EP1483314A1 - Membrane electrolytique conductrice de protons pour des applications a hautes temperatures et utilisation desdites membranes dans des piles a combustible - Google Patents

Membrane electrolytique conductrice de protons pour des applications a hautes temperatures et utilisation desdites membranes dans des piles a combustible

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Publication number
EP1483314A1
EP1483314A1 EP03711950A EP03711950A EP1483314A1 EP 1483314 A1 EP1483314 A1 EP 1483314A1 EP 03711950 A EP03711950 A EP 03711950A EP 03711950 A EP03711950 A EP 03711950A EP 1483314 A1 EP1483314 A1 EP 1483314A1
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EP
European Patent Office
Prior art keywords
membrane
group
acid
polymer
substituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03711950A
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German (de)
English (en)
Inventor
Oemer Uensal
Joachim Kiefer
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BASF Fuel Cell Research GmbH
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Pemeas GmbH
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Publication of EP1483314A1 publication Critical patent/EP1483314A1/fr
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
    • 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
    • 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
    • H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
    • 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
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • 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
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • 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
    • 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 proton-conducting electrolyte membrane for high-temperature applications based on polyvinylphosphonic acid, which can be used in a variety of ways due to its 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
  • a fuel cell usually contains an electrolyte and two electrodes separated by the electrolyte.
  • one of the two electrodes is supplied with a fuel, such as hydrogen gas or a methanol / water mixture, and the other electrode with an oxidizing agent, such as oxygen gas or air, and chemical energy from the fuel oxidation is thereby converted directly into electrical energy. Protons and electrons are formed in the oxidation reaction.
  • the electrolyte is for hydrogen ions, i.e. Protons, but not for reactive ones
  • Fuels such as hydrogen gas or methanol and the oxygen gas are permeable.
  • a fuel cell typically includes a plurality of single cells, so-called MEA 's (membrane electrode assembly), which in each case an electrolyte and two by the
  • Electrolytes contain separate electrodes.
  • Solids such as electrolyte for the fuel cell come
  • Polymer electrolyte membranes or liquids such as phosphoric acid are used. Recently, polymer electrolyte membranes have been used as electrolytes for
  • the first category includes cation exchange membranes consisting of a polymer backbone which covalently binds acid groups
  • the sulfonic acid group changes into an anion with the release of a hydrogen ion and therefore conducts protons.
  • the mobility of the proton and thus the proton conductivity is directly linked to the water content. Due to the very good miscibility of methanol and water, such Cation exchange membranes have a high methanol permeability and are therefore unsuitable for applications in a direct methanol fuel cell. If the membrane dries out, for example as a result of high temperature, the " conductivity of the membrane and consequently the performance of the fuel cell decrease drastically.
  • Cation exchange membranes are thus limited to the boiling point of the water.
  • the humidification of the fuels represents a major technical challenge for the use of polymer electrolyte membrane fuel cells (PEMBZ), in which conventional, sulfonated membranes such as e.g. National used.
  • PEMBZ polymer electrolyte membrane fuel cells
  • perfluorosulfonic acid polymers are used as materials for polymer electrolyte membranes.
  • the perfluorosulfonic acid polymer (such as Nafion) generally has a perfluorocarbon backbone, such as a copolymer of tetrafluoroethylene and trifluorovinyl, and a side chain attached thereto with a sulfonic acid group, such as a side chain with a sulfonic acid group attached to a perfluoroalkylene group.
  • the cation exchange membranes are preferably organic polymers with covalently bonded acid groups, in particular
  • This polymer can be brought into solution as described in US Pat. No. 4,453,991 and then used as an ionomer.
  • Cation exchange membranes are also obtained by filling a porous support material with such an ionomer.
  • Expanded Teflon is preferred as the carrier material (US 5635041).
  • Another perfluorinated cation exchange membrane can, as described in US5422411, be copolymerized from trifluorostyrene and sulfonyl-modified
  • Trifuorostyrol are produced.
  • Composite membranes consisting of a porous carrier material, in particular expanded Teflon, filled with ionomers consisting of such sulfonyl-modified trifluorostyrene copolymers are in
  • US6110616 describes copolymers of butadiene and styrene and their subsequent sulfonation for the production of cation exchange membranes for fuel cells.
  • Another class of partially fluorinated cation exchange membranes can by
  • Radiation plugs and subsequent sulfonation can be produced.
  • a grafting reaction is preferably carried out on a previously irradiated polymer film using styrene.
  • the sulfonation of the side chains then takes place in a subsequent sulfonation reaction.
  • Crosslinking can also be carried out at the same time as the grafting, and the mechanical properties can thus be changed.
  • Polyphenylene sulfide (DE19527435) is known. Ionomers made from sulfonated polyether ketones are described in WO 00/15691.
  • acid-base blend membranes are known which are produced as described in DE19817374 or WO 01/18894 by mixtures of sulfonated polymers and basic polymers.
  • a cation exchange membrane known from the prior art can be mixed with a high-temperature stable polymer.
  • the production and properties of cation exchange membranes consisting of blends of sulfonated PEK and a) polysulfones (DE4422158), b) aromatic polyamides (42445264) or c) polybenzimidazole (DE19851498) are described.
  • the polymer membrane fulfills further essential functions, in particular it must have high mechanical stability and serve as a separator for the two fuels mentioned at the beginning.
  • Membrane is the fact that a fuel cell, in which such a polymer electrolyte membrane is used, can be operated at temperatures above 100 ° C. without the fuels otherwise having to be humidified. This is due to the property of phosphoric acid that the protons can be transported without additional water using the so-called Grotthus mechanism (K.-D. Kreuer, Chem. Mater. 1996, 8, 610-641).
  • CO is produced as a by-product in the reforming of the hydrogen-rich gas from carbon-containing compounds, such as natural gas, methanol or gasoline, or as an intermediate in the direct oxidation of methanol.
