WO2004039870A2 - Size for glass fibers and use thereof in cation exchange membranes - Google Patents
Size for glass fibers and use thereof in cation exchange membranes Download PDFInfo
- Publication number
- WO2004039870A2 WO2004039870A2 PCT/DE2003/003429 DE0303429W WO2004039870A2 WO 2004039870 A2 WO2004039870 A2 WO 2004039870A2 DE 0303429 W DE0303429 W DE 0303429W WO 2004039870 A2 WO2004039870 A2 WO 2004039870A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- reinforcing material
- reinforced
- polymer membrane
- membrane
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 45
- 238000005341 cation exchange Methods 0.000 title claims description 6
- 239000003365 glass fiber Substances 0.000 title description 8
- 229920005597 polymer membrane Polymers 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 239000000446 fuel Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 6
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 3
- 239000012779 reinforcing material Substances 0.000 claims description 48
- 230000002378 acidificating effect Effects 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- 230000008878 coupling Effects 0.000 claims description 15
- 238000010168 coupling process Methods 0.000 claims description 15
- 238000005859 coupling reaction Methods 0.000 claims description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 12
- 229910000077 silane Inorganic materials 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 10
- 230000009881 electrostatic interaction Effects 0.000 claims description 9
- -1 heterocyclic nitrogen compounds Chemical class 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920002959 polymer blend Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 239000012784 inorganic fiber Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920001197 polyacetylene Polymers 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920002480 polybenzimidazole Polymers 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 150000003140 primary amides Chemical class 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 150000003334 secondary amides Chemical class 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 150000003511 tertiary amides Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 150000003557 thiazoles Chemical class 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 150000002916 oxazoles Chemical class 0.000 claims 1
- 229920006393 polyether sulfone Polymers 0.000 claims 1
- 230000002787 reinforcement Effects 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229920000554 ionomer Polymers 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical class C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical class [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical class [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 150000002537 isoquinolines Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical class O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical class [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 150000003212 purines Chemical class 0.000 description 1
- 150000003216 pyrazines Chemical class 0.000 description 1
- 150000004892 pyridazines Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical class [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/108—Inorganic support material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/40—Organo-silicon compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
-
- 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
Definitions
- the invention relates to reinforced polymer membranes, methods for reinforcing polymer membranes, uses of the reinforced polymer membranes and polymer electrolyte membrane fuel cells.
- polymer electroly membranes e.g. in polymer ⁇ electrolyte membrane fuel cells requires a high chemical, thermal and mechanical stability of the membranes.
- the membrane materials usually show insufficient mechanical stability under operating conditions.
- the membranes can be stabilized by using the membranes either in an increased thickness or mechanically reinforced.
- the ionic conductivity of the membranes is limited by the thickness of the membranes.
- Mechanical reinforcement of the membranes by means of fibers, fabrics and / or nonwovens, which often consist of silicate glasses, is also known in the prior art.
- this reinforcement by glass fibers according to the prior art has the disadvantage that the polymer membrane binds only insufficiently to the reinforcing materials.
- covalently cross-linked composite polymer membranes consist of polymers and framework and / or layered silicates.
- the polymer membrane is covalently bound to the glass surface modified by aminosilane via allylic Cl groups.
- cation exchange polymer and anion exchange polymer blend membranes are known, which however have only a low mechanical stability.
- the term “sizing agent” is understood to mean the use of one or more substances for modifying the surface, for example the reinforcing material, which is applied to the reinforcing material from a preferably aqueous or alcoholic solution and preferably covers the surface thereof as a thin film.
- Another important influencing factor is the water balance of the fuel cells, since the membranes only show good conductivity when there is sufficient moisture.
- the subject matter of the invention relates to a reinforced polymer membrane, the reinforced polymer membrane comprising at least one polymer layer based on at least one polymer with acidic properties and at least one reinforcing material layer with basic properties, at least one outer surface of the polymer layer being adhesive at least one outer surface of the reinforcing material layer contacted, the liability based on an electrostatic interaction.
- the electrostatic interaction is preferably an interaction between an acidic and a basic group.
- An advantage of the reinforced polymer membrane according to the invention is that the combination of the material to be reinforced with the reinforcing material is based on electrostatic interaction.
- the polymer membrane according to the invention has in particular an improved resistance to changes in the moisture content in the fuel cell during operation and thus an improved mechanical integrity of the composite material compared to that of a covalent one Bonds to a rigid membrane bonded to reinforcement material.
- the term “reinforced” is understood to mean “stabilized”.
- the reinforced polymer membrane according to the invention shows, through an improved ability to adapt to different moisture conditions, a significantly reduced crack formation or splintering of the material composite due to changing moisture and thus a lower risk of the acid ionomer separating from the basic reinforcing material and a significantly increased long-term stability and thus a longer one Usability of the network in fuel cells.
- the reinforcing material comprises an oxidic material, the oxidic material preferably containing zirconium, silicon and / or titanium.
- Preferred oxidic materials are glasses of cooled melts of silicon oxides, zirconium oxides, titanium oxides, calcium oxides and / or sodium oxides, which can comprise additions of boron oxides, aluminum oxides, lead oxides, magnesium oxides, barium oxides and / or potassium oxides, in particular silicate glasses are preferred.
- the oxidic reinforcing material can have further customary additives and / or components.
- the reinforcing material layer preferably comprises inorganic fibers or filaments, nonwovens and / or fabrics, the length and diameter of the fibers or filaments being generally variable, glass fibers having a small diameter are preferred, with a large surface area of the reinforcing material. Furthermore, the fibers and filaments can form nonwovens and / or fabrics, nonwovens forming a preferred reinforcing material layer.
- the surface of the reinforcing material can be modified, preferred sizing agents for modification in particular are special basic sizing agents.
- the sizing agent according to the invention comprises a coupling reagent and preferably suitable additives, for example film formers, surface-active substances, plasticizers and / or stabilizers.
- a “coupling reagent” in the sense of this invention means an agent which contributes to the formation of the composite according to the invention between a polymer layer based on at least one polymer with acid properties and at least one reinforcing material layer with basic properties.
- Preferred coupling reagents in the sense of the invention are silanes "The present invention particularly relates to the use of coupling agents with amino functional side groups or aminosilane coupling agents. Any aminosilane coupling agent which condenses on a glass and has an amino functional group on the modified surface can be used for the purposes of the invention. ***"
- the oxidic materials or glasses used according to the invention can be sized untreated or pretreated. Pre-treatment of the surface of the glass fibers is preferred according to the invention. Suitable basic solutions or bases, for example sodium hydroxide or potassium hydroxide bases, can act on the fibers at room temperature or at elevated temperatures and etch their surface.
- an advantageous embodiment of the invention is that the reinforcing material is modified with a coupling reagent, preferably silane, this coupling reagent preferably being applied to the reinforcing material by condensation.
- a coupling reagent preferably silane
- the condensation reaction can be catalyzed basic or acidic.
- n, m is identical or independent of one another 1, 2 or 3; n + is 4;
- R is an alkyl or aryl group
- B is a basic group, in particular a nitrogen compound, selected from the group comprising primary, secondary or tertiary amines, primary, secondary or tertiary amides, heterocyclic nitrogen compounds, in particular 5-ring or 6-ring heterocycles, e.g. Pyrazoles, imidazoles, triazoles, 0-xazoles, thiazoles, pyridines, pryridines or condensed nitrogen-containing ring systems.
