WO2009138172A1 - Protonenleitende membran und deren verwendung - Google Patents
Protonenleitende membran und deren verwendung Download PDFInfo
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- WO2009138172A1 WO2009138172A1 PCT/EP2009/003163 EP2009003163W WO2009138172A1 WO 2009138172 A1 WO2009138172 A1 WO 2009138172A1 EP 2009003163 W EP2009003163 W EP 2009003163W WO 2009138172 A1 WO2009138172 A1 WO 2009138172A1
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- 0 CC(*)=NC(*)[Al](*CC(*1)N=C1[Al])C1N=C(C)*1 Chemical compound CC(*)=NC(*)[Al](*CC(*1)N=C1[Al])C1N=C(C)*1 0.000 description 6
Classifications
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- 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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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- 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
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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- 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
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
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- 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]
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- 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]
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- 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
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
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- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/06—Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0045—Room temperature molten salts comprising at least one organic ion
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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
Definitions
- the present invention relates to a novel proton-conducting polymer membrane based on polyazoles, which can be used in many ways due to their excellent chemical and thermal properties and is particularly suitable as a polymer electrolyte membrane (PEM) in so-called PEM fuel cells.
- PEM polymer electrolyte membrane
- Polymer electrolyte membranes are already known and are used in particular in fuel cells. Sulfonic acid-modified polymers, in particular perfluorinated polymers, are frequently used here. A prominent example of this is Nafion TM by DuPont de Nemours, Willmington USA. Proton conduction requires a relatively high water content in the membrane, typically 4-20 molecules of water per sulfonic acid group. The necessary water content, but also the stability of the polymer in conjunction with acidic water and the reaction gases hydrogen and oxygen, limits the operating temperature of the PEM fuel cell stack usually at 80-100 0 C. Under pressure, the operating temperatures can be increased to> 120 0 C. Otherwise, higher operating temperatures can not be realized without a power loss of the fuel cell.
- step B) applying a layer using the mixture according to step A) on a support
- step B) heating of the sheet / layer obtainable according to step B) under inert gas to temperatures of up to 350 0 C, preferably up to 280 0 C to form the polyazole polymer.
- the object of the present invention was therefore to provide polymer electrolyte membranes having an improved property profile.
- the best possible mechanical properties and at the same time the best possible conductivity properties were sought.
- the membranes should have one hand, the performance advantages of the polymer membrane based on polyazoles and on the other hand an increased specific conductivity, in particular at operating temperatures above 100 0 C, point and do not require fuel gas humidification possible.
- the membranes should be relatively inexpensive to produce in a relatively simple manner.
- the present invention accordingly provides a proton-conducting polymer membrane comprising at least one polyazole, at least one ionic liquid and at least one compound of the formula (P1)
- R 1 in each case independently of one another, is a radical which comprises C, O and / or H and, if appropriate, further atoms different therefrom, it being possible for two radicals R 1 to be linked to one another.
- the polyazole preferably contains recurring azole units of the general formula (I) and / or (II) and / or (III) and / or (IV) and / or (V) and / or (VI) and / or (VII) and / or (VIII) and / or (IX) and / or (X) and / or (XI) and / or (XII) and / or (XIII) and / or (XIV) and / or (XV) and / or ( XVI) and / or (XVII) and / or (XVIII) and / or (XIX) and / or (XX) and / or (XXI) and / or (XVIII) and / or (XIX) and / or (XX) and / or (XXI) and / or (XXII) and / or (XXII)) and / or (XXII)) and / or (X
- Ar are the same or different and represent a four-membered aromatic or heteroaromatic group which may be mononuclear or polynuclear,
- Ar 1 are the same or different and represent a divalent aromatic or heteroaromatic group which may be mononuclear or polynuclear,
- Ar 2 are the same or different and represent a two or trivalent aromatic or heteroaromatic group which may be mononuclear or polynuclear
- Ar 3 are the same or different and are a trivalent aromatic or heteroaromatic group which may be mononuclear or polynuclear
- Ar 4 are the same or different and represent a trivalent aromatic or heteroaromatic group which may be mononuclear or polynuclear
- Ar 5 are the same or different and are a four-membered aromatic or heteroaromatic group which may be mononuclear or polynuclear
- Ar 6 are the same or different and are a divalent aromatic or heteroaromatic group which may be mononuclear or polynuclear
- Ar 7 is the same or are different and represent a divalent aromatic or heteroaromatic group which may be mononuclear or polynuclear
- Ar 8 are the same or different and are a trivalent aromatic or heteroaromatic group which may be mononuclear or polynu
- Amino group which represents a hydrogen atom, a 1-20 carbon atoms group, preferably a branched or unbranched
- Alkyl or alkoxy group, or an aryl group as a further radical R in all formulas other than formula (XX) is identical or different to hydrogen, an alkyl group or an aromatic group and in formula (XX) for a
- Alkylene group or an aromatic group and n, m is an integer greater than or equal to 10, preferably greater than or equal to 100.
- Preferred aromatic or heteroaromatic groups are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, quinoline, pyridine, bipyridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, pyrol, pyrazole, anthracene, benzopyrrole, benzotriazole, Benzooxathiadiazole, benzooxadiazole, benzopyridine, benzopyrazine, benzopyrazidine, benzopyrimidine, benzopyrazine, benzotriazine, indolizine, quinolizine, pyridopyridine, imidazopyrimidine, pyrazinyl pyrimidine, carbazole, aciridine, phenazine, benzoquinoline
- the substitution pattern of Ar 1 , Ar 4 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 , Ar 11 is arbitrary, in the case of phenylene, for example, Ar 1 , Ar 4 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 , Ar 11 are ortho, meta and para-phenylene. Particularly preferred groups are derived from benzene and biphenylene, which may optionally also be substituted.
- Preferred alkyl groups are short chain alkyl groups of 1 to 4 carbon atoms, such as. For example, methyl, ethyl, n- or i-propyl and t-butyl groups.
- Preferred aromatic groups are phenyl or naphthyl groups.
- the alkyl groups and the aromatic groups may be substituted.
- Preferred substituents are halogen atoms such as. For example, fluorine, amino groups, hydroxy groups or short-chain alkyl groups, such as. For example, methyl or ethyl groups.
- the polyazoles can also have different recurring units which differ, for example, in their radical X. Preferably, however, it has only the same X radicals in a repeating unit.
- polyazole polymers are polyimidazoles, polybenzothiazoles, polybenzoxazoles, polyoxadiazoles, polyquinoxalines, polythiadiazoles, poly (pyridines), poly (pyrimidines) and poly (tetrazapyrenes).
- the polyazole is a copolymer containing at least two units of the formulas (I) to (XXII) which differ from one another.
- the polymers can be present as block copolymers (diblock, triblock), random copolymers, periodic copolymers and / or alternating polymers.
- the polyazole is a homopolymer containing only units of the formula (I) and / or (II).
- the number of repeating azole units in the polymer is preferably an integer greater than or equal to 10.
- Particularly preferred polymers contain at least 100 recurring azole units.
- polymers containing recurring benzimidazole units are preferred.
- Some examples of the most useful polymers containing benzimidazole recurring units are represented by the following formulas:
- n and m are integers greater than or equal to 10, preferably greater than or equal to 100.
- the polyazoles have at least one sulfonic acid and / or phosphonic acid group.
- Such polymers are described in the publication DE 102 46 459 A1, the disclosure of which is hereby incorporated by reference.
- the polyazoles used, but especially the polybenzimidazoles are characterized by a high molecular weight. Measured as intrinsic viscosity, this is at least 0.2 dl / g, preferably 0.8 to 10 dl / g, in particular 1 to 10 dl / g.
- Preferred polybenzimidazoles are commercially available under the trade name ⁇ Celazole.
- the proton-conducting polymer membrane of the present invention further contains at least one ionic liquid.
- ionic liquid these are to be understood as meaning those substances which exclusively contain ions and are therefore present as liquid salts, without the salt being dissolved in a solvent such as water.
- Ionic liquids in the context of the present invention are preferably salts of the general formula
- n 1, 2, 3 or 4
- [A] + is a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation
- [Y] n - is a one- or two-membered cation -, tri- or tetravalent anion stands;
- [A 1 ] + , [A 2 J + , [A 3 ] + and [A 4 ] + are independently selected from the groups mentioned for [A] + and [Y] n "is the meaning mentioned under (A) owns; or
- [A 1 ] + , [A 2 ] + and [A 3 J + are independently selected from the groups mentioned for [A] + , [Yf has the meaning given under (A) and [M 1 J + , [ M 2 ] + , [M 3 J + monovalent metal cations, [M 4 J 2+ divalent metal cations and [M 5 J 3+ trivalent metal cations.
- the ionic liquids have a melting point of less than 18O 0 C.
- the melting point is in a range of -50 0 C to 15O 0 C, more preferably in the range of -20 0 C to 120 0 C, and further more preferably less 100 ° C.
- the melting point can be measured in a manner known per se.
- the method of differential scanning calorimetry (DSC) has proven particularly useful, in particular using a heating rate of 10 K / min.
- the ionic liquids of the invention are organic compounds, i. in that at least one cation or anion of the ionic liquid contains an organic radical.
- Compounds suitable for forming the cation [A] + of ionic liquids are e.g. B. from DE 102 02 838 A1.
- such compounds may contain oxygen, phosphorus, sulfur or in particular nitrogen atoms, for example at least one nitrogen atom, preferably 1-10 nitrogen atoms, particularly preferably 1-5, very particularly preferably 1-3 and in particular 1-2 nitrogen atoms.
- other heteroatoms such as oxygen, sulfur or phosphorus atoms may be included.
- the nitrogen atom is a suitable carrier of the positive charge in the cation of the ionic liquid from which, in equilibrium, a proton or an alkyl radical can then be transferred to the anion to produce an electrically neutral molecule.
- a cation can first be generated by quaternization on the nitrogen atom of, for example, an amine or nitrogen heterocycle.
- the quaternization can be carried out by alkylation of the nitrogen atom.
- salts with different anions are obtained.
- this can be done in a further synthesis step.