  • carbon-containing compounds such as natural gas, methanol or gasoline
  • the CO content of the fuel must be less than 100 ppm at temperatures ⁇ 100 ° C. At temperatures in the range of 150-200 ° C, however, 10,000 ppm CO or more can also be tolerated (NJ Bjerrum et. Al. Journal of Applied Electrochemistry, 2001, 31, 773-779).
  • a major advantage of fuel cells is the fact that the energy of the fuel is converted directly into electrical energy and heat during the electrochemical reaction.
  • the reaction product is water at the cathode. Heat is therefore a by-product of the electrochemical reaction.
  • Electric motors such as For automotive applications or as a diverse replacement for battery systems, the heat must be dissipated to prevent the system from overheating. Additional, energy-consuming devices are then required for cooling, which further reduce the overall electrical efficiency of the fuel cell.
  • the heat can be efficiently used using existing technologies such as Use heat exchanger. High temperatures are aimed at to increase efficiency. If the operating temperature is above 100 ° C and the temperature difference between the ambient temperature and the operating temperature is large, it becomes possible
  • phosphoric acid or polyphosphoric acid is present as an electrolyte, which is not permanently bound to the basic polymer due to ionic interactions and can be washed out by water. As described above, water is reacted at the electrochemical reaction
  • DMBZ direct methanol fuel cell
  • the present invention is therefore based on the object of providing a novel polymer electrolyte membrane in which washing out of the electrolyte is prevented.
  • the operating temperature should be able to be extended from ⁇ 0 ° C to 200 ° C and the system should not require humidification.
  • a fuel cell containing a polymer electrolyte membrane according to the invention is said to be suitable for pure hydrogen and for numerous carbon-containing fuels, in particular natural gas, gasoline, methanol and biomass.
  • the membrane should allow the highest possible activity of the fuels.
  • the methanol oxidation should be particularly high compared to known membranes.
  • a membrane according to the invention should be able to be produced inexpensively and simply. Furthermore, it was the task of the present one
  • a polymer electrolyte membrane should be created which has a high mechanical stability, for example a high modulus of elasticity, high tensile strength, low creep and high fracture toughness.
  • a polymer electrolyte membrane according to the invention has a very low methanol permeability and is particularly suitable for use in a DMBZ. This enables permanent operation of a fuel cell with a variety of fuels such as hydrogen, natural gas, gasoline, methanol or biomass.
  • membranes enable a particularly high activity of these fuels. Due to the high temperatures, the methanol oxidation can take place with high activity.
  • these membranes are suitable for operation in a so-called vapor DMBZ, in particular at temperatures in the range from 100 to 200 ° C.
  • CO is produced as a by-product in the reforming of the hydrogen-rich gas from carbon-containing compounds, e.g. Natural gas, methanol or gasoline or as an intermediate in the direct oxidation of methanol.
  • carbon-containing compounds e.g. Natural gas, methanol or gasoline or as an intermediate in the direct oxidation of methanol.
  • the CO content of the fuel can be greater than 5000 ppm at temperatures above 120 ° C. without the catalytic effect of the Pt catalyst being drastically reduced.
  • 10,000 ppm CO or more can also be tolerated (N.J. Bjerrum et. Al. Journal of Applied Electrochemistry, 2001, 31, 773-779). This leads to significant simplifications of the upstream reforming process and thus to cost reductions for the entire fuel cell system.
  • a membrane according to the invention exhibits a high conductivity over a wide temperature range, which is also achieved without additional moistening. Furthermore, a fuel cell that is equipped with a membrane according to the invention can also be operated at low temperatures, for example at 80 ° C., without the service life of the fuel cell being greatly reduced thereby.
  • membranes of the present invention show high mechanical stability, in particular high modulus of elasticity, high tensile strength, low creep and high fracture toughness. Furthermore, these membranes have a surprisingly long service life.
  • the present invention therefore relates to a stable proton-conducting electrolyte membrane which can be obtained by a process comprising the steps A) swelling of a polymer film with a liquid comprising vinyl-containing phosphonic acid and
  • step A Polymerization of the vinyl-containing phosphonic acid present in step A).
  • the polymer film used in step A) is a film which has a swelling of at least 3% in the liquid containing vinylphosphonic acid.
  • Swelling means an increase in weight of the film of at least 3% by weight.
  • the swelling is preferably at least 5%, particularly preferably at least 10%.
  • Determination of the swelling Q is determined gravimetrically from the mass of the film before swelling m 0 and the mass of the film after the polymerization according to step B), m 2 .
  • Q (m 2 -m 0 ) / mo x 100
  • the swelling is preferably carried out at a temperature above 0 ° C., in particular between room temperature (20 ° C.) and 180 ° C. in a liquid containing vinylphosphonic acid and containing at least 5% by weight of vinylphosphonic acid.
  • the swelling can also be carried out at elevated pressure. The limits result from economic considerations and technical possibilities.
  • the polymer film used for swelling generally has a thickness in the range from 5 to 3000 ⁇ m, preferably 10 to 1500 ⁇ m and particularly preferably.
  • the production of such films from polymers is generally known, some of which are commercially available.
  • the term polymer film means that the film to be used for swelling comprises polymers, wherein this film can contain further generally customary additives.
  • the preferred polymers include polyolefins such as
  • Polyacetal polyoxymethylene, polyether, polypropylene oxide, polyepichlorohydrin, " polytetrahydrofuran, polyphenylene oxide, polyether ketone, polyester, in particular polyhydroxyacetic acid, polyethylene terephthalate, polybutylene terephthalate,
  • Polyhydroxybenzoate polyhydroxypropionic acid, polypivalolactone, polycaprolactone,
  • Polymeric C-S bonds in the main chain for example polysulfide ether,
  • Polyimines polyisocyanides, polyetherimine, polyetherimides, polyaniline, polyaramides,
  • Liquid crystalline polymers especially Vectra and inorganic polymers, for example polysilanes, polycarbosilanes, polysiloxanes,
  • Polysilicic acid Polysilicates, silicones, polyphosphazenes and polythiazyl.