- a nitrogen compound selected from the group comprising primary, secondary or tertiary amines, primary, secondary or tertiary amides, heterocyclic nitrogen compounds, in particular 5-ring or 6-ring heterocycles, e.g. Pyrazoles, imidazoles, triazoles, 0-xazoles, thiazoles, pyridines, pryridines or condensed nitrogen-containing ring systems.
- nitrogen-containing groups B are, for example, pyrroles, pyrazines, pyridazines, triazines, indoles, quinolines, isoquinolines or purines.
- the condensation reaction leads to the formation of a modified surface of the glass fibers, the surface of the reinforcing material preferably having the basic or nitrogen-containing groups of the silane on the modified surface.
- a functional side group of the coupling reagent can also be a protected amino group.
- the side groups selected according to the invention are, independently of one another, nitrogen-containing side groups and alkoxy groups, which may have further functional groups.
- Preferred side groups of the silanes used in accordance with the invention are alkoxy groups, comprising short linear alkyl groups with 1 to 6 carbon atoms, particularly preferably methoxy or ethoxy groups.
- m is 1 or 3;
- 1 is an integer between 0 and 12;
- Me is a methyl group; v is 1 or 3; v + m is 4.
- 3-aminopropyltrimethoxysilane or aminopropyltriethoxysilane are used.
- the reinforcing material is preferably modified with a basic silane coupling reagent of the formula (MeO) 3 SiNH 2 .
- the modified reinforcing materials are preferably used in cation-exchange membranes.
- Another advantage of the polymer membrane reinforced according to the invention results from the fact that, according to the invention, the reinforced membrane is a polymer electrolyte membrane, preferably a cation-exchange membrane.
- polymer used with acidic properties comprising polymers, copolymers and / or polymer blends
- polymers suitable according to the invention are, for example, polyvinyl chloride, polystyrene, polymethyl methacrylate, polytetrafluoroethylene.
- the polymer particularly preferably has sulfonic acid groups.
- An inventively usable polymer having acidic properties is particularly Nafion ®, available from Du Pont.
- a further advantageous embodiment of the invention is that the reinforcing material of the polymer membrane modified with a coupling reagent, compared to the correspondingly unmodified polymer membrane, has a higher number of dry-wet cycles at 80 ° C. without loss of mechanical integrity and without destruction of the bond between the Polymer layer and the reinforcement material protruding.
- the comparison polymer membrane is a polymer membrane of identical composition, except that the reinforcing material layer of the comparison polymer membrane was not modified according to the invention. Another significant improvement is that the composite according to the invention is not destroyed even by frequent swelling and drying. The number of dry-wet cycles at 80 ° C.
- the reinforced polymer membrane according to the invention withstands without loss of mechanical integrity is preferably higher by a factor of> 1 than the corresponding polymer membranes not reinforced according to the invention, preferably by a factor of> 1.5 higher and particularly preferably at least twice as high.
- the adhesion between the polymer layer, based at least on a polymer with acid properties and the reinforcing material layer with basic properties is based exclusively on electrostatic interaction.
- the acidic ionomer is bound to the basic glass fiber by ionic interaction.
- the basic modified surface of the fleece occurs with a polymer in contact with acidic properties.
- the composite formed is preferably based on an ionic interaction between the acidic groups of the polymer and the basic, preferably nitrogen-containing, groups of the reinforcing material.
- detachment of the material to be reinforced from the reinforcing material is also avoided, for example under conditions which cause the ionomer to swell and shrink, such as conditions of changing moisture.
- the method advantageously comprises the following steps: a) modification of the reinforcing material with a basic silane; b) contacting the modified basic reinforcing material with a polymer with acidic properties, the polymer with acidic properties binding to the basic modified reinforcing material via electrostatic interaction.
- An advantageous embodiment of the invention is that a polymer membrane reinforced according to the invention is used as the polymer electrolyte membrane in a polymer electrolyte membrane fuel cell.
- a polymer membrane reinforced according to the invention is used as the polymer electrolyte membrane for the production of electrochemically generated energy.
- a polymer membrane reinforced according to the invention is preferably used as the membrane in dialysis and / or separation processes.
- fuel cells in particular polymer electrolyte membrane fuel cells, have at least one polymer membrane reinforced according to the invention.
- the following exemplary embodiment describes a preferred possibility of representing a polymer membrane reinforced according to the invention without restricting the invention thereto.
- a thin glass fiber fleece was etched on the surface by immersion in 1 molar sodium hydroxide solution at 50 ° C. for 10 seconds and then rinsed thoroughly with deionized water.
- the fleece was dried at 30 ° C. in a forced air oven for 10 minutes and then immersed in a 50% solution of 3-aminopropyltrimethoxysilane in ethanol at room temperature for 10 seconds. Excess solution was removed by shaking and the fleece was dried at room temperature for 30 minutes and then at 100 ° C. for 10 minutes.
- the membrane obtained was then removed from the glass surface in a water bath, dried with lint-free paper, fixed to the edges on a further glass plate with adhesive tape and dried for 2 minutes at an oven temperature of 120 ° C.
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Abstract
The invention relates to a reinforced polymer membrane comprising at least one polymer layer that is based on at least one polymer having acid properties and at least one layer of reinforcement material having alkaline properties. At least one outer surface of the polymer layer is in contact with an outer surface of the layer of reinforcement material so as to adhere thereto, the adhesion being based on a mutual electrostatic effect. The invention further relates to a method for reinforcing a polymer membrane, the use of reinforced polymer membranes, and fuel cells, especially polymer electrolyte membrane fuel cells, comprising at least one inventive reinforced polymer membrane.
Description
DaimlerChrysler AGDaimlerChrysler AG
Eine neue Schlichte für Glasfasern und deren Einsatz in Katio- nenaustauschermembranenA new size for glass fibers and their use in cation exchange membranes
Die Erfindung betrifft verstärkte Polymermembranen, Verfahren zur Verstärkung von Polymermembranen, Verwendungen der verstärkten Polymermembranen sowie Polymer-Elektrolyt-Membran- Brennstoffzellen.The invention relates to reinforced polymer membranes, methods for reinforcing polymer membranes, uses of the reinforced polymer membranes and polymer electrolyte membrane fuel cells.
Die Verwendung von Polymer-Elektroly -Membranen z.B. in Poly- mer-Ξlektrolyt-Membran-Brennstoffzellen erfordert eine hohe chemische, thermische und mechanische Stabilität der Membranen. Die Membranmaterialien zeigen unter Betriebsbedingungen meist eine zu geringe mechanische Stabilität.The use of polymer electroly membranes e.g. in polymer Ξ electrolyte membrane fuel cells requires a high chemical, thermal and mechanical stability of the membranes. The membrane materials usually show insufficient mechanical stability under operating conditions.
Möglichkeiten der Stabilisierung der Membranen bestehen darin, die Membranen entweder in einer erhöhten Dicke oder mechanisch verstärkt einzusetzen. Die Ionenleitfähigkeit der Membranen wird jedoch durch die Dicke der Membranen begrenzt. Im Stand der Technik ist ebenfalls eine mechanische Verstärkung der Membranen mittels Fasern, Geweben und/oder Vliesen bekannt, die häufig aus Silicatgläsern bestehen. Diese Verstärkung durch Glasfasern gemäß dem Stand der Technik hat jedoch den Nachteil, dass die Polymermembran nur ungenügend an die Verstärkungsmaterialien bindet.The membranes can be stabilized by using the membranes either in an increased thickness or mechanically reinforced. The ionic conductivity of the membranes is limited by the thickness of the membranes. Mechanical reinforcement of the membranes by means of fibers, fabrics and / or nonwovens, which often consist of silicate glasses, is also known in the prior art. However, this reinforcement by glass fibers according to the prior art has the disadvantage that the polymer membrane binds only insufficiently to the reinforcing materials.