- the halide can be reacted with a Lewis acid to form a complex anion from halide and Lewis acid.
- replacement of a halide ion with the desired anion is possible. This can be done by adding a metal salt to precipitate the metal halide formed, via an ion exchanger, or by displacing the halide ion with a strong acid (to release the hydrohalic acid). Suitable methods are, for example, in Angew. Chem. 2000, 112, p. 3926-3945 and the literature cited therein.
- Suitable alkyl radicals by which the nitrogen atom in the amines or nitrogen heterocycles can be quaternized are Ci-C 8 alkyl, preferably C r Cio-alkyl, particularly preferably Ci-C ⁇ -alkyl and very particularly preferably methyl.
- the alkyl group may be unsubstituted or have one or more identical or different substituents.
- those compounds which contain at least one five- to six-membered heterocycle in particular a five-membered heterocycle, which has at least one nitrogen atom and optionally an oxygen or sulfur atom
- aromatic heterocycles are particularly preferred.
- Particularly preferred compounds are those which have a molecular weight below 1000 g / mol, very particularly preferably below 500 g / mol.
- radical R is hydrogen, a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 20 carbon atoms;
- radicals R 1 to R 9 independently of one another are hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups with 1 to 20 Carbon atoms, wherein the radicals R 1 to R 9 , which in the abovementioned formulas (IL-IV) are bonded to a carbon atom (and not to a heteroatom) may additionally also be F or a functional group; or
- two adjacent radicals from the series R 1 to R 9 together also for a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or substituted 1 to 30 carbon atoms.
- the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable.
- the radicals R 1 to R 9 are, in the cases in which those in the above formulas (IL-IV) are bonded to a carbon atom (and not to a heteroatom) bound also be bound directly via the heteroatom.
- Functional groups and heteroatoms can also be directly adjacent, so that combinations of several adjacent atoms, such as -O- (ether), -COO- (ester), -CONH- (secondary amide) or -CONR'- (tertiary amide ), are also included, for example, di- (CrC 4 - alkyl) amino, dC 4 alkyloxycarbonyl or Ci-C4 alkyloxy.
- the radicals R 1 are the remaining part of the carbon-containing radical.
- the radical R preferably stands for
- Ci-C 18 alkyl having a total of 1 to 20 carbon atoms, such as methyl, ethyl , 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-i-pentyl,
- N, N-di-C 1 -C 6 -alkyl-amino such as N, N-dimethylamino and N, N-diethylamino.
- the radical R particularly preferably represents unbranched and unsubstituted C 1 -C 6 -alkyl, such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-decyl, 1 -dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, especially for methyl, ethyl, 1-butyl and 1-octyl and for CH 3 O- (CH 2 CH 2 O) n - CH 2 CH 2 - and CH 3 CH 2 O- (CH 2 CH 2 O) n -CH 2 CH 2 - with n equal to 0 to 3.
- C 1 -C 6 -alkyl such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-hepty
- radicals R 1 to R 9 are preferably each independently
- aryl, alkyl, aryloxy, alkyloxy, F, heteroatoms and / or heterocycles substituted and / or interrupted by one or more oxygen atoms and / or one or more substituted or unsubstituted imino Ci-Ci ⁇ -alkyl;
- C 2 -C 18 -alkenyl which is substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, F, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen atoms and / or one or more substituted or unsubstituted imino groups;
- aryl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, F, heteroatoms and / or heterocycles substituted C 6 -C 2 -aryl;
- An unsaturated, saturated or aromatic ring optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, F, heteroatoms and / or heterocycles and optionally interrupted by one or more oxygen atoms and / or one or more substituted or unsubstituted imino groups.
- aryl, alkyl, aryloxy, alkyloxy, F 1 heteroatoms and / or heterocycles substituted C-rCi ⁇ -alkyl is preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2- Butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl 1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-i-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-i-pentyl , 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 4-methyl-2-penty
- aryl, alkyl, aryloxy, alkyloxy, F, heteroatoms and / or heterocycles C 6 -C 12 aryl is preferably phenyl, ToIyI, XyIyI, ⁇ -naphthyl, ß-naphthyl, 4- Diphenylyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, / so-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4, 6-trimethylphen
- An optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, F, heteroatoms and / or heterocycles substituted five- to six-membered, oxygen and / or nitrogen atoms heterocycle is preferably furyl, pyrryl, pyridyl, indolyl, benzoxazolyl , Dioxolyl, dioxy, benzimidazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.
- Two adjacent radicals together form an unsaturated, saturated or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, F, heteroatoms and / or heterocycles and optionally substituted by one or more oxygen atoms and / or one or more substituted or unsubstituted imino groups interrupted ring, it is preferably 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3-propylene, 2-oxa -1, 3-propylene, 1 -Oxa-1, 3-propenylene, 3-oxa-1, 5-pentylene, 1-aza-1, 3-propenylene, idC A -alkyl-i-aza-I .S- propenylene, 1, 4-buta-1, 3-dienylene, 1-aza-1, 4-buta-1, 3-dienylene or 2-aza-1, 4-buta-1, 3-dienylene.
- radicals contain oxygen atoms and / or substituted or unsubstituted imino groups
- the number of oxygen atoms and / or imino groups is not limited. As a rule, it is not more than 5 in the radical, preferably not more than 4, and very particularly preferably not more than 3.
- radicals R 1 to R 9 are each independently
- Ci-Ci 8 alkyl having a total of 1 to 20 carbon atoms, such as methyl, ethyl , 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1 - Hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 2-methyl-2-pentyl
- Glycols, butylene glycols and their oligomers having from 1 to 100 units and a hydrogen or a C 1 to C 8 alkyl as end group, such as, for example, R A O- (CHR B -CH 2 -O) n -CHR B -CH 2 - or R 1 - (CH 2 CH 2 CH 2 CH 2 O) n -CH 2 CH 2 CH 2 CH 2 O-
- R A and R B are preferably hydrogen, methyl or ethyl and n is preferably 0 to 3, in particular 3-oxabutyl , 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9, 12-tetraoxatridecyl and 3,6,9,12 - tetraoxatetradecyl;
- N, N-di-C 6 alkyl-amino such as N, N-dimethylamino and N 1 N-diethylamino.
- the radicals R 1 to R 9 independently of one another are hydrogen or C 1 -C 18 -alkyl, such as, for example, methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, for phenyl, for 2-hydroxyethyl, for 2-cyanoethyl, for 2- (methoxycarbonyl) ethyl, for 2- (ethoxycarbonyl) ethyl, for 2- (n-butoxycarbonyl) ethyl, for N, N-dimethylamino, for N, N-diethylamino and for CH 3 O- (CH 2 CH 2 O) n -CH 2 CH 2 - and CH 3 CH 2 O- (CH 2 CH 2 O) n -CH
- pyridinium ions are those in which
- radicals R 1 to R 5 are methyl or ethyl and the remaining radicals R 1 to R 5 are hydrogen;
- R 3 is dimethylamino and the remaining radicals R 1 , R 2 , R 4 and R 5 are hydrogen;
- R 2 is carboxy or carboxamide and the remaining radicals R 1 , R 2 , R 4 and R 5 are hydrogen; or
- R 1 and R 2 or R 2 and R 3 is 1, 4-buta-1, 3-dienylene and the remaining.
- R 1 , R 2 , R 4 and R 5 are hydrogen;
- R 1 to R 5 are hydrogen
- radicals R 1 to R 5 are methyl or ethyl and the remaining radicals R 1 to R 5 are hydrogen.
- pyridinium ions there may be mentioned 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- ( 1-hexyl) -pyridinium, 1- (1-octyl) -pyridinium, 1- (1-dodecyl) -pyridinium, 1- (1-tetradecyl) -pyridinium, 1- (1-hexadecyl) -pyridinium, 1, 2 Dimethylpyridinium, 1-ethyl-2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1 - ( 1-dodecyl) -2-methylpyridinium
- pyridazinium ions are those in which
- R 1 to R 4 are hydrogen
- radicals R 1 to R 4 are methyl or ethyl and the remaining radicals R 1 to R 4 are hydrogen.
- pyrimidinium ions are those in which
- R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl; or
- R 1 is hydrogen, methyl or ethyl
- R 2 and R 4 are methyl and R 3 is hydrogen.
- IL-IVd Very particularly preferred pyrazinium ions
- R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl;
- R 1 is hydrogen, methyl or ethyl, R 2 and R 4 are methyl and R 3 is hydrogen;
- R 1 to R 4 are methyl
- R 1 to R 4 are hydrogen.
- Very particularly preferred imidazolium ions are those in which
- R 1 is hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 2-hydroxyethyl or 2-cyanoethyl and R 2 to R 4 are independently hydrogen, methyl or ethyl ,
- Very particularly preferred imidazolium ions are 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-Tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1 Butyl) -3-ethylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 1- (1-hexyl) -3-butylimidazolium, 1- (1-Octyl) -3
- IL-IVf very particularly preferred pyrazolium ions
- IL-IVg very particularly preferred pyrazolium ions
- IL-IVg ' Very particularly preferred pyrazolium ions
- R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl.
- Very particularly preferred pyrazolium ions are those in which • R 1 to R 4 are independently hydrogen or methyl.
- IL-IVi 1-pyrazolinium
- R 1 to R 6 are hydrogen or methyl.
- R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 6 are independently hydrogen or methyl.
- R 1 and R 2 are independently hydrogen, methyl, ethyl or phenyl and R 3 to R 6 are independently hydrogen or methyl.
- IL-IVI very particularly preferred imidazolinium ions
- R 1 and R 2 are independently hydrogen, methyl, ethyl, 1-butyl or phenyl
- R 3 and R 4 are independently hydrogen, methyl or ethyl
- R 5 and R 6 are independently hydrogen or methyl.
- R 1 and R 2 are independently hydrogen, methyl or ethyl and R 3 to R 6 are independently hydrogen or methyl.
- R 1 to R 3 are independently hydrogen, methyl or ethyl and R 4 to R 6 are independently hydrogen or methyl.
