/hexachloropropylene/tetrafluoroethylene trimer and polymonochlorotrifluoroethylene to be become in the group one of them.
18. method for making as claimed in claim 10, it is characterized in that the mode that makes this fluorine-containing styrene monomer graft on the polymeric membrane material is to be implemented by the mixture that this polymeric membrane material and fluorine-containing styrene monomer mix by any one irradiation of X-ray, electron beam, gamma-rays or electricity slurry.
19. method for making as claimed in claim 10 is characterized in that, is applicable to this film forming method of polymeric membrane material that is grafted with fluorine-containing styryl it is to be selected from by pressure sintering, to roll around membrane process, method of spin coating or extrusion process and become in the cohort one of them.
20. method for making as claimed in claim 10 is characterized in that, the graft(ing) degree of this fluorine-containing phenylacetyl monomer and polymeric membrane material is 10 to 100 weight %, and wherein, graft(ing) degree calculates according to following formula:
(gross weight after the grafting-original polymeric membrane material weight)/original polymeric membrane material weight.
21. a composite membrane is characterized in that, be the proton-conductive films with method for making as described in claim 10 preparation, forms with other proton-conductive films lamination or blending.
22. composite membrane as claimed in claim 21 is characterized in that, this other proton-conductive films is perfluor or the half fluorine polymeric membrane material that contains the ionic conduction functional group.
23. composite membrane as claimed in claim 21 is characterized in that, this other proton-conductive films is at least one in Nafion and the PVDF-grafting-sulfonated vinylbenzene.
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| US20110045381A1 (en) * | 2009-08-18 | 2011-02-24 | Gm Global Technology Operations, Inc. | Hydrocarbon PEM Membranes with Perfluorosulfonic Acid Groups for Automotive Fuel Cells |
| CN102324534B (en) * | 2011-08-02 | 2014-01-08 | 东华大学 | Polyamide membrane with proton conduction property, and preparation method thereof |
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