Aus der deutschen Patentanmeldung DE 100 54 233 sind kovalent vernetzte Komposit-Polymer-Membranen bekannt, die aus Polymeren und Gerüst- und/oder Schichtsilicaten bestehen. Die Polymermembran wird über allylische Cl-Gruppen kovalent an die durch Aminosilan modifizierte Glasoberfläche gebunden.
Weiterhin sind aus der Patentschrift DE 198 17 374 Kationenaustauscherpolymer- und Anionenaustauscherpolymer-Blend- membranen bekannt, die jedoch nur eine geringe mechanische Stabilität aufweisen.From German patent application DE 100 54 233, covalently cross-linked composite polymer membranes are known which consist of polymers and framework and / or layered silicates. The polymer membrane is covalently bound to the glass surface modified by aminosilane via allylic Cl groups. Furthermore, from the patent specification DE 198 17 374, cation exchange polymer and anion exchange polymer blend membranes are known, which however have only a low mechanical stability.
Bei dem vorgenannten Stand der Technik handelt es sich um Techniken der Verstärkung, die weitgehend von der Modifikation der Glasoberfläche durch das Verfahren des Schlichtens abhängen. Unter dem Begriff „Schlichtemittel" wird im Sinne dieser Erfindung die Verwendung einer oder mehrerer Substanzen zur Modifizierung der Oberfläche, z.B. des Verstärkungsmaterials verstanden, welche aus einer bevorzugt wässrigen oder alkoholischen Lösung auf das Verstärkungsmaterial aufgebracht wird und bevorzugt als ein dünner Film dessen Oberfläche bedeckt.The aforementioned prior art involves reinforcement techniques which largely depend on the modification of the glass surface by the finishing process. For the purposes of this invention, the term “sizing agent” is understood to mean the use of one or more substances for modifying the surface, for example the reinforcing material, which is applied to the reinforcing material from a preferably aqueous or alcoholic solution and preferably covers the surface thereof as a thin film.
Eine weitere wesentliche Einflussgrδße ist der Wasserhaushalt der Brennstoffzellen, da die Membranen nur bei ausreichender Feuchtigkeit eine gute Leitfähigkeit zeigen.Another important influencing factor is the water balance of the fuel cells, since the membranes only show good conductivity when there is sufficient moisture.
Das Entstehen eines Diffusionsstromes an der Oberfläche der Membran durch Zuführung des Reaktionsgases kann zu einer Austrocknung der Membran führen, während flüssiges Wasser die Poren der Membran füllen kann. Ein stabiles Feuchtigkeitsniveau in der Membran kann während des Betriebes bislang nicht völlig gesichert werden. Sind die Membranen einem schwankenden Wassergehalt ausgesetzt, so wird durch das dadurch verursachte Quellen und Trocknen der Membranen deren Anbindung an das Verstärkungsmaterial zerstört und die Dauer ihrer Einsatz- fähigkeit in einer Brennstoffzelle verkürzt .The formation of a diffusion current on the surface of the membrane by supplying the reaction gas can lead to drying out of the membrane, while liquid water can fill the pores of the membrane. A stable moisture level in the membrane has so far not been completely ensured during operation. If the membranes are exposed to a fluctuating water content, the resulting swelling and drying of the membranes will destroy their connection to the reinforcing material and shorten the period of their usability in a fuel cell.
Es ist daher die Aufgabe der vorliegenden Erfindung, verstärkte Polymermembranen zur Verfügung zu stellen, die durch eine verbesserte Verbindung der Verstärkungsmaterialschicht und der Polymer-Elektrolyt-Membran eine verbesserte mechanische Stabilität des Materialverbundes aufweist.
Diese Aufgabe wird hinsichtlich einer verstärkten Polymermembran gemäß dem Oberbegriff des Anspruchs 1 in Verbindung mit dessen kennzeichnenden Merkmalen gelöst ,It is therefore the object of the present invention to provide reinforced polymer membranes which, through an improved connection of the reinforcing material layer and the polymer-electrolyte membrane, have improved mechanical stability of the material composite. This object is achieved with regard to a reinforced polymer membrane according to the preamble of claim 1 in conjunction with its characterizing features,
Weitere vorteilhafte Ausführungsformen, Verfahren und Verwendungen sind in den Unteransprüchen und Nebenansprüchen angegeben.Further advantageous embodiments, methods and uses are specified in the subclaims and subclaims.
Der erfindungsgemäße Gegenstand betrifft eine verstärkte Polymermembran, wobei die verstärkte Polymermembran wenigstens eine Polymerschicht, basierend auf wenigstens einem Polymer mit sauren Eigenschaften, und wenigstens eine Verstärkungs- materialschicht mit basischen Eigenschaften umfasst, wobei wenigstens eine äußere Oberfläche der Polymerschicht wenigstens eine äußere Oberfläche der Verstärkungsmaterialschicht haftend kontaktiert, wobei die Haftung auf einer elektrostatischen Wechselwirkung beruht .The subject matter of the invention relates to a reinforced polymer membrane, the reinforced polymer membrane comprising at least one polymer layer based on at least one polymer with acidic properties and at least one reinforcing material layer with basic properties, at least one outer surface of the polymer layer being adhesive at least one outer surface of the reinforcing material layer contacted, the liability based on an electrostatic interaction.
Erfindungsgemäß wurde gefunden, dass ein Polymer mit sauren Eigenschaften, welches an eine Verstärkungsmaterialschicht mit basischen Eigenschaften über elektrostatische Wechselwirkungen gebunden ist, die für Anwendungen als Polymer-Elektrolyt- Membran in einer Brennstoffzelle notwendige Stabilität aufweist und der Verbund durch Veränderungen des Feuchtigkeitsgehaltes in der Brennstoffzelle nicht zerstört wird. Daher handelt es sich bei der elektrostatischen Wechselwirkung vorzugsweise um eine Wechselwirkung zwischen einer sauren und einer basischen Gruppe.According to the invention, it was found that a polymer with acidic properties, which is bound to a reinforcing material layer with basic properties via electrostatic interactions, has the stability necessary for applications as a polymer-electrolyte membrane in a fuel cell and the composite does not due to changes in the moisture content in the fuel cell gets destroyed. Therefore, the electrostatic interaction is preferably an interaction between an acidic and a basic group.