- Very particular preference is given to using thiazolium ions (IL-IVo) or (IL-IVo ') as well as oxazolium ions (IL-IVp) as those in which
- R 1 is hydrogen, methyl, ethyl or phenyl and R 2 and R 3 are independently hydrogen or methyl.
- IL-IVq 1,2,4-triazolium ions
- IL-IVq ' 1,2,4-triazolium ions
- IL-IVq 1,2,4-triazolium ions
- R 1 and R 2 are independently hydrogen, methyl, ethyl or phenyl and R 3 is hydrogen, methyl or phenyl.
- IL-IVr 1,3,3-triazolium ions
- IL-IVr 1 1,3,3-triazolium ions
- IL-IVr 2 1,3,3-triazolium ions
- R 1 is hydrogen, methyl or ethyl and R 2 and R 3 are independently hydrogen or methyl, or R 2 and R 3 together are 1, 4-buta-1, 3-dienylene.
- IL-IVs Very particularly preferred pyrrolidinium ions are those in which
- R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 9 are independently hydrogen or methyl.
- Imidazolidiniumionen are those in which
- R 1 and R 4 are independently hydrogen, methyl, ethyl or phenyl and R 2 and R 3 and R 5 to R 8 are independently hydrogen or methyl.
- R 1 to R 3 are independently C 1 to C 18 alkyl; or • R 1 and R 2 together are 1, 5-pentylene or 3-oxa-1, 5-pentylene and R 3 is ci-Cia-alkyl, 2-hydroxyethyl or 2-cyanoethyl.
- ammonium ions may be mentioned methyl tri (i-butyl) -ammonium, N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.
- Examples of the tertiary amines from which the quaternary ammonium ions of the general formula (IL-IVu) are derived by quaternization with the abovementioned radicals R are diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethyl hexylamine, diethyloctylamine, diethyl (2-ethylhexyl) amine, di-n-propylbutylamine, di-n-propyl-n-pentylamine, di-n-propylhexylamine, di-n-propyloctylamine, di-n-propyl (2 ethylhexyl) amine, diisopropylethylamine, diisopropyl n-propylamine, diisopropylbutylamine, diisopropylpentylamine, diisoprop
- Preferred quaternary ammonium salts of the general formula (IL-IVu) are those which can be derived from the following tertiary amines by quaternization with the abovementioned radicals R, such as diisopropylethylamine, diethyl-tert-butylamine, diisopropylbutylamine, di -n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines of pentyl isomers.
- R such as diisopropylethylamine, diethyl-tert-butylamine, diisopropylbutylamine, di -n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines of pentyl isomers.
- tertiary amines are di-n-butyl-n-pentylamine and tertiary amines of pentyl isomers.
- Another preferred tertiary amine having three identical residues is triallylamine.
- guanidinium ions are those in which • R 1 to R 5 are methyl.
- guanidinium is N, N, N ', N I N', N '-Hexamethylguanidinium.
- R 1 and R 2 are independently methyl, ethyl, 1-butyl or 1-octyl and R 3 is hydrogen, methyl, ethyl, acetyl, -SO 2 OH or -PO (OH) 2 ;
- R 1 is methyl, ethyl, 1-butyl or 1-octyl
- R 2 is a -CH 2 -CH 2 -OR 4 group and R 3 and R 4 are independently hydrogen, methyl, ethyl, acetyl, -SO 2 OH or -PO (OH) 2 ; or
- R 1 is a -CH 2 -CH 2 -OR 4 group
- R 2 is a -CH 2 -CH 2 -OR 5 group
- R 3 to R 5 are independently hydrogen, methyl, ethyl, acetyl, -SO 2 are OH or -PO (OH) 2 .
- Particularly preferred cholinium ions are those in which R 3 is selected from hydrogen, methyl, ethyl, acetyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 11- Methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9- Methoxy-5-oxa-nonyl, 14-methoxy-5,10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy-3,6, 9-trioxa undecyl, 7-ethoxy-4
- IL-IVx Very particularly preferred as phosphonium ions are those in which
- R 1 to R 3 are, independently of one another, C 1 -C 8 -alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl.
- the pyridinium ions, pyrazolinium, pyrazolium ions and imidazolinium and imidazolium ions are preferable. Furthermore, ammonium ions are preferred.
- the metal cations [M 1 ] + , [M 2 J + , [M 3 ] + , [M 4 J 2+ and [M 5 J 3+ mentioned in formulas (IIIa) to (MIj) are generally to metal cations of the 1st, 2nd, 6th, 7th, 8th, 9th, 10th, 11th, 12th and 13th group of the periodic table.
- Suitable metal cations are, for example, Li + , Na + , K + , Cs + , and Ag + .
- the anion [Y] n "of the ionic liquid is for example selected from
- R a , R b , R c and R d are each independently hydrogen, C 1 -C 30 -alkyl, optionally interrupted by one or more non-adjacent oxygen atoms and / or one or more substituted or unsubstituted imino groups interrupted C 2 -C 8 Alkyl, C 6 -C 4 -An / !, C 5 -Ci 2 -cycloalkyl or a five- to six-membered, oxygen and / or nitrogen atoms heterocycle, wherein two of them together an unsaturated, saturated or aromatic, optionally substituted by one or more oxygen atoms and / or one or more unsubstituted or substituted imino groups can form an interrupted ring, it being possible for the radicals mentioned in each case additionally to be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, F, heteroatoms and / or heterocycles.
- aryl, alkyl, aryloxy, alkyloxy, F, heteroatoms and / or heterocycles substituted C r C 18 alkyl for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl , Pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl, 1, 1, 3, 3 Tetramethylbutyl, benzyl, 1-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-tolylmethyl, i- (p-but)
- optionally interrupted by one or more non-adjacent oxygen and / or one or more substituted or unsubstituted imino interrupted C-2-Ci ⁇ -alkyl for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl, 11 - Hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 11-hydroxy-4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxo-octyl, 11-methoxy-3,6,9-trioxaundecyl, 7-methoxy-4-oxaheptyl, 11 -methoxy-4
- radicals can be taken together, for example, as fused building block 1, 3-propylene, 1,4-butylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propylene, 2-oxa 1, 3-propenylene, 1-az-1, 3-propenylene, 1 -dC 4 -alkyl-1-aza-1, 3-propenylene, 1, 4-buta-1, 3-dienylene, 1-aza- 1, 4-buta-1, 3-dienylene or 2-aza-1,4-buta-1,3-dienylene.
- the number of non-adjacent oxygen and / or imino groups is basically not limited, or is automatically limited by the size of the remainder or the ring building block. As a rule, it is not more than 5 in the respective radical, preferably not more than 4 or very particularly preferably not more than 3. Furthermore, at least one, preferably at least two, carbon atoms (e) are generally present between two heteroatoms.
- Substituted and unsubstituted imino groups may be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino.
- the term "functional groups” are, for example, to the following: carboxy, carboxamide, hydroxy, di- (Ci -C 4 alkyl) amino, C 1 -C 4 - alkyloxycarbonyl, cyano or C 4 alkoxy It is. C 1 to C 4 alkyl, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
- C 6 -C 4 -aryl substituted by functional groups are, for example, phenyl, ToIyI, XyIyI, ⁇ -naphthyl, ⁇ -naphthyl, 4-diphenylyl, difluorophenyl, Methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso -propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,
- aryl, alkyl, aryloxy, F, heteroatoms and / or heterocycles C 5 -C 2 -cycloalkyl are for example cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, Dimethoxycyclohexyl, Diethoxycyclohexyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.
- a five- to six-membered oxygen and / or nitrogen heterocycle is, for example, furyl, pyryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, dimethylpyridyl, methylquinolyl, dimethylpyryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.
- Particularly preferred anions are selected from the group consisting of F “ , BF 4 “ , PF 6 “ , CF 3 SO 3 “ , (CF 3 SO 3 ) 2 N “ , CF 3 CO 2 " , from the group of sulfates, sulfites and sulfonates of the general formula: SO 4 2 " , HSO 4 ' , SO 3 2" , HSO 3 ' , R a OSO 3 " , R 3 SO 3 " , from the group of phosphates of the general formula PO 4 3 " , HPO 4 2 “ , H 2 PO 4 “ , R 3 PO 4 2 “ , from the group of borates of the formula BO 3 3” , HBO 3 2 ' , H 2 BO 3 “ , from the group of silicates and silicic acid esters of the formula SiO 4 4 “ , HSiO 4 3” , H 2 SiO 4 2 “ , H 3 SiO 4 " , the carboxylic imides, bis
- the membrane according to the invention moreover comprises at least one compound of the formula (P1)
- R ' 4 POH (P1) where R 1 , in each case independently of one another, is a radical which contains C, O and / or H and optionally further atoms different therefrom, it being possible for two radicals R 1 to be linked to one another.
- each R independently represents a 1-20 carbon atom group, preferably an unbranched and unsubstituted C 1 -C 8 -alkyl, such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-decyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, especially for methyl, ethyl, 1-butyl and 1-octyl, or a radical OR V , where R v is H, a 1-20 carbon atoms group, preferably a straight-chain and unsubstituted C 1 -C 8 -alkyl, such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl
- R 1 each independently of one another have a 1-20 carbon atoms group, preferably an unbranched and unsubstituted C 1 -C 18 -alkyl, such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-decyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, in particular for methyl, ethyl, 1-butyl and 1-octyl, or a radical OR VI , R IV are each independently O or a 1-20 carbon atoms-containing group, preferably an unbranched and unsubstituted C 1 -C 8 -alkyl, such as methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1 -heptyl, 1-o
- R v ⁇ each independently of one another H or a 1-20 carbon atoms having group, preferably an unbranched and unsubstituted C 1 -C 18 -alkyl, such as methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1 -Heptyl, 1-octyl, 1-decyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, in particular for methyl, ethyl, 1-butyl and 1-octyl, q is a number greater than or equal to 1 means.
- Compounds of the formula (P1) include, in particular, commercial phosphoric acid, commercial polyphosphoric acids HWPnO 3n + I (n> 1), which are obtainable, for example, from Riedel-de Haen and preferably have a content calculated as P 2 O 5 (acidimetric) of at least 83%. and known phosphonic acids, preferably Ci-Ci ⁇ -alkylphosphonic.