  • high-temperature-stable polymers which have at least one nitrogen, oxygen and / or sulfur atom in one or in different
  • High-temperature stable in the sense of the present invention is a polymer which, as a polymer electrolyte, can be operated continuously in a fuel cell at temperatures above 120 ° C. Permanent means that an inventive
  • Membrane can be operated for at least 100 hours, preferably at least 500 hours at at least 120 ° C., preferably at least 160 ° C., without the output, which can be measured according to the method described in WO 01/18894 A2, being increased by more than 50%, related to the initial performance decreases.
  • the polymers used in step A) are preferably polymers which have a glass transition temperature or Vicat softening temperature VST / A / 50 of at least 100 ° C., preferably at least 150 ° C. and very particularly preferably at least 180 ° C.
  • Polymers which contain at least one nitrogen atom in a repeating unit are particularly preferred. Particularly preferred are polymers which have at least one aromatic ring with at least one nitrogen heteroatom per
  • the aromatic ring is preferably a five- or six-membered ring with one to three nitrogen atoms, which can be fused with another ring, in particular another aromatic ring.
  • Polymers based on polyazole contain 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 (XIII) and / or (XIV) and / or (XV) and / or (XVI) and / or ' (XVI) and / or (XVII) and / or (XVIII) and / or (XIX) and / or (XX) and / or (XXI) and / or (XXII) and / or (XXII) and / or (XXII))
  • Ar are identical or different and for a tetravalent aromatic or heteroaromatic group which can be mononuclear or polynuclear
  • - Ar 1 are identical or different and represent a divalent aromatic or heteroaromatic group which can be mononuclear or polynuclear
  • Ar 2 are the same or different and, for a two or three-membered aromatic or heteroaromatic group which may be mono- or polynuclear
  • Ar 3 are the same or different and for a three-membered aromatic or heteroaromatic group which may be mono- or polynuclear
  • Ar 4 are the same or different and for a three-membered aromatic or heteroaromatic group which may be mono- or polynuclear
  • Ar 5 are the same or different and for a four- membered aromatic or heteroaromatic group which may be mono- or polynuclear
  • Ar 6 is the same or different are and for a divalent aromatic or heteroaromatic group which can be mononuclear or polynuclear
  • Ar 7 are the same or different and, for a divalent aromatic or heteroaromatic group which may be mono- or polynuclear
  • Ar 8 are the same or different and for a trivalent aromatic or heteroaromatic group which may be mono- or polynuclear
  • Ar 9 is the same or are different and are the same or different for a two- or three- or four-membered aromatic or heteroaromatic group, which may be mono- or polynuclear
  • Ar 10 are the same or different and for a di- or tri-bonded aromatic or heteroaromatic group, which may be mono- or polynuclear
  • Ar 11 are the same or different and for a divalent aromatic or heteroaromatic group which may be mononuclear or polynuclear
  • X is the same or different and for oxygen, sulfur or an amino group which has a hydrogen atom, a group having 1-20 carbon atoms, preferably a branched or unbranched alkyl or alkoxy group, or an aryl group as further
  • R is the same or different for hydrogen, an alkyl group and an aromatic
  • Aromatic or heteroaromatic groups preferred according to the invention are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane,
  • Diphenyldimethylmethane bisphenone, diphenylsulfone, thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1, 3,4-oxadiazole, 2,5-diphenyl-1, 3,4-oxadiazole, 1, 3, 4-thiadiazole, 1, 3,4-triazole, 2,5-diphenyl-1, 3,4-triazole, 1, 2,5-triphenyl-1, 3,4-triazole, 1, 2,4-oxadiazole, 1, 2,4-thiadiazole, 1, 2,4-triazole, 1, 2,3-
  • REPLACEMENT SHEET (RULE 18) Triazole, 1, 2,3,4-tetrazole, benzo [b] thiophene, benzo [b] furan, indole, benzo [c] thiophene, benzo [c] furan, isoindole, benzoxazole, benzothiazole, benzimidazole, benzisoxazole, benzisothiazole, Benzopyrazole, benzothiadiazole, benzotriazole, dibenzofuran, dibenzothiophene, carbazole, pyridine, bipyridine, pyrazine, pyrazole, pyrimidine, pyridazine, 1, 3,5-triazine, 1, 2,4-triazine, 1, 2,4,5-triazine, Tetrazine, quinoline, isoquinoline, quinoxaline,
  • Ar 1 , Ar 4 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 , Ar 11 can be ortho-, meta- and para-phenylene.
  • Particularly preferred groups are derived from benzene and biphenylene, which may also be substituted.
  • Preferred alkyl groups are short-chain alkyl groups with 1 to 4
  • Carbon atoms such as B. 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 can be substituted.
  • Preferred substituents are halogen atoms such as. B. fluorine, amino groups, hydroxy groups or short-chain alkyl groups such as. B. methyl or ethyl groups.
  • the polyazoles can also have different recurring units which differ, for example, in their X radical. However, it preferably has only the same X radicals in a recurring unit.
  • the polymer containing recurring azole units is a copolymer or a blend which contains at least two units of the formulas (I) to (XXII) which differ from one another.
  • the polymers can be used as block copolymers (diblock, triblock), statistical copolymers, periodic copolymers and / or alternating polymers are present.
  • 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 repeating azole units.
  • polymers containing recurring benzimidazole units are preferred.
  • Some examples of the extremely useful polymers containing recurring benzimidazole units are represented by the following formulas:
  • n and m is an integer greater than or equal to 10, preferably greater than or equal to 100.
  • the polyazoles used in step A), but especially the polybenzimidazoles, are distinguished by a high molecular weight. Measured as intrinsic viscosity, this is preferably at least 0.2 dl / g, in particular 0.8 to 10 ° dl / g, particularly preferably 1 to 5 dl / g.