Vorteilhaft bei der erfindungsgemäßen verstärkten Polymermembran ist, dass der Verbund des zu verstärkenden Materials mit dem verstärkenden Material auf elektrostatischer Wechselwirkung beruht. Die erfindungsgemäße Polymermembran weist insbesondere eine verbesserte Beständigkeit gegenüber Veränderungen des Feuchtigkeitsgehaltes in der Brennstoffzelle während des Betriebes auf und somit eine verbesserte mechanische Integrität des Materialverbundes gegenüber einer durch kovalente
Bindungen an ein starres Verstärkungsmaterial gebundenen Membran. Unter dem Begriff „verstärkt" wird im Sinne dieser Erfindung entsprechend „stabilisiert" verstanden.An advantage of the reinforced polymer membrane according to the invention is that the combination of the material to be reinforced with the reinforcing material is based on electrostatic interaction. The polymer membrane according to the invention has in particular an improved resistance to changes in the moisture content in the fuel cell during operation and thus an improved mechanical integrity of the composite material compared to that of a covalent one Bonds to a rigid membrane bonded to reinforcement material. In the sense of this invention, the term “reinforced” is understood to mean “stabilized”.
Die erfindungsgemäße verstärkte Polymermembran zeigt durch eine verbesserte Fähigkeit zur Anpassung an unterschiedliche Feuchtigkeitsverhältnisse eine deutlich verringerte Rissbildung oder Splittern des Materialverbundes aufgrund wechselnder Feuchtigkeit und somit eine geringere Gefahr der Ablösung des sauren lonomers von dem basischen Verstärkungs- material und eine deutlich erhöhte Langzeitstabilität und somit eine längere Einsatzfähigkeit des Verbundes in Brennstoffzellen.The reinforced polymer membrane according to the invention shows, through an improved ability to adapt to different moisture conditions, a significantly reduced crack formation or splintering of the material composite due to changing moisture and thus a lower risk of the acid ionomer separating from the basic reinforcing material and a significantly increased long-term stability and thus a longer one Usability of the network in fuel cells.
Eine die Erfindung verbessernde Maßnahme sieht vor, dass das Verstärkungsmaterial ein oxidisches Material umfasst, wobei das oxidische Material vorzugsweise Zirkon, Silicium und/oder Titan enthält. Bevorzugte oxidische Materialien sind Gläser abgekühlter Schmelzen von Siliciumoxiden, Zirkonoxiden, Titanoxiden, Calciumoxiden und/oder Natriumoxiden, welche Zusätze von Boroxiden, Aluminiumoxiden, Bleioxiden, Magnesiumoxiden, Bariumoxiden und/oder Kaliumoxiden umfassen können, insbesondere sind Silicatgläser bevorzugt. Ferner kann das oxidische Verstärkungsmaterial weitere übliche Zusätze und/oder Komponenten aufweisen.One measure improving the invention provides that the reinforcing material comprises an oxidic material, the oxidic material preferably containing zirconium, silicon and / or titanium. Preferred oxidic materials are glasses of cooled melts of silicon oxides, zirconium oxides, titanium oxides, calcium oxides and / or sodium oxides, which can comprise additions of boron oxides, aluminum oxides, lead oxides, magnesium oxides, barium oxides and / or potassium oxides, in particular silicate glasses are preferred. Furthermore, the oxidic reinforcing material can have further customary additives and / or components.
Die Verstärkungsmaterialschicht umfasst vorzugsweise anorganische Fasern oder Filamente, Vliese und/oder Gewebe, wobei Länge und Durchmesser der Fasern oder Filamente generell variabel sind, bevorzugt sind Glasfasern mit geringem Durchmesser unter Ausbildung einer großen Oberfläche des Verstärkungsmaterials. Ferner können die Fasern und Filamente Vliese und/oder Gewebe ausbilden, wobei Vliese eine bevorzugte Verstärkungsmaterial- Schicht ausbilden.The reinforcing material layer preferably comprises inorganic fibers or filaments, nonwovens and / or fabrics, the length and diameter of the fibers or filaments being generally variable, glass fibers having a small diameter are preferred, with a large surface area of the reinforcing material. Furthermore, the fibers and filaments can form nonwovens and / or fabrics, nonwovens forming a preferred reinforcing material layer.
Die Oberfläche des Verstärkungsmaterials kann modifiziert werden, wobei bevorzugte Schlichtemittel zur Modifizierung insbe-
sondere basische Schlichtemittel sind. Das erfindungsgemäße Schlichtemittel umfasst ein Kupplungsreagenz und bevorzugt geeignete Zusätze, beispielsweise Filmbildner, oberflächenaktive Substanzen, Weichmacher und/oder Stabilisatoren. Unter einem „Kupplungsreagenz" im Sinne dieser Erfindung wird ein Mittel verstanden, welches zur Ausbildung des erfindungsgemäßen Verbundes zwischen einer Polymerschicht, basierend auf wenigstens einem Polymer mit sauren Eigenschaften und wenigstens einer Verstärkungsmaterialschicht mit basischen Eigenschaften, beiträgt. Bevorzugte Kupplungsreagenzien im Sinne der Erfindung sind Silane, die vorliegende Erfindung betrifft insbesondere die Verwendung von Kupplungsmitteln mit aminofunktionalen Seitengruppen oder Aminosilan-Kupplungsmittel . Jedes beliebige A- minosilan-Kupplungsmittel, welches sich an ein Glas kondensiert und eine aminofunktionale Gruppe auf der modifizierten Oberfläche aufweist, kann im Sinne der Erfindung verwendet werden.The surface of the reinforcing material can be modified, preferred sizing agents for modification in particular are special basic sizing agents. The sizing agent according to the invention comprises a coupling reagent and preferably suitable additives, for example film formers, surface-active substances, plasticizers and / or stabilizers. A “coupling reagent” in the sense of this invention means an agent which contributes to the formation of the composite according to the invention between a polymer layer based on at least one polymer with acid properties and at least one reinforcing material layer with basic properties. Preferred coupling reagents in the sense of the invention are silanes "The present invention particularly relates to the use of coupling agents with amino functional side groups or aminosilane coupling agents. Any aminosilane coupling agent which condenses on a glass and has an amino functional group on the modified surface can be used for the purposes of the invention. ***"
Die erfindungsgemäß verwendeten oxidischen Materialien oder Gläser können unbehandelt oder vorbehandelt geschlichtet werden. Erfindungsgemäß bevorzugt ist eine Vorbehandlung der 0- berflache der Glasfasern. Geeignete basische Lösungen oder Laugen, beispielsweise Natriumhydroxid- oder Kaliumhydroxid- laugen, können bei Raumtemperatur oder unter erhöhten Temperaturen auf die Fasern einwirken und deren Oberfläche anätzen.The oxidic materials or glasses used according to the invention can be sized untreated or pretreated. Pre-treatment of the surface of the glass fibers is preferred according to the invention. Suitable basic solutions or bases, for example sodium hydroxide or potassium hydroxide bases, can act on the fibers at room temperature or at elevated temperatures and etch their surface.
Eine vorteilhafte Ausgestaltung der Erfindung ist es, dass das Verstärkungsmaterial mit einem Kupplungsreagenz, vorzugsweise Silan, modifiziert ist, wobei dieses Kupplungsreagenz bevorzugt durch Kondensation auf das Verstärkungsmaterial aufgebracht ist . Das Inkontaktbringen des Kupplungsreagenzes mit dem Verstärkungsmaterial, bevorzugt mit einem durch Anätzen der Oberfläche vorbehandelten Glasvlies, führt zur Ausbildung einer Bindung, vorzugsweise einer kovalenten Bindung, zwischen dem Verstärkungsmaterial und dem Silan durch eine Kondensationsreaktion. Die Kondensationsreaktion kann basisch oder sauer katalysiert sein.