- the proportions of the polyazole, the ionic liquid and the compounds of the formula (P1) are in principle not particularly limited and can be chosen freely. However, particularly favorable properties are exhibited by polymer membranes which, based in each case on their total weight, a. From 0.5% to 40.0% by weight of polyazole, b. 1, 0 wt .-% to 50.0 wt% ionic liquid and c. 10.0 wt .-% to 98.5 wt.% Compound of formula (P1).
- the polyazole and the ionic liquid are present in a weight ratio in the range from 1: 2 to 1: 100.
- the weight ratio of ionic liquid to compound of the formula (P1) should be selected in the range from 1: 1 to 1:20, in particular in the range from 1: 5 to 1:15.
- the polymer membrane according to the invention also contains at least one polymer which is not a polyazole (polymer (B).
- the weight ratio of polyazole to polymer (B) is preferably in the range of 0.1 to 50, preferably in the range of 0.2 to 20, particularly preferably in the range of 1 to 10.
- polystyrene resin such as polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, such as polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polyst
- Polyarmethylene polystyrene, polymethylstyrene, polyvinylalcohol, polyvinylacetate,
- Polyvinyl ether polyvinylamine, poly (N-vinylacetamide), polyvinylimidazole,
- Polyvinylcarbazole polyvinylpyrrolidone, polyvinylpyridine, polyvinylchloride,
- Trifluoronitrosomethane with sulfonyl fluoride vinyl ether, with carbalkoxy perfluoroalkoxy vinyl ether, polychlorotrifluoroethylene, polyvinyl fluoride,
- Polyvinylidene fluoride polyacrolein, polyacrylamide, polyacrylonitrile, polycyanoacrylates,
- Polyacetal polyoxymethylene, polyether, polypropylene oxide, polyepichlorohydrin,
- Polyhydroxyacetic acid Polyethylene terephthalate, polybutylene terephthalate,
- Polyhydroxybenzoate polyhydroxypropionic acid, polypivalolactone, polycaprolactone,
- Polymers C-S bonds in the main chain for example polysulfide ethers,
- Polyimines polyisocyanides, polyetherimine, polyaniline, polyamides, polyhydrazides,
- Polyurethanes polyimides, polyazoles, polyazines
- Liquid crystalline polymers especially Vectra and
- Inorganic polymers for example polysilanes, polycarbosilanes, polysiloxanes,
- Polysilicic acid Polysilicates, silicones, polyphosphazenes and polythiazyl.
- the preferred polymers (B) also include polymers with covalently bonded acid groups. These acid groups include in particular sulfonic acid groups.
- the polymers modified with sulfonic acid groups preferably have a content of sulfonic acid groups in the range from 0.5 to 3 meq / g. This value is determined by the so-called ion exchange capacity (IEC).
- the sulfonic acid groups are converted into the free acid.
- the polymer is treated in a known manner with acid, wherein excess acid is removed by washing. This becomes the sulfonated polymer initially treated for 2 hours in boiling water. Subsequently, excess water is blotted and the sample is dried for 15 hours at 160 ° C in a vacuum oven at p ⁇ 1 mbar. Then the dry weight of the membrane is determined. The thus dried polymer is then dissolved in DMSO at 80 ° C for 1 h. The solution is then titrated with 0.1 M NaOH. From the consumption of the acid to the equivalent point and the dry weight, the ion exchange capacity (IEC) is then calculated.
- IEC ion exchange capacity
- polymers containing sulfonic acid groups can be prepared by sulfonation of polymers.
- Methods for sulfonating polymers are described in F. Kucera et. al. Polymer Engineering and Science 1988, Vol. 38, No. 5, 783-792.
- the sulfonation conditions can be chosen so that a low degree of sulfonation is formed (D E-A-19959289).
- non-fluorinated polymers were developed by sulfonation of high-temperature-stable thermoplastics.
- sulfonated polyether ketones WO96 / 29360
- sulfonated polysulfones J. Membr. Sei. 83 (1993) p.211
- sulfonated polyphenylene sulfide D E-A-19527435
- US-A-6110616 describes copolymers of butadiene and styrene and their subsequent sulfonation for use in fuel cells.
- perfluorinated polymers can be prepared as described in US-A-5422411 by copolymerization of trifluorostyrene and sulfonyl-modified trifuorostyrene.
- Preferred acid group polymers include, among others, sulfonated polyether ketones, sulfonated polysulfones, sulfonated polyphenylene sulfides, perfluorinated sulfonic acid group-containing polymers as described in US-A-3692569, US-A-5422411 and US-A-6110616.
- polymers (B) which have a glass transition temperature or Vicat softening temperature VST / A / 50 of at least 100 0 C, preferably at least 150 0 C and most preferably at least 180 0 C have.
- polysulfones having a Vicat softening temperature VST / A / 50 of 180 0 C to 230 0 C are preferred.
- the weight decreases only insignificantly by treatment with 85% phosphoric acid.
- the weight ratio of the plate after the phosphoric acid treatment to the weight of the plate before the treatment is greater than or equal to 0.8, in particular greater than or equal to 0.9, and particularly preferably greater than or equal to 0.95. This value is measured on a sheet of polymer (B) which is 2 mm thick, 5 cm long and 2 cm wide. This plate is placed in phosphoric acid, wherein the weight ratio of phosphoric acid to plate is 10. Subsequently, the phosphoric acid is heated with stirring for 24 hours at 100 0 C. The plate is then freed from excess phosphoric acid by washing with water and dried. After this, the plate is weighed again.
- Preferred polymers include polysulfones, especially polysulfone having aromatics in the backbone. According to a particular aspect of the present invention, preferred polysulfones and polyether sulfones have a melt volume rate MVR 300/21, 6 is less than or equal to 40 cm 3/10 min, especially less than or equal to 30 cm 3/10 min and particularly preferably less than or equal to 20 cm 3 / 10 min measured to ISO 1133.
- the polymer membrane contains phosphonic acid containing polymers which are obtainable by polymerization of monomers comprising phosphonic acid groups.
- the polymers are preferably obtainable by a process comprising the steps
- Imbibing is understood to mean an increase in weight of the porous polyazole of at least 3% by weight.
- the weight increase is preferably at least 5% by weight, more preferably at least 10% by weight.
- the weight increase is determined gravimetrically from the mass of the porous carrier material before imbibing rrio and the mass of the polymer membrane after the polymerization according to step B), r ⁇ i2.
- the imbibing is preferably carried out at a temperature above 0 0 C, in particular between room temperature (2O 0 C) and 18O 0 C in a liquid containing preferably at least 5 wt .-% phosphonic acid monomers. Furthermore, the imbibing can also be carried out at elevated pressure and with the aid of ultrasound. Here are the limits of economic considerations and technical possibilities.
- the polyazole used for imbibing generally has a thickness in the range from 5 to 1000 .mu.m, preferably 10 to 500 .mu.m, in particular 15 and 300 .mu.m and particularly preferably between 30 and 250 .mu.m.
- the preparation of such support materials is generally known, some of which are commercially available.
- Porous means that the polyazole has a large proportion of a free volume that can be filled with a liquid.
- the free volume is preferably at least 30%, preferably at least 50%, at least 70% and most preferably at least 90% by volume, based on the volume of the polyazole.
- the pores of the polyazole may generally have a size in the range of 1 nm to 4000 nm, preferably 10 to 1000 nm.
- the pores of the polyazole may generally have a volume in the range of 1 nm 3 to 1 ⁇ m 3 , preferably 10 nm 3 to 10,000 nm 3 .
- the pore volume of the polyazole results, for example, from the increase in weight due to imbibing with liquid. Furthermore, this size can also be determined by BET method (Brunauer, Emmett & Teller). For example, porous carriers of woven, nonwoven, foam or other porous materials can be used.
- polymer films with an open pore structure are more as 30% preferably more than 50% and most preferably more than 70%.
- the glass transition temperature of the organic base polymer of such a membrane is higher than the operating temperature of the fuel cell and is preferably at least 150 0 C, preferably at least 160 0 C and most preferably at least 180 0 C.
- Such membranes are used as separation membranes for ultrafiltration, gas separation, pervaporation , Nanofiltration, microfiltration or hemodialysis.
- the liquid containing monomers comprising phosphonic acid groups may be a solution, which liquid may also contain suspended and / or dispersed components.
- the viscosity of the liquid containing monomers containing phosphonic acid groups can be within a wide range, with an addition of solvents or an increase in temperature being able to be carried out to adjust the viscosity.
- the dynamic viscosity is preferably in the range from 0.1 to 1 000 000 mPa * s, in particular from 0.2 to 2000 mPa * s, where these values can be measured, for example, in accordance with DIN 53015.
- Monomers comprising phosphonic acid groups are known in the art. These are compounds which have at least one carbon-carbon double bond and at least one phosphonic acid group. Preferably, the two carbon atoms that form the carbon-carbon double bond have at least two, preferably three, bonds to groups that result in little steric hindrance of the double bond. Among these groups include hydrogen atoms and halogen atoms, in particular fluorine atoms.
- the polymer comprising phosphonic acid groups results from the polymerization product which is obtained by polymerization of the monomer comprising phosphonic acid groups alone or with further monomers and / or crosslinkers.
- the monomer comprising phosphonic acid groups may comprise one, two, three or more carbon-carbon double bonds. Furthermore, the monomer comprising phosphonic acid groups may contain one, two, three or more phosphonic acid groups.
- the monomer comprising phosphonic acid groups contains 2 to 20, preferably 2 to 10, carbon atoms.