  • “Other preferred polyazole polymers are polyimidazoles, polybenzthiazoles, polybenzoxazoles, polytriazoles, polyoxadiazoles, polythiadiazoles, polypyrazoles, polyquinoxalines, poly (pyridines), poly (pyrimidines), and poly (tetrazapyrenes).
  • Celazole from Celanese is particularly preferred, in particular one in which the screened polymer described in German patent application No. 10129458.1 is used.
  • the preferred polymers include polysulfones, in particular polysulfones with aromatic and / or heteroaromatic groups in the main chain.
  • 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 according to ISO 1133.
  • Polysulfones with a Vicat softening temperature VST / A / 50 of 180 ° C. to 230 ° C. are preferred.
  • the number average molecular weight is from
  • Polysulfone-based polymers include, in particular, polymers which have recurring units with linking sulfone groups corresponding to the general formulas A, B, C, D, E, F and / or G:
  • radicals R independently of one another, represent the same or different aromatic or heteroaromatic groups, these radicals being explained in more detail above. These include in particular 1, 2-phenylene, 1, 3-phenylene, 1, 4-phenylene, 4,4'-biphenyl, pyridine, quinoline, naphthalene, phenanthrene.
  • polysulfones preferred in the context of the present invention include homopolymers and copolymers, for example statistical copolymers.
  • Particularly preferred polysulfones comprise repeating units of the formulas H to N:
  • the polysulfones described above can be obtained commercially under the trade names ® Victrex 200 P, ® Victrex 720 P, ® Ultrason E, ® Ultrason S, ® Mindel, ® Radel A, ® Radel R, ® Victrex HTA, ® Astrel and ® Udel.
  • polyether ketones polyether ketone ketones
  • polyether ether ketones polyether ketone ketones
  • polyaryl ketones are particularly preferred. These high-performance polymers are known per se and can be obtained commercially under the trade names Victrex® PEEK TM, ® Hostatec, ® Kadel.
  • Blends containing polyazoles and / or polysulfones are particularly preferred.
  • the use of blends can improve the mechanical properties and reduce the material costs.
  • the polymer film can have further modifications, for example by crosslinking as in German patent application No. 10110752.8 or in WO 00/44816.
  • the polymer film used for swelling consists of a basic polymer and at least one blend component additionally contains a crosslinking agent as described in German patent application No. 10140147.7.
  • the polyazole-containing polymer membranes can also be used as described in German patent applications No. 10117686.4, 10144815.5, 10117687.2. For this purpose, they are freed of the polyphosphoric acid and / or phosphoric acid and used in step A).
  • the polymer membrane according to the invention can also have further additions of fillers and / or auxiliaries.
  • fillers in particular proton-conducting fillers, and additional acids can also be added to the membrane.
  • the addition can take place, for example, in step A).
  • these additives if they are in liquid form, can also be added after the polymerization in step B).
  • Non-limiting examples of proton-conducting fillers are:
  • Sulfates such as: CsHS0 4 , Fe (S0 4 ) 2 , (NH 4 ) 3 H (S0 4 ) 2 , LiHS0 4 , NaHS0 4 , KHS0 4 ,
  • RbS0 4 LiN 2 H 5 S0 4 , NH 4 HS0 4 , phosphates such as Zr 3 (P0 4 ) 4 , Zr (HP0 4 ) 2 , HZr 2 (P0 4 ) 3 , U0 2 P0 4 .3H 2 0, H 8 U0 2 P0 4l
  • Oxides such as Al 2 0 3 , Sb 2 0 5 , Th0 2 , Sn0 2 , Zr0 2> Mo0 3
  • Silicates such as zeolites, zeolites (NH 4 +), layered silicates, framework silicates, H-natrolites, H-mordenites, NH -analyses, NH 4 -sodalites, NH-gallates, H-montmorillonites acids such as HCI0 4 , SbF 5
  • Fillers such as carbides, in particular SiC, Si 3 N, fibers, in particular glass fibers, glass powders and / or polymer fibers, preferably based on polyazoles.
  • the membrane after the polymerization in step B) comprises at most 80% by weight, preferably at most 50% by weight and particularly preferably at most 20% by weight of additives.
  • this membrane can also contain perfluorinated sulfonic acid additives (preferably 0.1-20% by weight, preferably 0.2-15% by weight, very preferably 0.2- 10 wt .-%) included. These additives improve performance, increase proximity to the cathode to increase oxygen solubility and diffusion, and decrease 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, very preferably 0.2- 10 wt .-%) included.
  • These additives improve performance, increase proximity to the cathode to increase oxygen solubility and diffusion, and decrease the adsorption of phosphoric acid and phosphate to platinum.
  • Trifluomethanesulfonic acid potassium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, lithium trifluoromethanesulfonate, ammonium trifluoromethanesulfonate, potassium perfluorohexanesulfonate, sodium perfluorohexanesulfonate, lithium perfluorohexanesulfonate, ammonium perfluorohexanesulfonate, peroxide
  • Potassium nonafluorobutane sulfonate sodium nonafluorobutane sulfonate, lithium nonafluorobutane sulfonate, ammonium nonafluorobutane sulfonate, cesium nonafluorobutane sulfonate, triethylammonium perfluorohexasulfonate and perflurosulfoimide.
  • Vinyl-containing phosphonic acids are known in the art. These are compounds which have at least one carbon-carbon double bond and at least one phosphonic acid group.
  • the two carbon atoms which form the carbon-carbon double bond preferably have at least two, preferably 3, bonds to groups which are of a low steric nature
  • the polyvinylphosphonic acid results from the polymerization product which is obtained by polymerizing the vinyl-containing phosphonic acid alone or with further monomers and / or crosslinking agents.
  • the vinyl-containing phosphonic acid can comprise one, two, three or more carbon-carbon double bonds. Furthermore, the vinyl-containing phosphonic acid can contain one, two, three or more phosphonic acid groups.
  • the vinyl-containing phosphonic acid contains 2 to 20, preferably 2 to 10, carbon atoms.