Eine die Erfindung verbessernde Maßnahme sieht vor, dass das Verstärkungsmaterial mit einem basischen Silan der nachstehenden Formel (1) :An advantageous embodiment of the invention is that the reinforcing material is modified with a coupling reagent, preferably silane, this coupling reagent preferably being applied to the reinforcing material by condensation. The contacting of the coupling reagent with the reinforcing material, preferably with a glass fleece pretreated by etching the surface, leads to the formation of a bond, preferably a covalent bond, between the reinforcing material and the silane through a condensation reaction. The condensation reaction can be catalyzed basic or acidic. One measure improving the invention provides that the reinforcing material with a basic silane of the following formula (1):
(1) (RO)nSiBm (1) (RO) n SiB m
modifiziert ist, wobei: n, m ist gleich oder unabhängig voneinander 1, 2 oder 3; n + ist 4;is modified, wherein: n, m is identical or independent of one another 1, 2 or 3; n + is 4;
R ist eine Alkyl- oder Arylgruppe;R is an alkyl or aryl group;
B ist eine basische Gruppe, insbesondere eine StickstoffVerbindung, ausgewählt aus der Gruppe umfassend primäre, sekundäre oder tertiäre A ine, primäre, sekundäre oder tertiäre Amide, heterocyclische StickstoffVerbindungen, insbesondere 5-Ring- oder 6-Ring- Heterocyclen, z.B. Pyrazole, Imidazole, Triazole, 0- xazole, Thiazole, Pyridine, Pryri idine oder kondensierte stickstoffhaltige Ringsysteme.B is a basic group, in particular a nitrogen compound, selected from the group comprising primary, secondary or tertiary amines, primary, secondary or tertiary amides, heterocyclic nitrogen compounds, in particular 5-ring or 6-ring heterocycles, e.g. Pyrazoles, imidazoles, triazoles, 0-xazoles, thiazoles, pyridines, pryridines or condensed nitrogen-containing ring systems.
Weitere geeignete stickstoffhaltige Gruppen B sind beispielsweise Pyrrole, Pyrazine, Pyridazine, Triazine, Indole, Chino- line, Isochinoline oder Purine. Die Kondensationsreaktion führt erfindungsgemäß zur Ausbildung einer modifizierten Oberfläche der Glasfasern, wobei die Oberfläche des Verstärkungs- materials bevorzugt die basischen oder stickstoffhaltigen Gruppen des Silans an der modifizierten Oberfläche aufweist. Eine funktionale Seitengruppe des Kupplungsreagenzes kann im Sinne der vorliegenden Erfindung auch eine geschützte Amino- gruppe sein. In vorteilhafter Weise sind die erfindungsgemäß ausgewählten Seitengruppen unabhängig voneinander stickstoffhaltige Seitengruppen und Alkoxygruppen, welche weitere funktionale Gruppen aufweisen können.Other suitable nitrogen-containing groups B are, for example, pyrroles, pyrazines, pyridazines, triazines, indoles, quinolines, isoquinolines or purines. According to the invention, the condensation reaction leads to the formation of a modified surface of the glass fibers, the surface of the reinforcing material preferably having the basic or nitrogen-containing groups of the silane on the modified surface. For the purposes of the present invention, a functional side group of the coupling reagent can also be a protected amino group. Advantageously, the side groups selected according to the invention are, independently of one another, nitrogen-containing side groups and alkoxy groups, which may have further functional groups.
Bevorzugte Seitengruppen der er indungsgemäß verwendeten Sila- ne sind Alkoxygruppen, umfassend kurze lineare Alkylgruppen
mit 1 bis 6 Kohlenstoffatomen, besonders bevorzugt Methoxy- o- der Ethoxygruppen.Preferred side groups of the silanes used in accordance with the invention are alkoxy groups, comprising short linear alkyl groups with 1 to 6 carbon atoms, particularly preferably methoxy or ethoxy groups.
Eine vorteilhafte Weiterbildung der Erfindung sieht vor, dass das Verstärkungsmaterial bevorzugt mit einem basischen Silan- Kupplungsreagenz der Formel (2)An advantageous further development of the invention provides that the reinforcing material preferably with a basic silane coupling reagent of the formula (2)
(2 ) (MeO) mSi [ (CH2) ιNH2] v (2) (MeO) m Si [(CH 2 ) ιNH 2 ] v
modifiziert ist, wobei: m 1 oder 3 ist;is modified, wherein: m is 1 or 3;
1 eine ganze Zahl zwischen 0 und 12 ist;1 is an integer between 0 and 12;
Me eine Methylgruppe ist; v 1 oder 3 ist; v + m 4 ist.Me is a methyl group; v is 1 or 3; v + m is 4.
Erfindungsgemäß werden beispielsweise 3-Aminopropyl-trimeth- oxysilan oder Aminopropyltriethoxysilan verwendet .According to the invention, for example 3-aminopropyltrimethoxysilane or aminopropyltriethoxysilane are used.
Eine noch vorteilhaftere Weiterbildung der Erfindung sieht vor, dass das Verstärkungsmaterial bevorzugt mit einem basischen Silan-Kupplungsreagenz der Formel (MeO)3SiNH2 modifiziert ist .An even more advantageous development of the invention provides that the reinforcing material is preferably modified with a basic silane coupling reagent of the formula (MeO) 3 SiNH 2 .
Bevorzugt werden die modifizierten Verstärkungsmaterialien in Kationen-Austauscher-Membranen eingesetzt. Ein weiterer Vorteil der erfindungsgemäß verstärkten Polymermembran ergibt sich dadurch, dass er indungsgemäß die verstärkte Membran eine Polymerelektrolytmembran, bevorzugt eine Kationen-Austausσher- Membran ist.The modified reinforcing materials are preferably used in cation-exchange membranes. Another advantage of the polymer membrane reinforced according to the invention results from the fact that, according to the invention, the reinforced membrane is a polymer electrolyte membrane, preferably a cation-exchange membrane.
Eine vorteilhafte Ausgestaltung der Erfindung ist es, dass das verwendete Polymer mit sauren Eigenschaften umfassend Polymere, Copolymere und/oder Polymerblends, vorzugsweise ausgewählt ist aus der Gruppe umfassend Polymethylmethacrylat , perfluorierte Polystyrole, Polytetrafluorethylen, Copolymerisate aus sulfoniertem Styroldivinylbenzol , sulfonierte Polyethersulfo-
ne, Polysulfone, Polyetheretherketone, Polyimide, Polybenzimi- dazole, Polyacetylene, Polypyrrole, Polythiophene, Polyaniline und/oder Polyphenylene. Weitere erfindungsgemäß geeignete Polymere sind beispielsweise Polyvinylchlorid, Polystyren, Poly- methylmethacrylat, Polytetrafluorethylen. Besonders bevorzugt weist das Polymer Sulfonsäuregruppen auf. Ein erfindungsgemäß verwendbares Polymer mit sauren Eigenschaften ist insbesondere Nafion®, erhältlich bei der Firma Du Pont.An advantageous embodiment of the invention is that the polymer used with acidic properties comprising polymers, copolymers and / or polymer blends, is preferably selected from the group comprising polymethyl methacrylate, perfluorinated polystyrenes, polytetrafluoroethylene, copolymers of sulfonated styrene-divinylbenzene, sulfonated polyether sulfo- ne, polysulfones, polyether ether ketones, polyimides, polybenzimidazoles, polyacetylenes, polypyrroles, polythiophenes, polyanilines and / or polyphenylenes. Other polymers suitable according to the invention are, for example, polyvinyl chloride, polystyrene, polymethyl methacrylate, polytetrafluoroethylene. The polymer particularly preferably has sulfonic acid groups. An inventively usable polymer having acidic properties is particularly Nafion ®, available from Du Pont.