- the monomer comprising phosphonic acid groups used to prepare the phosphonic acid groups are preferably compounds of the formula wherein
- R represents a bond, a C1-C15 divalent alkylene group, C1-C15 divalent alkyleneoxy group, for example ethyleneoxy group or C5-C20 double aryl or heteroaryl group, the above radicals themselves being halogen, -OH, COOZ, -CN, NZ 2 can be substituted,
- Z independently of one another hydrogen, C1-C15-alkyl group, C1-C15-
- Alkoxy group ethyleneoxy group or C5-C20-aryl or heteroaryl group, where the above radicals may themselves be substituted by halogen, -OH, -CN, and x is an integer 1, 2, 3, 4, 5, 6, 7, 8 , 9 or 10, y is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 and / or the formula wherein
- R represents a bond, a C1-C15 divalent alkylene group, C1-C15 divalent alkyleneoxy group, for example ethyleneoxy group or C5-C20 double aryl or heteroaryl group, the above radicals themselves being halogen, -OH, COOZ, -CN, NZ 2 can be substituted,
- Z independently of one another hydrogen, C1-C15-alkyl group, C1-C15-
- Alkoxy group ethyleneoxy group or C5-C20-aryl or heteroaryl group, where the above radicals may themselves be substituted by halogen, -OH, -CN, and x is an integer 1, 2, 3, 4, 5, 6, 7, 8 , 9 or 10 means and / or the formula wherein
- A represents a group of the formulas COOR 2 , CN, CONR 2 2 , OR 2 and / or R 2 , wherein R 2 is hydrogen, a C 1 -C 15 alkyl group, C 1 -C 15 alkoxy group, ethyleneoxy group or C 5 -C 20 aryl or heteroaryl group means where the above radicals can themselves be substituted by halogen, -OH, COOZ, -CN, NZ 2
- R represents a bond, a C1-C15 double-alkylene group, C1-C15 double-alkyleneoxy group, for example ethyleneoxy group or C5-C20 double-aryl or heteroaryl group, the above radicals themselves being halogen, -OH, COOZ, -CN, NZ 2 can be substituted,
- Z independently of one another hydrogen, C1-C15-alkyl group, C1-C15-
- Alkoxy group ethyleneoxy group or C5-C20-aryl or heteroaryl group, where the above radicals may themselves be substituted by halogen, -OH, -CN, and x is an integer 1, 2, 3, 4, 5, 6, 7, 8 , 9 or 10 means.
- the monomers comprising preferred phosphonic acid groups are, inter alia, alkenes having phosphonic acid groups, such as ethenephosphonic acid, propenephosphonic acid, butenephosphonic acid; Acrylic acid and / or methacrylic acid compounds which have phosphonic acid groups, for example 2-phosphonomethylacrylic acid, 2-phosphonomethyl-methacrylic acid, 2-phosphonomethylacrylamide and 2-phosphonomethyl-methacrylamide.
- vinylphosphonic acid ethenphosphonic acid
- ethenphosphonic acid such as is obtainable, for example, from Aldrich, BASF SE or Archimica GmbH, is particularly preferred.
- a preferred vinylphosphonic acid has a purity of more than 70%, in particular 90% and particularly preferably more than 97% purity.
- the monomers comprising phosphonic acid groups can furthermore also be used in the form of derivatives which can subsequently be converted into the acid, wherein the conversion to the acid can also take place in the polymerized state.
- derivatives include, in particular, the salts, the esters, the amides and the halides of the monomers comprising phosphonic acid groups.
- the liquid used in step A) preferably comprises at least 20% by weight, in particular at least 30% by weight and particularly preferably at least 50% by weight, based on the total weight of the mixture, of monomers comprising phosphonic acid groups.
- the liquid used in step A) may additionally contain further organic and / or inorganic solvents.
- the organic solvents include in particular polar aprotic solvents, such as dimethyl sulfoxide (DMSO), esters, such as ethyl acetate, and polar protic solvents, such as alcohols, such as ethanol, propanol, isopropanol and / or butanol.
- polar aprotic solvents such as dimethyl sulfoxide (DMSO)
- esters such as ethyl acetate
- polar protic solvents such as alcohols, such as ethanol, propanol, isopropanol and / or butanol.
- the inorganic solvents include in particular water, phosphoric acid and polyphosphoric acid.
- the content of monomers comprising phosphonic acid groups in such liquids is generally at least 5% by weight, preferably at least 10% by weight, particularly preferably between 10 and 97% by weight.
- compositions containing sulfonic acid group-containing monomers can be used to prepare the phosphonic acid group-containing polymers.
- Monomers comprising sulfonic acid groups are known in the art. These are compounds which have at least one carbon-carbon double bond and at least one sulfonic acid group. Preferably, the two carbon atoms that form the carbon-carbon double bond have at least two, preferably three, bonds to groups that result in little steric hindrance of the double bond. These groups include, among others, hydrogen atoms and halogen atoms, especially fluorine atoms.
- the polymer comprising sulfonic acid groups results from the polymerization product which is obtained by polymerization of the monomer comprising sulfonic acid groups alone or with further monomers and / or crosslinkers.
- the monomer comprising sulfonic acid groups may comprise one, two, three or more carbon-carbon double bonds. Further, the monomer comprising sulfonic acid groups may contain one, two, three or more sulfonic acid groups.
- the monomer comprising sulfonic acid groups contains 2 to 20, preferably 2 to 10, carbon atoms.
- the monomer comprising sulfonic acid groups are preferably compounds of the formula wherein
- R represents a bond, a C1-C15 divalent alkylene group, C1-C15 divalent alkyleneoxy group, for example ethyleneoxy group or C5-C20 double aryl or heteroaryl group, the above radicals themselves being halogen, -OH, COOZ, -CN, NZ 2 can be substituted,
- Z independently of one another hydrogen, C1-C15-alkyl group, C1-C15-
- Alkoxy group ethyleneoxy group or C5-C20-aryl or heteroaryl group, where the above radicals may themselves be substituted by halogen, -OH, -CN, and x is an integer 1, 2, 3, 4, 5, 6, 7, 8 , 9 or 10, y is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10
- R denotes a bond, a C1-C15 double-alkylene group, C1-C15 double-alkyleneoxy group, for example ethyleneoxy group or C5-C20 double-aryl or heteroaryl group, where the above radicals themselves, with halogen, -OH, COOZ, -CN, NZ 2 can be substituted,
- Z independently of one another hydrogen, C1-C15-alkyl group, C1-C15-
- Alkoxy group ethyleneoxy group or C5-C20-aryl or heteroaryl group, where the above radicals may themselves be substituted by halogen, -OH, -CN, and x is an integer 1, 2, 3, 4, 5, 6, 7, 8 , 9 or 10 means
- A represents a group of the formulas COOR 2 , CN, CONR 2 2 , OR 2 and / or R 2 , wherein R 2 is hydrogen, a C 1 -C 15 alkyl group, C 1 -C 15 alkoxy group, ethyleneoxy group or C 5 -C 20 aryl or heteroaryl group means where the above radicals can themselves be substituted by halogen, -OH, COOZ, -CN, NZ 2
- R represents a bond, a C1-C15 double-alkylene group, C1-C15 double-alkyleneoxy group, for example ethyleneoxy group or C5-C20 double-aryl or heteroaryl group, the above radicals themselves being halogen, -OH, COOZ, -CN, NZ 2 can be substituted,
- Z independently of one another hydrogen, C1-C15-alkyl group, C1-C15-
- Alkoxy group ethyleneoxy group or C5-C20-aryl or heteroaryl group, where the above radicals may themselves be substituted by halogen, -OH, -CN, and x is an integer 1, 2, 3, 4, 5, 6, 7, 8 , 9 or 10 means.
- Included among the preferred monomers comprising sulfonic acid include alkenes having sulfonic acid groups, such as ethene sulfonic acid, propylene sulfonic acid, butene sulfonic acid; Acrylic acid and / or methacrylic acid compounds which have sulfonic acid groups, such as, for example, 2-sulfonomethylacrylic acid, 2-sulfonomethylmethacrylic acid, 2-sulfonomethylacrylamide and 2-sulfonomethylmethacrylamide.
- alkenes having sulfonic acid groups such as ethene sulfonic acid, propylene sulfonic acid, butene sulfonic acid
- Acrylic acid and / or methacrylic acid compounds which have sulfonic acid groups, such as, for example, 2-sulfonomethylacrylic acid, 2-sulfonomethylmethacrylic acid, 2-sulfonomethylacrylamide and 2-sulfono
- vinyl sulfonic acid ethene sulfonic acid
- a preferred vinylsulfonic acid has a purity of more than 70%, in particular 90% and particularly preferably more than 97% purity.
- the monomers comprising sulfonic acid groups can furthermore also be used in the form of derivatives, which can then be converted into the acid, wherein the conversion to the acid can also take place in the polymerized state.
- derivatives include, in particular, the salts, the esters, the amides and the halides of the monomers comprising sulfonic acid groups.
- the weight ratio of monomers comprising sulfonic acid groups to monomers comprising phosphonic acid groups can be in the range from 100: 1 to 1: 100, preferably 10: 1 to 1:10 and more preferably 2: 1 to 1: 2.
- monomers which are capable of crosslinking in the preparation of the polymer membrane can be used. These monomers can be added to the liquid according to step A).
- the monomers capable of crosslinking are in particular compounds which have at least 2 carbon-carbon double bonds. Preference is given to dienes, trienes, tetraenes, dimethyl acrylates, trimethyl acrylates, tetramethyl acrylates, diacrylates, triacrylates, tetraacrylates.
- R is a C 1 -C 15 -alkyl group, C 5 -C 20 -aryl or heteroaryl group, NR ' , -SO 2 ,
- Alkoxy group, C5-C20-aryl or heteroaryl group and n is at least 2.
- the substituents of the above radical R are preferably halogen, hydroxyl, carboxyl, carboxyl, carboxyl esters, nitriles, amines, silyl, siloxane radicals.
- crosslinkers are allyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetra- and polyethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, glycerol dimethacrylate, diurethane dimethacrylate, trimethylpropane trimethacrylate, epoxy acrylates, for example, Ebacryl, N ' , N-methylenebisacrylamide, carbinol, butadiene, isoprene, chloroprene, divinylbenzene and / or bisphenol A-dimethylacrylate. These compounds are commercially available, for example, from Sartomer Company Exton, Pennsylvania under the names CN-120, CN104 and CN-980.