  • the vinyl-containing phosphonic acid used in step A) is preferably a compound of the formula
  • R is a bond, a C1-C15-alkyl group, C1-C15-alkoxy group,
  • R represents a bond, a C1-C15-alkyl group, C1-C15-alkoxy group, ethyleneoxy group or C5-C20-aryl or heteroaryl group, the above radicals in turn being substituted by halogen, -OH, COOZ, -CN, NZ 2 , Z independently of one another hydrogen, C1-C15-alkyl group, C1-C15-
  • A represents a group of the formulas COOR ⁇ , CN, CONR ⁇ 2 , OR 2 and / or *, wherein R 2 is hydrogen, a C1-C15-alkyl group, C1-C15-alkoxy group, ethyleneoxy group or C5-C20-aryl or heteroaryl group, the above radicals in turn being substituted by halogen, -OH, COOZ, -CN, NZ 2 R is a bond, a divalent C1-C15 alkylene group, divalent C1-C15-
  • Alkyleneoxy group for example ethyleneoxy group or divalent C5-C20-aryl or heteroaryl group, where the above radicals may in turn be substituted with halogen, -OH, COOZ, -CN, NZ 2 , 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 can in turn be substituted by halogen, -OH, -CN, and x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 means.
  • the preferred vinyl-containing phosphonic acids include alkenes which have phosphonic acid groups, such as ethenephosphonic acid, propenephosphonic acid, butenephosphonic acid; Acrylic acid and / or methacrylic acid compounds which have phosphonic acid groups, such as 2-phosphonomethyl-acrylic acid, 2-phosphonomethyl-methacrylic acid, 2-phosphonomethyl-acrylic acid amide and 2-phosphonomethyl-methacrylic acid amide.
  • vinylphosphonic acid ethenephosphonic acid
  • a preferred vinylphosphonic acid has a purity of more than 70%, in particular 90% and particularly preferably more than
  • the vinyl-containing phosphonic acids can also be used in the form of derivatives, which can subsequently be converted into the acid, the conversion to the acid also being able to take place in the polymerized state.
  • derivatives include in particular the salts, the esters, the amides and the halides of the vinyl-containing phosphonic acids.
  • the swollen polymer film produced in step A) preferably comprises at least 10% by weight, in particular at least 50% by weight and particularly preferably at least 70% by weight, based on the total weight, of vinyl-containing phosphonic acid.
  • the swollen polymer film produced in step A) comprises at most 60% by weight of polymer film, in particular at most 50% by weight of polymer film and particularly preferably at most 30% by weight of polymer film, based on the total weight. This size can be determined from the weight gain caused by the swelling.
  • the liquid used for swelling 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
  • the swelling of the membrane can be improved by adding the organic solvent.
  • the content of vinyl-containing phosphonic acid in such solutions is at least 5% by weight, preferably at least 10% by weight, particularly preferably between 10 and 97% by weight.
  • the liquid comprising vinyl-containing phosphonic acid contains further monomers capable of crosslinking. These are in particular compounds which have at least 2 carbon-carbon double bonds. Dienes, trienes, tetraenes, dimethylacrylates, trimethylacrylates, tetramethylacrylates, diacrylates, triacrylates, tetraacrylates are preferred.
  • R is a C1-C15-alkyl group, C5-C20-aryl or heteroaryl group, NR ' , -S0 2 ,
  • PR ' , Si (R ' ) 2 means, where the above radicals may in turn be substituted, R ' independently of one another hydrogen, a C1-C15-alkyl group, C1-C15-
  • the substituents of the above radical R are preferably halogen, hydroxyl, carboxy, carboxyl, carboxyl esters, nitriles, amines, silyl, siloxane radicals.
  • crosslinkers are allyl methacrylate, ethylene glycol dimethacrylate,
  • Diethylene glycol dimethacrylate triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and tetra-, 1, 3-butanediol dimethacrylate.
  • crosslinking agents are optional, these compounds usually being in the range between 0.05 to 30% by weight, preferably 0.1 to 20% by weight, particularly preferably 1 to 10% by weight, based on the vinyl-containing phosphonic acid , can be used.
  • the liquid comprising vinyl-containing phosphonic acid can be a solution, the liquid also being suspended and / or dispersed
  • the viscosity of the liquid comprising vinyl-containing phosphonic acid can be in a wide range, and solvents can be added or the temperature increased to adjust the viscosity.
  • the dynamic viscosity is preferably in the range from 0.1 to 10,000 mPa * s, in particular 0.2 to 2000 mPa * s, these values being able to be measured, for example, in accordance with DIN 53015.
  • the swelling of the film in step A) is preferably carried out at temperatures above 0 ° C., particularly preferably between room temperature (20 ° C.) and 160 ° C. In principle, swelling can also take place at lower temperatures, but the time required for swelling is increased and thus the economy is reduced. If the temperature is too high, the film used for swelling can be damaged.
  • the duration of the swelling depends on the selected temperature. The duration of treatment should be chosen so that the desired swelling is achieved.
  • the polymerization of the vinyl-containing phosphonic acid in step B) is preferably carried out by free radicals.
  • the radical formation can take place thermally, photochemically, chemically and / or electrochemically.
  • a starter solution which contains at least one substance capable of forming radicals can be added to the liquid according to step A).
  • a starter solution can be applied to the swollen sheet-like structure. This can be done by means of measures known per se (e.g. spraying, dipping, etc.) which are known from the prior art.
  • Suitable radical formers include azo compounds, peroxy compounds, persulfate compounds or azoamidines.
  • Non-limiting examples are dibenzoyl peroxide, dicumol peroxide, cumene hydroperoxide, diisopropyl peroxidicarbonate, bis (4-t-butylcyclohexyl) peroxidicarbonate,
  • radical formers can also be used which form radicals when irradiated.