Eine weitere vorteilhafte Ausgestaltung der Erfindung ist, dass das mit einem Kupplungsreagenz modifizierte Verstärkungsmaterial der Polymermembran im Vergleich zu der entsprechend nicht-modifizierten Polymermembran eine höhere Anzahl von trocken-naß Zyklen bei 80 °C ohne Verlust der mechanischen Integrität und ohne Zerstörung des Verbundes zwischen der Polymerschicht und der Verstärkungsmaterialschient übersteht. Die Vergleichspolymermembran ist eine Polymermembran identischer Zusammensetzung, bis auf den Unterschied, dass die Verstärkungsmaterialschicht der Vergleichspolymermembran nicht erfindungsgemäß modifiziert wurde. Eine weitere wesentliche Verbesserung ist, dass der erfindungsgemäße Verbund auch durch häufiges Quellen und Trocknen nicht zerstört wird. Bevorzugt ist die Anzahl von trocken-naß Zyklen bei 80 °C, die die erfindungsgemäße verstärkte Polymermembran ohne Verlust der mechanischen Integrität übersteht, im Vergleich zu den entsprechenden nicht erfindungsgemäß verstärkten Polymermembranen um den Faktor > 1 höher, vorzugsweise um den Faktor > 1,5 höher und besonders bevorzugt mindestens doppelt so hoch.A further advantageous embodiment of the invention is that the reinforcing material of the polymer membrane modified with a coupling reagent, compared to the correspondingly unmodified polymer membrane, has a higher number of dry-wet cycles at 80 ° C. without loss of mechanical integrity and without destruction of the bond between the Polymer layer and the reinforcement material protruding. The comparison polymer membrane is a polymer membrane of identical composition, except that the reinforcing material layer of the comparison polymer membrane was not modified according to the invention. Another significant improvement is that the composite according to the invention is not destroyed even by frequent swelling and drying. The number of dry-wet cycles at 80 ° C. which the reinforced polymer membrane according to the invention withstands without loss of mechanical integrity is preferably higher by a factor of> 1 than the corresponding polymer membranes not reinforced according to the invention, preferably by a factor of> 1.5 higher and particularly preferably at least twice as high.
Noch eine weitere vorteilhafte Weiterbildung der Erfindung sieht vor, dass die Haftung zwischen der Polymerschicht, basierend wenigstens auf einem Polymer mit sauren Eigenschaften und der Verstärkungsmaterialschicht mit basischen Eigenschaften, ausschließlich auf elektrostatischer Wechselwirkung beruht. Erfindungsgemäß wird das saure Ionomer durch ionische Wechselwirkung an die basische Glasfaser gebunden. Die basisch modifizierte Oberfläche des Vlieses tritt mit einem Polymer
mit sauren Eigenschaften in Kontakt. Der gebildete Verbund beruht bevorzugt auf einer ionischen Wechselwirkung zwischen den sauren Gruppen des Polymers und den basischen, bevorzugt stickstoffhaltigen, Gruppen des Verstärkungsmaterials. Bei der erfindungsgemäß verstärkten Polymermembran wird eine Ablösung des zu verstärkenden Materials von dem verstärkenden Material auch beispielsweise unter Bedingungen die ein Quellen und Schrumpfen des Ionomers hervorrufen, wie Bedingungen wechselnder Feuchtigkeit, vermieden.Yet another advantageous development of the invention provides that the adhesion between the polymer layer, based at least on a polymer with acid properties and the reinforcing material layer with basic properties, is based exclusively on electrostatic interaction. According to the invention, the acidic ionomer is bound to the basic glass fiber by ionic interaction. The basic modified surface of the fleece occurs with a polymer in contact with acidic properties. The composite formed is preferably based on an ionic interaction between the acidic groups of the polymer and the basic, preferably nitrogen-containing, groups of the reinforcing material. In the polymer membrane reinforced according to the invention, detachment of the material to be reinforced from the reinforcing material is also avoided, for example under conditions which cause the ionomer to swell and shrink, such as conditions of changing moisture.
In vorteilhafter Weise umfasst das Verfahren die folgenden Schritte, a) Modifizierung des Verstärkungsmaterials mit einem basischen Silan; b) Kontaktieren des modifizierten basischen Verstärkungsmaterials mit einem Polymer mit sauren Eigenschaften, wobei das Polymer mit sauren Eigenschaften über elektrostatische Wechselwirkung an das basisch modifizierte Verstärkungsmaterial bindet .The method advantageously comprises the following steps: a) modification of the reinforcing material with a basic silane; b) contacting the modified basic reinforcing material with a polymer with acidic properties, the polymer with acidic properties binding to the basic modified reinforcing material via electrostatic interaction.
Eine vorteilhafte Ausgestaltung der Erfindung ist es, dass man eine erfindungsgemäß verstärkte Polymermembran als Polymer- Elektrolyt-Membran in einer Polymer-Elektrolyt-Membran- Brennstoffzelle verwendet. In weiterhin vorteilhafter Weise wird eine erfindungsgemäß verstärkte Polymermembran als Polymer-Elektrolyt-Membran zur Gewinnung elektrochemisch erzeugter Energie verwendet . Vorzugsweise wird eine erfindungsgemäß verstärkte Polymermembran als Membran in Dialyse- und/oder Trennverfahren verwendet .An advantageous embodiment of the invention is that a polymer membrane reinforced according to the invention is used as the polymer electrolyte membrane in a polymer electrolyte membrane fuel cell. In a further advantageous manner, a polymer membrane reinforced according to the invention is used as the polymer electrolyte membrane for the production of electrochemically generated energy. A polymer membrane reinforced according to the invention is preferably used as the membrane in dialysis and / or separation processes.
Eine vorteilhafte Weiterbildung der Erfindung sieht vor, dass Brennstoffzellen, insbesondere Polymer-Elektrolyt-Membran- Brennstoffzellen wenigstens eine erfindungsgemäß verstärkte Polymermembran aufweisen.
Das folgenden Ausführungsbeispiel beschreibt eine bevorzugte Möglichkeiten, eine erfindungsgemäß verstärkte Polymermembran darzustellen, ohne die Erfindung auf dieses einzuschränken.An advantageous development of the invention provides that fuel cells, in particular polymer electrolyte membrane fuel cells, have at least one polymer membrane reinforced according to the invention. The following exemplary embodiment describes a preferred possibility of representing a polymer membrane reinforced according to the invention without restricting the invention thereto.
Ausführungsbeispielembodiment
Ein dünnes Glasfaservlies wurde durch Eintauchen in 50 °C warme 1 molare Natronlauge für 10 Sekunden oberflächlich angeätzt und anschließend mit entionisiertem Wasser gründlich gespült. Das Vlies wurde bei 30 °C in einem Umluftofen für 10 Minuten getrocknet und anschließend bei Raumtemperatur für 10 Sekunden in eine 50%ige Lösung von 3-Aminopropyltrimethoxysilan in E- thanol getaucht. Überschüssige Lösung wurde durch Abschütteln entfernt und das Vlies 30 Minuten bei Raumtemperatur sowie anschließend 10 Minuten bei 100 °C getrocknet.A thin glass fiber fleece was etched on the surface by immersion in 1 molar sodium hydroxide solution at 50 ° C. for 10 seconds and then rinsed thoroughly with deionized water. The fleece was dried at 30 ° C. in a forced air oven for 10 minutes and then immersed in a 50% solution of 3-aminopropyltrimethoxysilane in ethanol at room temperature for 10 seconds. Excess solution was removed by shaking and the fleece was dried at room temperature for 30 minutes and then at 100 ° C. for 10 minutes.