- crosslinkers are optional, these compounds usually in the range between 0.05 to 30 wt .-%, preferably 0.1 to 20 wt .-%, particularly preferably 1 and 10 wt .-%, based on the weight of Phosphonic acid groups comprising monomers can be used.
- fillers in particular proton-conductive fillers, and additional acids may be added.
- Non-limiting examples of proton-conducting fillers are:
- Sulfates such as: CsHSO 4 , Fe (SO 4 ) 2 , (NH 4 ) SH (SO 2 O 2 , LiHSO 4 , NaHSO 4 , KHSO 4 ,
- RbSO 4 LiN 2 H 5 SO 4 , NH 4 HSO 4 , phosphates such as Zr 3 (PO 4 J 4 , Zr (HPO 4 J 2 , HZr 2 (PO 4 J 3 , UO 2 PO 4 .3H 2 O, H 8 UO 2 PO 4 ,
- HTiTaO 5 , HSbTeO 6 , H 5 Ti 4 O 9 , HSbO 3 , H 2 MoO 4 selenites and arsenides such as (NH 4 J 3 H (SeO 4 J 2 , UO 2 AsO 4 , (NH 4 J 3 H (SeO 4 J 2 , KH 2 AsO 4 ,
- Oxides such as Al 2 O 3 , Sb 2 O 5 , ThO 2 , SnO 2 , ZrO 2 , MoO 3 silicates such as zeolites, zeolites (NH 4 +), phyllosilicates, framework silicates, H-natrolites,
- H-mordenites NH 4 -alcines, NH 4 -sodalites, NH 4 -gallates, H-
- Montmorillonite acids such as HCIO 4 , SbF 5 fillers such as carbides, in particular SiC, Si 3 N 4 , fibers, in particular glass fibers,
- Glass powders and / or polymer fibers preferably based on
- the membrane comprises at most 80% by weight, preferably at most 50% by weight and more preferably at most 20% by weight of additives.
- the polymer membrane may also contain perfluorinated sulfonic acid additives (preferably 0.1-20% by weight, preferably 0.2-15% by weight, more preferably 0.2-10% by weight). These additives improve performance near the cathode to increase oxygen solubility and oxygen diffusion and reduce the adsorption of phosphoric acid and phosphate to platinum.
- perfluorinated sulfonic acid additives preferably 0.1-20% by weight, preferably 0.2-15% by weight, more preferably 0.2-10% by weight.
- Non-limiting examples of persulfonated additives are: trifluoromethanesulfonic acid, potassium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, lithium, Ammoniumtrifluormethansulfonat, Kaliumperfluorohexansulfonat, Natriumperfluorohexansulfonat perfluorohexanesulphonate, lithium, ammonium perfluorohexanesulphonate, perfluorohexanesulphonic acid, potassium nonafluorobutanesulphonate, Natriumnonafluorbutansulfonat, Lithiumnonafluorbutansulfonat, Ammoniumnonafluorbutansulfonat, Cäsiumnonafluorbutansulfonat, Triethylammoniumperfluorohexasulfonat, Perflurosulfoimide and Nafion.
- the preparation of the membrane according to the invention can be carried out in a manner known per se, for example by preparing a solution of the components polyazole, ionic liquid and compound of the formula (P1), lolling and solidifying.
- the preparation of the polyazole already takes place in the presence of at least one compound of the formula (P1) or at least one compound which on hydrolysis yields at least one compound of the formula (P1), more preferably in the presence of polyphosphoric acid ,
- the compound of formula (P1) or the compound which gives on hydrolysis at least one compound of formula (P1), one or more compounds are added which are capable of forming polyazoles under the action of heat.
- Suitable compounds which upon hydrolysis provide at least one compound of the formula (P1) include polyphosphoric acid and organic phosphonic anhydrides, in particular cyclic compounds of the formula
- Anhydrides of polyorganically phosphonic acids e.g. the formula of anhydrides of diphosphonic acid
- radical R and R ' are identical or different and represent a C 1 -C 20 -carbon-containing group.
- radicals C 1 -C 20 -alkyl particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t, among a C 1 -C 20 -carbon-containing group Butyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl or cyclooctyl, Ci - C20 - alkenyl, more preferably ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, octenyl or cyclooctenyl , Ci - C 20 - alkynyl, more preferably ethynyl, propyn
- one or more non-adjacent CH 2 groups may be replaced by -O-, -S-, -NR 1 - or -CONR 2 - and one or more H atoms can be replaced by F.
- Ci or -CONR 2 may be replaced and one or more H atoms can be replaced by F.
- radicals R 1 and R 2 are identical or different at each occurrence H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C-atoms.
- organic phosphonic anhydrides which are partially or perfluorinated.
- the said organic phosphonic anhydrides are commercially available, for example the product ® T3P (propane-phosphonic anhydride) from Archimica.
- the organic phosphonic anhydrides can also be used in combination with polyphosphoric acid and / or with P 2 O 5 .
- the polyphosphoric acid is commercially available polyphosphoric acids such as those available from Riedel-de Haen, for example.
- the polyphosphoric acids H n + 2 PnO 3 n + i (n> 1) usually have a content calculated as P 2 O 5 (acidimetric) of at least 83%. Instead of a solution of the monomers, it is also possible to produce a dispersion / suspension.
- organic phosphonic anhydrides can also be used in combination with simple and / or multiple organic phosphonic acids.
- the simple and / or multiple organic phosphonic acids are compounds of the formula
- radical R is identical or different and represents a C 1 -C 20 -carbon-containing group.
- the radicals C 1 -C 20 -alkyl particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-butyl, Butyl, t-butyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl or cyclooctyl, C 6 -C 2 o-aryl, particularly preferably phenyl, biphenyl, naphthyl or anthracenyl, Ci - C.
- o-fluoroalkyl particularly preferably trifluoromethyl, pentafluoroethyl or 2,2,2-trifluoroethyl, C 6 -C 20 -aryl, more preferably phenyl, biphenyl, naphthyl, anthracenyl, triphenylenyl, [1, r; 3 ', 1 "] Terphenyl-2'-yl, binaphthyl or phenanthrenyl, C 6 -C 2 o-fluoroaryl, particularly preferably tetrafluorophenyl or heptafluoronaphthyl, C 1 -C 20 -alkoxy, particularly preferably methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy , i-butoxy, s-butoxy or t-butoxy, C6-C 2 o-aryloxy, particularly preferred phenoxy, naphthoxy, biphenyl
- one or more non-adjacent CH 2 groups may be replaced by -O-, -S-, -NR 1 - or -CONR 2 - and one or more H atoms can be replaced by F.
- one or more non-adjacent CH groups may be replaced by -O-, -S-, -NR 1 - or -CONR 2 and one or more H - Atoms can be replaced by F.
- radicals R 1 and R 2 are identical or different at each occurrence H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C-atoms.
- organic phosphonic acids which are partially or perfluorinated.
- organic phosphonic acids are commercially available, for example the products of the company Clariant or Aldrich.
- Vinyl-containing phosphonic acids as described in German Patent Application No. 10213540.1, are preferably not used.
- the compound of the formula (P1) or the compound which on hydrolysis yields at least one compound of the formula (P1) is preferably in a weight ratio of all compound of the formula (P1) and of all compounds which on hydrolysis produce at least one compound of the formula ( P1), to sum of all monomers from 1: 10000 to 10000: 1, preferably 1: 1000 to 1000: 1, in particular 1: 100 to 100: 1, used.
- suitable mixtures comprise one or more aromatic and / or heteroaromatic tetra-amino Compounds and one or more aromatic and / or heteroaromatic carboxylic acids or derivatives thereof containing at least two acid groups per carboxylic acid monomer.
- aromatic and / or heteroaromatic diaminocarboxylic acids can be used for the preparation of polyazoles.
- the aromatic and heteroaromatic tetra-amino compounds include inter alia 3,3 ', 4,4'-tetraaminobiphenyl, 2,3,5,6-tetraaminopyridine, 1, 2,4,5-tetraaminobenzene, 3,3', 4,4'-tetraaminodiphenylsulfone, 3,3 ', 4,4'-tetraaminodiphenyl ether, 3,3', 4,4'-tetraaminobenzophenone, 3,3 ', 4,4'-tetraaminodiphenylmethane and 3,3', 4, 4'-Tetraaminodiphenyldimethylmethan and salts thereof, in particular their mono-, di-, tri- and tetrahydrochloride derivatives.
- 3,3 ', 4,4'-tetraaminobiphenyl, 2,3,5,6-tetraaminopyridine and 1,2,4,5-tetraaminobenzene are
- the mixture may comprise aromatic and / or heteroaromatic carboxylic acids.
- aromatic and / or heteroaromatic carboxylic acids are dicarboxylic acids and tricarboxylic acids and tetracarboxylic acids or their esters or their anhydrides or their acid halides, in particular their acid halides and / or acid bromides.
- aromatic dicarboxylic acids to isophthalic acid, phthalic acid, 5-hydroxyisophthalic acid, 4- hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 5-aminoisophthalic acid, 5-N 1 N- Dimethylaminoisophthalcic Acid, 5-N, N-Diethylaminoisophthalcic Acid, 2.5 Dihydroxyterephthalic acid, 2,6-dihydroxyisophthalic acid, 4,6-dihydroxyisophthalic acid, 2,3-dihydroxyphthalic acid, 2,4-dihydroxyphthalic acid.
- aromatic tricarboxylic acids or their C1-C20-alkyl-esters or C5-C12-
- Aryl esters or their acid anhydrides or their acid chlorides are preferably trimethylic acid, 1,3,5-benzenetricarboxylic acid (trimesic acid), 1,4-benzenetricarboxylic acid (trimellitic acid),
- aromatic tetracarboxylic acids or their C 1 -C 20 -alkyl esters or C 5 -C 12 -aryl esters or their acid anhydrides or their acid chlorides are preferably 3,5,3 ', 5'-biphenyltetracarboxylic acid, 1, 2,4, 5-Benzoltetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,2', 3,3-biphenyltetracarboxylic acid, 1, 2,5,6-naphthalenetetracarboxylic acid, 1, 4,5,8-naphthalenetetracarboxylic acid.