  • the preferred compounds include ⁇ . ⁇ -diethoxyacetophenone (DEAP, Upjon Corp), n-butylbenzoin ether (®Trigonal-14, AKZO) and 2,2-dimethoxy-2-phenylacetophenone (®Igacure 651) and 1-benzoylcyclohexanol ( ( Dlgacure 184), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (®lrgacure 819) and 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-phenylpropan-1-one ( ⁇ Irgacure 2959), which are each commercially available from Ciba Geigy Corp.
  • radical generator % By weight (based on the vinyl-containing phosphonic acid) of radical generator added.
  • the amount of radical generator can be varied depending on the desired degree of polymerization.
  • NIR Near IR, i.e. H.
  • the polymerization can also be carried out by exposure to UV light with a wavelength of less than 400 nm.
  • This polymerization method is known per se and is described, for example, in Hans Joerg Elias, Macromolecular Chemistry, ⁇ .auflage, Volume 1, p.492-51 1; D. R. Arnold, N. C. Baird, J. R. Bolton, J. C. D. Brand, P. W. M Jacobs, P.de Mayo, W. R. Ware, Photochemistry-An Introduction, Academic Press, New York and M.K. Mishra, Radical Photopolymerization of Vinyl Monomers, J. Macromol.
  • the polymerization can also be achieved by the action of ⁇ , ⁇ and / or electron beams.
  • the polymerization of the vinyl-containing phosphonic acid in step B) is preferably carried out at temperatures above room temperature (20 ° C.) and below
  • the polymerization is preferably carried out under normal pressure, but can also be carried out under the action of pressure.
  • the Polymerization leads to solidification of the swollen polymer film according to step A), this solidification being able to be followed by microhardness measurement.
  • the increase in hardness due to the polymerization is preferably at least 20%, based on the hardness of the polymer film swollen in step A).
  • the membranes have high mechanical stability. This size results from the hardness of the membrane, which is determined by means of microhardness measurement in accordance with DIN 50539.
  • the membrane is successively loaded with a Vickers diamond up to a force of 3 mN within 20 s and the depth of penetration is determined.
  • the hardness at room temperature is at least 0.01 N / mm 2 , preferably at least 0.1 N / mm 2 and very particularly preferably at least 1 N / mm 2 , without any intention that this should impose a restriction.
  • the force is then kept constant at 3 mN for 5 s and the creep is calculated from the penetration depth.
  • the creep CHU 0.003 / 20/5 under these conditions is less than 20%, preferably less than 10% and very particularly preferably less than 5%.
  • the module determined by means of microhardness measurement is YHU at least 0.5 MPa, in particular at least 5 MPa and very particularly preferably at least 10 MPa, without this being intended to impose a restriction.
  • the flat structure which is obtained by the swelling of the polymer film and subsequent polymerization, is a self-supporting membrane.
  • the degree of polymerization is preferably at least 2, in particular at least 5, particularly preferably at least 30 repeat units, in particular at least 50 repeat units, very particularly preferably at least 100 repeat units.
  • This degree of polymerization is determined by the number average molecular weight M n , which can be determined by GPC methods. Due to the problems in the
  • Conversion achieved in a comparative polymerization is preferably greater than or equal to 20%, in particular greater than or equal to 40% and particularly preferably greater than or equal to 75%, based on the vinyl-containing phosphonic acid used.
  • the polymer membrane according to the invention contains between 0.5 and 97% by weight of the polymer and between 99.5 and 3% by weight of polyvinylphosphonic acid.
  • the polymer membrane according to the invention preferably contains between 3 and 95% by weight of the polymer and between 97 and 5% by weight of polyvinylphosphonic acid, particularly preferably between 5 and 90% by weight of the polymer and between 95 and 10
  • polyvinylphosphonic acid % By weight polyvinylphosphonic acid.
  • polymer membrane according to the invention can also contain further fillers and / or auxiliaries.
  • the membrane can be crosslinked thermally, photochemically, chemically and / or electrochemically on the surface. This hardening of the membrane surface additionally improves the properties of the membrane.
  • the membrane can be heated to a temperature of at least 150 ° C., preferably at least 200 ° C. and particularly preferably at least 250 ° C.
  • the thermal crosslinking is preferably carried out in the presence of oxygen.
  • the oxygen concentration in this process step is usually in the range from 5 to 50% by volume, preferably 10 to 40% by volume, without any intention that this should impose a restriction.
  • Another method is radiation with ⁇ , ⁇ and / or electron beams.
  • the radiation dose is preferably between 5 and 200 kGy, in particular 10 to 100 kGy. Irradiation can take place in air or under inert gas. This improves the performance properties of the membrane, in particular its durability.
  • the duration of the crosslinking reaction can be in a wide range. In general, this reaction time is in the range from 1 second to 10 hours, preferably 1 minute to 1 hour, without this being intended to impose any restriction.
  • the polymer membrane according to the invention has improved material properties compared to the previously known doped polymer membranes. In particular, they already show an intrinsic conductivity in comparison with known undoped polymer membranes. This is due in particular to an existing polymeric polyvinylphosphonic acid.
  • the intrinsic conductivity of the membrane according to the invention is generally at least 0.001 S / cm, preferably at least 10 mS / cm, in particular at least 15 mS / cm and particularly preferably at least 20 mS / cm at temperatures of 160 ° C. These values are achieved without humidification.
  • the specific conductivity is measured by means of impedance spectroscopy in a 4-pole arrangement in potentiostatic mode and using platinum electrodes (wire, 0.25 mm diameter). The distance between the current-consuming electrodes is 2 cm.
  • the spectrum obtained is calculated using a simple model consisting of a parallel arrangement of an ohmic one
  • the sample cross-section of the membrane doped with phosphoric acid is measured immediately before the sample assembly.
  • the measuring cell is brought to the desired temperature in an oven and controlled via a Pt-100 thermocouple positioned in the immediate vicinity of the sample. After reaching the
  • the sample is kept at this temperature for 10 minutes before starting the measurement.