Auf einer Glasplatte wurde eine 15 %ige Lösung von Nafion® der Fa. Du Pont mit einem Äquivalentgewicht von 1100 in einer Schichtdicke von ca. 100 μm gleichmäßig vorgelegt. Das modifizierte Vlies wurde langsam auf die vorbereitete Nafion®-Lδsung aufgebracht. Die Lösung wurde anschließend auf der Glasplatte für 15 Minuten bei einer Ofentemperatur von 140 °C getrocknet. Die erhaltene Oberfläche wurde erneut mit einer Nafion®-Lösung einer Schichtdicke von 200 μm beschichtet und für 15 Minuten bei einer Ofentemperatur von 140 °C getrocknet.On a glass plate in a 15% solution of Nafion ® from was. Du Pont presented microns uniformly having an equivalent weight of 1100 in a layer thickness of about 100. The modified fleece was slowly applied to the prepared Nafion ® solution. The solution was then dried on the glass plate for 15 minutes at an oven temperature of 140 ° C. The surface was again coated with a Nafion ® solution having a film thickness of 200 microns and dried for 15 minutes at an oven temperature of 140 ° C.
Im Anschluss wurde die erhaltene Membran im Wasserbad von der Glasoberfläche abgelöst, mit fusselfreiem Papier getrocknet, auf einer weiteren Glasplatte mit Klebeband an den Rändern fixiert und für 2 Minuten bei einer Ofentemperatur von 120 °C getrocknet .The membrane obtained was then removed from the glass surface in a water bath, dried with lint-free paper, fixed to the edges on a further glass plate with adhesive tape and dried for 2 minutes at an oven temperature of 120 ° C.
Zur Begutachtung der mechanischen Integrität des erfindungsgemäßen Materialverbundes wurden wiederholte Zyklen aus Quellen und Trocknen durchgeführt. Die modifizierten Membranen wurden hierzu in 20 Zyklen in 80 °C heißem Wasser befeuchtet und für
10 Minuten bei einer Ofentemperatur von 95 °C getrocknet. Die Begutachtung des Bruchverhaltens der verstärkten Membran erfolgte optisch, eine Zersplitterung der modifizierten Membran zeigte sich nicht.
Repeated cycles of swelling and drying were carried out to assess the mechanical integrity of the material composite according to the invention. The modified membranes were moistened in 20 cycles in 80 ° C hot water and for Dried for 10 minutes at an oven temperature of 95 ° C. The fracture behavior of the reinforced membrane was assessed visually; there was no fragmentation of the modified membrane.
Claims
Verstärkte Polymermembran, d a d u r c h g e k e n n z e i c h n e t , dass die verstärkte Polymermembran wenigstens eine Polymerschicht, basierend auf wenigstens einem Polymer mit sauren Eigenschaften, und wenigstens eine Verstärkungs- materialschicht mit basischen Eigenschaften umfasst, wobei wenigstens eine äußere Oberfläche der Polymerschicht wenigstens eine äußere Oberfläche der Verstärkungsmaterial- Schicht haftend kontaktiert, wobei die Haftung auf einer elektrostatischen Wechselwirkung beruht .Reinforced polymer membrane, characterized in that the reinforced polymer membrane comprises at least one polymer layer based on at least one polymer with acidic properties, and at least one reinforcing material layer with basic properties, at least one outer surface of the polymer layer making adhesive contact with at least one outer surface of the reinforcing material layer , the liability based on an electrostatic interaction.
Verstärkte Polymermembran nach Anspruch 1 , d a d u r c h g e k e n n z e i c h n e t , dass das Verstärkungsmaterial ein oxidisches Material umfasst, wobei das oxidische Material bevorzugt Zirkon, Si- licium und/oder Titan enthält.Reinforced polymer membrane according to claim 1, so that the reinforcing material comprises an oxidic material, the oxidic material preferably containing zirconium, silicon and / or titanium.
Verstärkte Polymermembran nach Anspruch 1 oder 2 , d a d u r c h g e k e n n z e i c h n e t , dass die Verstärkungsmaterialschicht bevorzugt anorganische Fasern oder Filamente, Vliese und/oder Gewebe umfasst .Reinforced polymer membrane according to claim 1 or 2, so that the reinforcing material layer preferably comprises inorganic fibers or filaments, nonwovens and / or fabrics.
Verstärkte Polymermembran nach einem der vorherigen Ansprüche, d a d u r c h g e k e n n z e i c h n e t , dass das Verstärkungsmaterial mit einem Kupplungsreagenz, bevorzugt Silan, modifiziert ist, wobei dieses Kupplungs- reagenz bevorzugt durch Kondensation auf das Verstarkungs- material aufgebracht ist.Reinforced polymer membrane according to one of the preceding claims, characterized in that the reinforcing material is modified with a coupling reagent, preferably silane, this coupling reagent is preferably applied to the reinforcing material by condensation.
5. Verstärkte Polymermembran nach einem der vorherigen Ansprüche, d a d u r c h g e k e n n z e i c h n e t , dass das Verstärkungsmaterial mit einem basischen Silan der Formel (1)5. Reinforced polymer membrane according to one of the preceding claims, d a d u r c h g e k e n n z e i c h n e t that the reinforcing material with a basic silane of the formula (1)
(1) (RO)nSiBm wobei : n, m ist gleich oder unabhängig voneinander 1, 2 oder 3; n + m ist 4;(1) (RO) n SiB m where: n, m is identical or independent of one another 1, 2 or 3; n + m is 4;
R ist eine Alkyl- oder Arylgruppe, bevorzugt eine Methylgruppe ;R is an alkyl or aryl group, preferably a methyl group;
B ist eine basische Gruppe, insbesondere eine StickstoffVerbindung, ausgewählt aus der Gruppe umfassend primäre, sekundäre oder tertiäre Amine, primäre, sekundäre oder tertiäre A ide, heterocyclische Stickstoffverbindungen, insbesondere 5-Ring- oder 6-Ring-Heterocyclen, z.B. Pyrazole, I- midazole, Triazole, Oxazole, Thiazole, Pyridine, Pryrimidine oder kondensierte stickstoffhaltige Ringsysteme; modifiziert ist.B is a basic group, in particular a nitrogen compound, selected from the group comprising primary, secondary or tertiary amines, primary, secondary or tertiary amides, heterocyclic nitrogen compounds, in particular 5-ring or 6-ring heterocycles, e.g. Pyrazoles, imidazoles, triazoles, oxazoles, thiazoles, pyridines, pryrimidines or condensed nitrogen-containing ring systems; is modified.