- heteroaromatic carboxylic acids are preferably heteroaromatic dicarboxylic acids and tricarboxylic acids and tetracarboxylic acids or their esters or their anhydrides.
- Heteroaromatic carboxylic acids are aromatic systems which contain at least one nitrogen, oxygen, sulfur or phosphorus atom in the aromatic.
- pyridine-2,5-dicarboxylic acid pyridine-3,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, 4-phenyl-2,5-pyridinedicarboxylic acid, 3,5 Pyrazole dicarboxylic acid, 2,6-pyrimidine dicarboxylic acid, 2,5-pyrazine dicarboxylic acid, 2,4,6-pyridine tricarboxylic acid, benzimidazole-5,6-dicarboxylic acid and their C1-C20 alkyl esters or C5-C12 aryl esters, or the like Acid anhydrides or their acid chlorides.
- the content of tricarboxylic acid or tetracarboxylic acids is between 0 and 30 mol%, preferably 0.1 and 20 mol%, in particular 0.5 and 10 mol%.
- aromatic and heteroaromatic diaminocarboxylic acids include, inter alia, diaminobenzoic acid, 4-phenoxycarbonyl-3, '4'-diaminodiphenylether and their mono- and dihydrochloride derivatives. Preference is given to using mixtures of at least 2 different aromatic carboxylic acids. Particular preference is given to using mixtures which, in addition to aromatic carboxylic acids, also contain heteroaromatic carboxylic acids. The mixing ratio of aromatic carboxylic acids to heteroaromatic carboxylic acids is between 1:99 and 99: 1, preferably between 1:50 to 50: 1.
- mixtures are, in particular, mixtures of N-heteroaromatic dicarboxylic acids and aromatic dicarboxylic acids.
- dicarboxylic acids are isophthalic acid, terephthalic acid, phthalic acid, 2,5-dihydroxyterephthalic acid, 2,6-dihydroxyisophthalic acid, 4,6-dihydroxyisophthalic acid, 2,3-dihydroxyphthalic acid, 2,4-dihydroxyphthalic acid.
- the molar ratio of carboxylic acid groups to amino groups in the reaction of tetra-amino compounds with one or more aromatic carboxylic acids or their esters containing at least two acid groups per carboxylic acid monomer is preferably in the vicinity of 1: 2.
- At least 0.5% by weight, in particular from 1 to 30% by weight and particularly preferably from 2 to 15% by weight, of monomers are preferably used for the preparation of polyazoles, in each case based on the resulting weight of the composition to be used.
- the polyazoles are prepared directly from the monomers in the compound of the formula (P1) or the compound which on hydrolysis gives at least one compound of the formula (P1), the polyazoles are distinguished by a high molecular weight. This is especially true for the polybenzimidazoles. Measured as intrinsic viscosity, this is in the range of 0.3 to 10 dl / g, preferably in the range of 1 to 5 dl / g. Insofar as tricarboxylic acids or tetracarboxylic acid are used, this results in a branching / crosslinking of the polymer formed. This contributes to the improvement of the mechanical property.
- compounds which are heat-reactive to form polyazoles, which compounds are prepared by reacting one or more aromatic and / or heteroaromatic tetra-amino compounds with one or more aromatic and / or heteroaromatic carboxylic acids or their derivatives which contain at least two acid groups per carboxylic acid monomer, or of one or more aromatic and / or heteroaromatic diaminocarboxylic acids in the melt at temperatures of up to 400 0 C, in particular up to 350 0 C, preferably up to 280 0 C are available.
- the compounds to be used for preparing these prepolymers have been previously set forth.
- step B) applying a layer using the mixture according to step A) on a carrier or on an electrode
- step B) heating of the sheet / layer obtainable according to step B) under inert gas to temperatures of up to 350 0 C, preferably up to 280 0 C to form the polyazole polymer,
- step D) treatment of the membrane formed in step C) (until it is self-supporting).
- the mixture produced in step A) preferably has a weight ratio sum of all compounds of the formula (P1) and of all compounds which on hydrolysis give at least one compound of the formula (P1) to sum of all monomers of 1: 10,000 to 10,000: 1, preferably 1: 1000 to 1000: 1, in particular 1: 100 to 100: 1, on.
- the layer formation according to step B) takes place by means of measures known per se, in particular casting, spraying and / or doctoring, which are known from the prior art for polymer film production.
- Suitable carriers are all suitable carriers under the conditions as inert.
- the solution may optionally be treated with phosphoric acid (concentrated phosphoric acid, 85%). This allows the viscosity to be adjusted to the desired value and the formation of the membrane can be facilitated.
- the layer produced according to step B) preferably has a thickness between 20 and 4000 ⁇ m, preferably between 30 and 3500 ⁇ m, in particular between 50 and 3000 ⁇ m.
- the sheet-like structure or the layer, obtainable in step B) under inert gas to temperatures of up to 350 0 C, preferably up to 280 0 C, heated.
- step A) by heating the mixture of step A) to temperatures of up to 350 0 C, preferably up to 280 0 C, already the formation of oligomers and / or polymers are effected. Depending on the selected temperature and duration, then the heating in step C) can be omitted partially or completely.
- aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, 2,5-dihydroxyterephthalic acid, 4,6-dihydroxyisophthalic acid, 2,6-dihydroxyisophthalic acid, diphenic acid, 1,8-dihydroxynaphthalene-3, 6-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, 4-trifluoromethylphthalic acid, pyridine-2,5- dicarboxylic acid, pyridine-3,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, 4-phenyl-2,5-pyridinedicarboxylic acid,
- Polyphosphoric acid is used in the method, the treatment of the membrane in step D), preferably at temperatures above 0 0 C and less than 15O 0 C, preferably at temperatures between 10 0 C and 12O 0 C, in particular between room temperature (20 0 C) and 90 0 C, in the presence of moisture or water and / or water vapor and / or water-containing phosphoric acid of up to 85%.
- the treatment is preferably carried out under normal pressure, but can also be effected under the action of pressure. It is essential that the treatment is carried out in the presence of sufficient moisture, whereby the present polyphosphoric acid contributes to the solidification of the membrane by partial hydrolysis to form low molecular weight polyphosphoric acid and / or phosphoric acid.
- the partial hydrolysis of the polyphosphoric acid in step D) leads to a solidification of the membrane and a decrease in the layer thickness and formation of a membrane having a thickness preferably between 15 and 3000 .mu.m, preferably between 20 and 2000 .mu.m, in particular between 20 and 1500 .mu.m, the is self-supporting.
- the intra- and intermolecular structures (interpenetrating networks IPN) present in the polyphosphoric acid layer according to step B) result in an orderly membrane formation in step C) which is responsible for the particular properties of the membrane formed.
- the upper temperature limit of the treatment according to step D) is generally 150 ° C. In the case of extremely short exposure to moisture, for example superheated steam, this steam may also be hotter than 150 ° C. Essential for the upper temperature limit is the duration of the treatment.
- the partial hydrolysis (step D) can also be carried out in climatic chambers in which the hydrolysis can be controlled in a controlled manner under defined action of moisture.
- the moisture can be specifically adjusted by the temperature or saturation of the contacting environment, for example gases such as air, nitrogen, carbon dioxide or other suitable gases, or water vapor.
- gases such as air, nitrogen, carbon dioxide or other suitable gases, or water vapor.
- the duration of treatment depends on the parameters selected above.
- the duration of treatment depends on the thickness of the membrane.
- the treatment time is between a few seconds to minutes, for example under the action of superheated steam, or up to full days, for example in air at room temperature and low relative humidity.
- the treatment time is preferably between 10 seconds and 300 hours, in particular 1 minute to 200 hours. If the partial hydrolysis is carried out at room temperature (2O 0 C) with ambient air at a relative humidity of 40-80%, the treatment time is between 1 and 200 hours.
- the membrane obtained according to step D) can be made self-supporting, i. It can be detached from the carrier without damage and then optionally further processed directly.
- the concentration of phosphoric acid and thus the conductivity of the polymer membrane according to the invention is adjustable.
- the concentration of phosphoric acid is given as mol of acid per mole of repeat unit of the polymer.
- a concentration (moles of phosphoric acid relative to a repeating unit of the formula (III), i.e. polybenzimidazole) of between 10 and 50, in particular between 12 and 40, is preferred.
- Such high doping levels (concentrations) are very difficult or even impossible to access by the addition of polyazoles with commercially available ortho-phosphoric acid.
- the membrane can still be crosslinked by the action of heat in the presence of atmospheric oxygen at the surface. This hardening of the membrane surface additionally improves the properties of the membrane.
- IR infra red, ie light with a wavelength of more than 700 nm
- NIR near IR, ie light with a wavelength in the range of about 700 to 2000 nm or an energy in the range of about 0.6 to 1.75 eV).
- Another method is the irradiation with ß-rays.
- the radiation dose is between 5 and 200 kGy.
- the introduction of the ionic liquid into the membrane is carried out in the context of the present invention preferably by
- step A) the ionic liquid is added to the solution or dispersion of step A) and the subsequent steps B), C) and D) are carried out in the presence of the ionic liquid or (ii) the ionic liquid is subsequently introduced into the membrane formed.
- the first variant assumes that the ionic liquid under the reaction conditions of the subsequent steps B), C) and D) and optionally further Steps behaves inertly or at least does not adversely affect the properties of the resulting membrane. It has the advantage that the composition of the resulting membrane can be adjusted comparatively easily and directly.
- the second variant has the advantage that it is also possible to use those ionic liquids which, under the reaction conditions of the subsequent steps B), C) and D) and optionally further steps, can not be inert and / or washed out again.
- the second variant can be realized in particular by first preparing the membrane, then the compound of the formula (P1) or the compound which on hydrolysis yields at least one compound of the formula (P1), in particular polyphosphoric acid and / or phosphoric acid, completely or partially rinsed and then the membrane again with at least one compound of formula (P1), preferably phosphoric acid and / or polyphosphoric acid, and the ionic liquid impregnated, for example by immersing the membrane in a bath containing the desired impregnating composition.