  • the membranes according to the invention have a particularly low methanol permeability (methanol crossover).
  • This quantity can be expressed in terms of the cross over current density.
  • the passage current density is preferably less than 100 mA / cm 2 , in particular less than 70 mA / cm 2, particularly preferably less than 50 mA / cm 2 and when operating with 0.5 M methanol solution and 90 ° C. in a so-called liquid direct methanol fuel cell very particularly preferably less than 10 mA / cm 2 .
  • the passage current density when operating with a 2 M methanol solution and 160 ° C. in a so-called gaseous direct methanol fuel cell is preferably less than 100 mA / cm 2 , in particular less than 50 mA / cm 2, very particularly preferably less than 10 mA / cm 2 .
  • the amount of carbon dioxide released at the cathode is measured by means of a C0 2 sensor. From the value of the amount of CO 2 thus obtained, as described by P. Zelenay,
  • the passage current density is calculated.
  • Possible areas of application of the polymer membranes according to the invention include use in fuel cells, in electrolysis, in capacitors and in battery systems. Due to their property profile, the polymer membranes are preferably used in fuel cells.
  • the present invention also relates to a membrane electrode assembly which has at least one polymer membrane according to the invention.
  • the membrane electrode assembly has a high performance even with a low content of catalytically active substances, such as platinum, ruthenium or palladium.
  • catalytically active substances such as platinum, ruthenium or palladium.
  • platinum, ruthenium or palladium for this purpose can be provided with a catalytically active layer
  • Gas diffusion layers are used.
  • the gas diffusion layer generally shows electron conductivity.
  • Flat, electrically conductive and acid-resistant structures are usually used for this. These include, for example, carbon fiber papers, graphitized carbon fiber
  • the catalytically active layer contains a catalytically active substance.
  • catalytically active substance include precious metals, in particular platinum, palladium, rhodium,
  • Iridium and / or ruthenium These substances can also be used with one another in the form of alloys. Furthermore, these substances can also be used in alloys with base metals, such as Cr, Zr, Ni, Co and / or Ti. In addition, the oxides of the aforementioned noble metals and / or base metals can also be used
  • the catalytically active compounds are used in the form of particles which preferably have a size in the range from 1 to 1000 nm, in particular 10 to 200 nm and preferably 20 to 100 nm.
  • the catalytically active particles which comprise the aforementioned substances, can be used as metal powder, so-called black noble metal, in particular platinum and / or platinum alloys.
  • black noble metal in particular platinum and / or platinum alloys.
  • Such particles generally have a size in the range from 5 nm to 200 nm, preferably in the range from 10 nm to 100 nm.
  • the metals can also be used on a carrier material.
  • This carrier preferably comprises carbon, which can be used in particular in the form of carbon black, graphite or graphitized carbon black.
  • the metal content of these supported particles based on the total weight of the particles, is generally in the range from 1 to 80% by weight, preferably 5 to 60% by weight and particularly preferably 10 to 50% by weight, without being restricted thereby should.
  • the particle size of the carrier in particular the size of the carbon particles, is preferably in the range from 20 to 100 nm, in particular
  • the size of the metal particles located thereon is preferably in the range from 1 to 20 nm, in particular 1 to 10 nm and particularly preferably 2 to 6 nm.
  • the sizes of the different particles represent mean values of the weight average and can be determined using transmission electron microscopy.
  • the catalytically active particles set out above can generally be obtained commercially.
  • the catalytically active layer can contain conventional additives. These include fluoropolymers such as Polytetrafluoroethylene (PTFE) and surface-active substances.
  • fluoropolymers such as Polytetrafluoroethylene (PTFE) and surface-active substances.
  • the surface-active substances include in particular ionic surfactants, for example fatty acid salts, in particular sodium laurate, potassium oleate; and alkyl sulfonic acids, alkyl sulfonic acid salts, in particular sodium perfluorohexane sulfonate, lithium perfluorohexane sulfonate, ammonium perfluorohexane sulfonate, perfluorohexane sulfonic acid, potassium nonafluorobutane sulfonate, as well as nonionic surfactants, especially ethoxylated fatty alcohols and polyethylene glycols.
  • ionic surfactants for example fatty acid salts, in particular sodium laurate, potassium oleate
  • alkyl sulfonic acids, alkyl sulfonic acid salts in particular sodium perfluorohexane sulfonate, lithium perfluorohexane sulfonate
  • Particularly preferred additives are fluoropolymers, in particular tetrafluoroethylene polymers. According to a particular embodiment of the present invention, the weight ratio of fluoropolymer is too
  • Catalyst material comprising at least one noble metal and optionally one or more support materials, greater than 0.1, this ratio preferably being in the range from 0.2 to 0.6.
  • Catalyst layer has a thickness in the range from 1 to 1000 ⁇ m, in particular from 5 to 500, preferably from 10 to 300 ⁇ m. This value represents an average value that can be determined by measuring the layer thickness in the cross section of images that can be obtained with a scanning electron microscope (SEM).
  • the noble metal content of the catalyst layer is 0.1 to 10.0 mg / cm 2 , preferably 0.3 to 6.0 mg / cm 2 and particularly preferably 0.3 to 3.0 mg / cm 2 , These values can be determined by elemental analysis of a flat sample.
  • a membrane-electrode unit can be produced by hot pressing, among other things.
  • the composite of electrode consisting of gas diffusion layers provided with catalytically active layers, and a membrane are heated to a temperature in the range from 50 ° C. to 200 ° C. and pressed at a pressure of 0.1 to 5 MPa. In general, a few seconds are enough to complete the
  • This time is preferably in the range from 1 second to 5 minutes, in particular 5 seconds to 1 minute.
  • the present invention also relates to a proton-conducting coating according to the invention coated with a catalyst layer
  • a support can be used which is provided with a coating containing a catalyst in order to provide the membrane according to the invention with a catalyst layer.