6. Verstärkte Polymermembran nach einem der vorherigen Ansprüche, d a du r c h g e k e n n z e i c h n e t , dass das Verstärkungsmaterial bevorzugt mit einem basischen Silan-Kupplungsreagenz der Formel (2)6. Reinforced polymer membrane according to one of the preceding claims, that the reinforcing material preferably with a basic silane coupling reagent of the formula (2)
(2) (MeO)mSi[(CH2)1NH2]v wobei : m 1, 2 oder 3 ist;(2) (MeO) m Si [(CH 2 ) 1 NH 2 ] v where: m is 1, 2 or 3;
1 eine ganze Zahl zwischen 0 und 12 ist; Me eine Methylgruppe ist; v 1, 2 oder 3 ist; v + m 4 ist; modifiziert ist, wobei (MeO)3SiNH2 als Silan- Kupplungsreagenz besonders bevorzugt ist.1 is an integer between 0 and 12; Me is a methyl group; v is 1, 2 or 3; v + m is 4; is modified, with (MeO) 3 SiNH 2 being particularly preferred as the silane coupling reagent.
7. Verstärkte Polymermembran nach einem der vorherigen Ansprüche, d a d u r c h g e k e n n z e i c h n e t , dass die verstärkte Membran eine Polymerelektrolytmembran, bevorzugt eine Kationen-Austauscher-Membran ist.7. Reinforced polymer membrane according to one of the preceding claims, so that the reinforced membrane is a polymer electrolyte membrane, preferably a cation exchange membrane.
8. Verstärkte Polymermembran nach einem der vorherigen Ansprüche, d a d u r c h g e k e n n z e i c h n e t , dass das verwendete Polymer mit sauren Eigenschaften umfassend Polymere, Copolymere und/oder Polymerblends, bevorzugt ausgewählt aus der Gruppe umfassend Polymethyl- methacrylat, perfluorierte Polystyrole, Polytetrafluor- ethylen, Copolymerisate aus sulfoniertem Styroldivinylben- zol, sulfonierte Polyet ersulföne, Polysulfone, Polyether- etherketone, Polyimide, Polybenzimidazole, Polyacetylene, Polypyrrole, Polythiophene, Polyaniline und/oder Polyphe- nylene ist .8. Reinforced polymer membrane according to one of the preceding claims, characterized in that the polymer used with acidic properties comprising polymers, copolymers and / or polymer blends, preferably selected from the group comprising polymethyl methacrylate, perfluorinated polystyrenes, polytetrafluoroethylene, copolymers of sulfonated styrene-divinylbene zol, sulfonated polyethersulfones, polysulfones, polyether ether ketones, polyimides, polybenzimidazoles, polyacetylenes, polypyrroles, polythiophenes, polyanilines and / or polyphenylenes.
. Verstärkte Polymermembran nach einem der vorherigen Ansprüche, d a d u r c h g e k e n n z e i c h n e t , dass das mit einem Kupplungsreagenz modifizierte Verstärkungsmaterial der Polymermembran im Vergleich zu der entsprechend nicht-modifizierten Polymermembran eine höhere Anzahl von trocken-naß Zyklen bei 80 °C ohne Verlust der mechanischen Integrität und ohne Zerstörung des Verbundes zwischen der Polymerschicht und der Verstärkungsmaterial- Schicht übersteht ., Reinforced polymer membrane according to one of the preceding claims, characterized in that the reinforcing material of the polymer membrane modified with a coupling reagent, compared to the correspondingly unmodified polymer membrane, has a higher number of dry-wet cycles at 80 ° C without loss of mechanical integrity and without destroying the composite protrudes between the polymer layer and the reinforcing material layer.
10. Verstärkte Polymermembran nach einem der vorherigen Ansprüche, d a d u r c h g e k e n n z e i c h n e t , dass die Haftung zwischen der Polymerschicht, basierend wenigstens auf einem Polymer mit sauren Eigenschaften und der Verstärkungsmaterialschicht mit basischen Eigenschaften, ausschließlich auf elektrostatischer Wechselwirkung beruht .10. Reinforced polymer membrane according to one of the preceding claims, characterized in that the adhesion between the polymer layer is based based at least on a polymer with acidic properties and the reinforcing material layer with basic properties, exclusively on electrostatic interaction.
11. Verfahren zur Verstärkung einer Polymermembran g e k e n n z e i c h n e t d u r c h die folgenden Schritte, a) Modifizierung des Verstärkungsmaterials mit einem basischen Silan; b) Kontaktieren des modifizierten basischen Verstärkungsmaterials mit einem Polymer mit sauren Eigenschaften, wobei das Polymer mit sauren Eigenschaften über elektrostatische Wechselwirkung an das basisch modifizierte Verstärkungsmaterial bindet .11. Method for reinforcing a polymer membrane, the following steps, a) modification of the reinforcing material with a basic silane; b) contacting the modified basic reinforcing material with a polymer with acidic properties, the polymer with acidic properties binding to the basic modified reinforcing material via electrostatic interaction.
12. Verwendung einer verstärkten Polymermembran nach einem der vorherigen Ansprüche als Polymer-Elektrolyt-Membran in einer Polymer-Elektrolyt-Membran-Brennstoffzelle .12. Use of a reinforced polymer membrane according to one of the preceding claims as a polymer electrolyte membrane in a polymer electrolyte membrane fuel cell.
13. Verwendung einer verstärkten Polymermembran nach einem der vorherigen Ansprüche als Polymer-Elektrolyt-Membran zur Gewinnung elektrochemisch erzeugter Energie.13. Use of a reinforced polymer membrane according to one of the preceding claims as a polymer electrolyte membrane for the production of electrochemically generated energy.
14. Verwendung einer verstärkten Polymermembran nach einem der vorherigen Ansprüche als Membran in Dialyse- und/oder Trennverfahren.14. Use of a reinforced polymer membrane according to one of the preceding claims as a membrane in dialysis and / or separation processes.
15. Brennstoffzelle, insbesondere Polymer-Elektrolyt-Membran- Brennstoffzelle , d a du r c h g e k e n n z e i c h n e t , dass die Brennstoffzelle wenigstens eine verstärkte Polymermembran nach einem der Ansprüche 1 bis 10 aufweist. 15. Fuel cell, in particular polymer electrolyte membrane fuel cell, so that the fuel cell has at least one reinforced polymer membrane according to one of claims 1 to 10.
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AU2003277822A AU2003277822A1 (en) | 2002-10-29 | 2003-10-16 | Size for glass fibers and use thereof in cation exchange membranes |
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DE10250314A DE10250314A1 (en) | 2002-10-29 | 2002-10-29 | Reinforced polymer membrane, used as electrolyte membrane in fuel cell or as dialysis or separation membrane, has acid polymer and basic reinforcement layers adhering by electrostatic interaction |
DE10250314.1 | 2002-10-29 |
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CN102605552A (en) * | 2012-02-17 | 2012-07-25 | 山东大学 | Method for preparing nitrogen-doped nanometer TiO2 fiber cloth |
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EA010336B1 (en) * | 2004-06-16 | 2008-08-29 | АйТиЭм ФЬЮЭЛ СЕЛЛЗ ЛТД. | Membrane electrode assembly with controlled management of water and/or ion flow |
DE102004063030A1 (en) * | 2004-12-28 | 2006-08-17 | Johannes-Gutenberg-Universität Mainz | Multilayer system, process for its production and its use in electro-optical components |
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WO2000073235A1 (en) * | 1999-05-28 | 2000-12-07 | Bayer Aktiengesellschaft | Sizing composition, sized glass fibers and their use |
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AU2003277822A8 (en) | 2004-05-25 |
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