- the procedure of completely washing out the compound of the formula (P1) or the compound which on hydrolysis gives at least one compound of the formula (P1) offers the advantage that the ratio of compound of the formula (P1) to ionic liquid in can adjust the resulting membrane targeted.
- the polymer membrane according to the invention has improved material properties compared to previously known doped polymer membranes. In particular, they show better performance compared to known doped polymer membranes. This is due in particular to an improved proton conductivity. This is at temperatures of 120 0 C at least 0.1 S / cm, preferably at least 0.1 1 S / cm, in particular at least 0.12 S / cm. Furthermore, the polymer membrane according to the invention is characterized by improved mechanical properties, in particular by an improved modulus of elasticity, improved fracture toughness and improved elongation at break. Thus, the polymer membrane according to the invention exhibits a fracture toughness which is at least 20% higher than that of a membrane which comprises the same composition but no ionic liquid. In addition, the elongation at break of the polymer membrane according to the invention is preferably at least 200%, in particular at least 250%, and the stress is preferably at least 2.6 MPa, in particular at least 2.8 MPa.
- the doped polymer membranes according to the invention include, inter alia, use in fuel cells, in electrolysis, in capacitors and in battery systems. Because of their property profile, the doped polymer membranes are preferably used in fuel cells.
- the present invention also relates to a membrane-electrode assembly comprising at least one polymer membrane according to the invention.
- a membrane-electrode assembly comprising at least one polymer membrane according to the invention.
- the membrane formation can also take place directly on the electrode instead of on a support.
- the treatment according to step D) can be shortened accordingly, since the membrane no longer has to be self-supporting.
- Such a membrane is also the subject of the present invention.
- Another object of the present invention is an electrode having a proton-conducting polymer coating comprising at least one polyazole, at least one ionic liquid and at least one compound of formula (P1).
- a coated electrode may be incorporated in a membrane-electrode assembly optionally comprising at least one polymer membrane of the invention.
- the invention is further illustrated by an example and a comparative example, without this being intended to limit the inventive concept.
- the resulting solution was stirred at 220 C for 2 h 0, and finally increased to 240 0 C for 1 h.
- the highly viscous solution was laced at this temperature with a preheated doctor blade on a glass plate.
- a transparent, dark brown colored poly (2,2 '- (m-phenylene) -5,5'-bibenzimidazole (PBI) membrane was obtained and the membrane was then allowed to stand at RT for 1 h to obtain a self-supporting membrane.
- the polybenzimidazole H 3 PO 4 membrane of the comparative example was washed with water. The wet membrane was then immersed twice in an IL (EMIMEtOSO 3 (1-ethyl-3-methylimidazoliumethylsulfate)): H 3 PO 4 bath at room temperature (Weight ratio 1: 9) inserted. Subsequently, the membrane was taken out of the bath and blotted.
- IL EMIMEtOSO 3 (1-ethyl-3-methylimidazoliumethylsulfate
- the specific conductivity is measured by means of impedance spectroscopy in a 4-PoI arrangement in the potentiostatic mode and using platinum electrodes (wire, 0.25 mm diameter). The distance between the current-collecting electrodes is 2 cm.
- the obtained spectrum is evaluated with a simple model consisting of a parallel arrangement of an ohmic resistor and a capacitor.
- the sample cross-section of the phosphoric acid-doped membrane is measured immediately prior to sample assembly. To measure the temperature dependence, the measuring cell is brought to the desired temperature in an oven and controlled by a Pt-100 thermocouple placed in the immediate vicinity of the sample. After reaching the temperature, the sample is held at this temperature for 10 minutes before starting the measurement.
- the measurement of the elongation at break / stress is carried out on strip-shaped samples with a width of 15 mm and a length of 120 mm.
- the tensile test is carried out at a temperature of 30 0 C with a strain rate of 50 mm / min.
- the fracture toughness is obtained as the area under the elongation at break / stress curve.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Conductive Materials (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09745506A EP2289122A1 (de) | 2008-05-15 | 2009-05-02 | Protonenleitende membran und deren verwendung |
CN2009801173700A CN102047479A (zh) | 2008-05-15 | 2009-05-02 | 质子导电膜和其用途 |
JP2011508813A JP2011523496A (ja) | 2008-05-15 | 2009-05-02 | プロトン伝導性の膜及びこれを使用する方法 |
CA2723283A CA2723283A1 (en) | 2008-05-15 | 2009-05-02 | Proton-conducting membrane and use thereof |
US12/992,146 US20110065020A1 (en) | 2008-05-15 | 2009-05-02 | Proton-conducting membrane and its use |
BRPI0912651A BRPI0912651A2 (pt) | 2008-05-15 | 2009-05-02 | membrana polimérica condutora de próton, método para produzir uma membrana polimérica condutora de próton, eletrodo com um revestimento polimérico condutor de prótons, unidade de membrana-eletrodo, e, célula de combustível |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08008975 | 2008-05-15 | ||
EP08008975.8 | 2008-05-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009138172A1 true WO2009138172A1 (de) | 2009-11-19 |
Family
ID=40943665
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2009/003163 WO2009138172A1 (de) | 2008-05-15 | 2009-05-02 | Protonenleitende membran und deren verwendung |
Country Status (9)
Country | Link |
---|---|
US (1) | US20110065020A1 (de) |
EP (1) | EP2289122A1 (de) |
JP (1) | JP2011523496A (de) |
KR (1) | KR20110036878A (de) |
CN (1) | CN102047479A (de) |
BR (1) | BRPI0912651A2 (de) |
CA (1) | CA2723283A1 (de) |
RU (1) | RU2010151121A (de) |
WO (1) | WO2009138172A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120142830A1 (en) * | 2009-12-21 | 2012-06-07 | Dawkins Bobby G | Polybenzimidazole solution in an ionic liquid |
DE102014009675A1 (de) * | 2014-06-30 | 2015-12-31 | Forschungszentrum Jülich GmbH | Elektolytsystem für eine Brennstoffzelle |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10361832A1 (de) * | 2003-12-30 | 2005-07-28 | Celanese Ventures Gmbh | Protonenleitende Membran und deren Verwendung |
DE10361932A1 (de) * | 2003-12-30 | 2005-07-28 | Celanese Ventures Gmbh | Protonenleitende Membran und deren Verwendung |
US20130183603A1 (en) | 2012-01-17 | 2013-07-18 | Basf Se | Proton-conducting membrane, method for their production and their use in electrochemical cells |
US9812725B2 (en) | 2012-01-17 | 2017-11-07 | Basf Se | Proton-conducting membrane and use thereof |
EP2804889B1 (de) * | 2012-01-17 | 2019-03-13 | Basf Se | Protonenleitende membran, verfahren zu ihrer herstellung und ihre verwendung in elektrochemischen zellen |
KR101470926B1 (ko) * | 2013-09-11 | 2014-12-09 | 한국에너지기술연구원 | 고체산 프로톤 전도체, 그 제조방법, 및 그를 이용한 기체분리막 모듈, 암모니아 합성모듈 및 연료전지 |
JP6523306B2 (ja) * | 2014-01-21 | 2019-05-29 | カウンシル オブ サイエンティフィック アンド インダストリアル リサーチ | ポリベンズイミダゾール(pbi)及びポリマーイオン性液体(pil)系ブレンド膜、並びにその調製プロセス |
US9765196B2 (en) * | 2014-02-20 | 2017-09-19 | Rutgers, The State University Of New Jersey | Inorganic ionomers made from minerals |
CN111836849B (zh) * | 2018-03-09 | 2023-04-07 | 巴斯夫欧洲公司 | 制备聚吲哚聚合物(p)的纤维、膜和模制品的方法 |
CN112820919A (zh) * | 2019-11-18 | 2021-05-18 | 坤艾新材料科技(上海)有限公司 | 纤维增强高温质子交换膜及其制备方法、电化学设备 |
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2009
- 2009-05-02 WO PCT/EP2009/003163 patent/WO2009138172A1/de active Application Filing
- 2009-05-02 JP JP2011508813A patent/JP2011523496A/ja not_active Withdrawn
- 2009-05-02 BR BRPI0912651A patent/BRPI0912651A2/pt not_active Application Discontinuation
- 2009-05-02 CN CN2009801173700A patent/CN102047479A/zh active Pending
- 2009-05-02 CA CA2723283A patent/CA2723283A1/en not_active Abandoned
- 2009-05-02 US US12/992,146 patent/US20110065020A1/en not_active Abandoned
- 2009-05-02 KR KR1020107025658A patent/KR20110036878A/ko not_active Application Discontinuation
- 2009-05-02 RU RU2010151121/07A patent/RU2010151121A/ru not_active Application Discontinuation
- 2009-05-02 EP EP09745506A patent/EP2289122A1/de not_active Withdrawn
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EP1826846A1 (de) * | 2004-11-10 | 2007-08-29 | Toyo Boseki Kabushiki Kasisha | Aromatische kohlenwasserstoffbasenprotonen-austauschmembran und direktmethanol-brennstoffzelle damit |
EP1760110A1 (de) * | 2005-09-03 | 2007-03-07 | Samsung SDI Co., Ltd. | Polybenzoxazin Verbindung, Elektrolyt-Membran enthaltend dieser Verbindung und Elektrolyt-Membran benutzende Brenndstofzell |
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US9447242B2 (en) * | 2009-12-21 | 2016-09-20 | Pbi Performance Products, Inc. | Polybenzimidazole solution in an ionic liquid |
DE102014009675A1 (de) * | 2014-06-30 | 2015-12-31 | Forschungszentrum Jülich GmbH | Elektolytsystem für eine Brennstoffzelle |
Also Published As
Publication number | Publication date |
---|---|
BRPI0912651A2 (pt) | 2016-01-26 |
CN102047479A (zh) | 2011-05-04 |
CA2723283A1 (en) | 2009-11-19 |
RU2010151121A (ru) | 2012-06-20 |
EP2289122A1 (de) | 2011-03-02 |
US20110065020A1 (en) | 2011-03-17 |
KR20110036878A (ko) | 2011-04-12 |
JP2011523496A (ja) | 2011-08-11 |
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