  • the membrane can be provided with a catalyst layer on one or both sides. If the membrane is only provided with a catalyst layer on one side, the opposite side of the membrane must be pressed with an electrode that has a catalyst layer. If both sides of the membrane are to be provided with a catalyst layer, the following methods can also be used in combination in order to achieve an optimal result.
  • the catalyst layer can be applied by a method in which a catalyst suspension is used. Powders comprising the catalyst can also be used.
  • the catalyst suspension contains a catalytically active substance.
  • the catalyst suspension can contain conventional additives. These include, among others, fluoropolymers such as polytetrafluoroethylene (PTFE), thickeners, in particular water-soluble polymers such as cellulose derivatives, polyvinyl alcohol, polyethylene glycol, and surface-active substances, which were previously explained in connection with the catalytically active layer.
  • fluoropolymers such as polytetrafluoroethylene (PTFE)
  • thickeners in particular water-soluble polymers such as cellulose derivatives, polyvinyl alcohol, polyethylene glycol, and surface-active substances, which were previously explained in connection with the catalytically active layer.
  • the surface-active substances include in particular ionic surfactants, for example fatty acid salts, in particular sodium laurate, potassium oleate; and alkyl sulfonic acids, alkyl sulfonic acid salts, in particular sodium perfluorohexane sulfonate, lithium perfluorohexane sulfonate,
  • ionic surfactants for example fatty acid salts, in particular sodium laurate, potassium oleate
  • alkyl sulfonic acids, alkyl sulfonic acid salts in particular sodium perfluorohexane sulfonate, lithium perfluorohexane sulfonate
  • the catalyst suspension can be liquid at room temperature
  • the catalyst suspension preferably contains 1 to 99% by weight, in particular 10 to 80% by weight, of liquid constituents.
  • the polar, organic solvents include in particular alcohols, such as ethanol, propanol, isopropanol and / or butanol.
  • the organic, non-polar solvents include known thin-film thinners, such as thin-film thinner 8470 from DuPont, which
  • Particularly preferred additives are fluoropolymers, in particular tetrafluoroethylene polymers. According to a particular embodiment of the present invention, the weight ratio of fluoropolymer is too
  • Catalyst material comprising at least one noble metal and optionally one or more support materials, greater than 0.1, this ratio preferably being in the range from 0.2 to 0.6.
  • the catalyst suspension can be applied to the process according to the invention using customary methods
  • Membrane are applied.
  • various methods are known with which the suspension can be applied.
  • Processes for coating films, fabrics, textiles and / or papers, in particular spray processes, are suitable and printing processes, such as, for example, stencil and screen printing processes, inkjet processes, roller application, in particular anilox rollers, slot nozzle application and doctor blades.
  • the particular process and the viscosity of the catalyst suspension depend on the hardness of the membrane.
  • the viscosity can be influenced by the solids content, in particular the proportion of catalytically active particles, and the proportion of additives.
  • the viscosity to be set depends on the method of application of the catalyst suspension, the optimum values and their determination being familiar to the person skilled in the art.
  • the binding of catalyst and membrane can be improved by heating and / or pressing.
  • the catalyst layer is applied using a powder process.
  • a powder process is a powder process.
  • Catalyst powder used which may contain additional additives, which have been exemplified above.
  • Spray and sieve processes can be used to apply the catalyst powder.
  • the powder mixture is sprayed onto the membrane using a nozzle, for example a slot nozzle.
  • the membrane provided with a catalyst layer is then heated in order to improve the connection between the catalyst and membrane. Heating can take place, for example, using a hot roller.
  • Such methods and devices for applying the powder are, inter alia, in
  • the catalyst powder is applied to the membrane with a vibrating sieve.
  • a device for applying a catalyst powder to a membrane is described in WO 00/26982. After applying the
  • Catalyst powder can improve the binding of catalyst and membrane by heating.
  • the membrane provided with at least one catalyst layer can be heated to a temperature in the range from 50 to 200 ° C., in particular 100 to 180 ° C.
  • the catalyst layer can be applied by a method in which a coating containing a catalyst is applied to a support and then containing the coating on the support transfers a catalyst to the membrane according to the invention.
  • a method is described by way of example in WO 92/15121.
  • the carrier provided with a catalyst coating can be produced, for example, by producing a previously described catalyst suspension. This catalyst suspension is then applied to a carrier film, for example made of polytetrafluoroethylene. After the suspension has been applied, the volatile constituents are removed.
  • the coating containing a catalyst can be transferred, inter alia, by hot pressing.
  • the composite comprising a catalyst layer and a membrane and a carrier film is heated to a temperature in the range from 50 ° C. to 200 ° C. and pressed at a pressure of 0.1 to 5 MPa. In general, a few seconds are sufficient to connect the catalyst layer to the membrane. This time is preferably in the range from 1 second to 5 minutes, in particular 5 seconds to 1 minute.
  • the catalyst layer has a thickness in the range from 1 to 1000 ⁇ m, in particular from 5 to 500, preferably from 10 to 300 ⁇ m.
  • This value represents an average value that can be determined by measuring the layer thickness in the cross section of images that can be obtained with a scanning electron microscope (SEM).
  • the membrane provided with at least one catalyst layer comprises 0.1 to 10.0 mg / cm 2 , preferably 0.3 to 6.0 mg / cm 2 and particularly preferably 0.3 to 3.0 mg / cm 2 . These values can be determined by elemental analysis of a flat sample.
  • the membrane obtained can be crosslinked thermally, photochemically, chemically and / or electrochemically.
  • This hardening of the membrane additionally improves the properties of the membrane.
  • the membrane can be heated to a temperature of at least 150 ° C., preferably at least 200 ° C. and particularly preferably at least 250 ° C.
  • the crosslinking takes place in the presence of oxygen. The oxygen concentration is at this
  • the method step is usually in the range from 5 to 50% by volume, preferably 10 to 40% by volume, without any intention that this should impose a restriction.
  • Another method is radiation with ⁇ , ⁇ and / or electron beams.
  • the radiation dose is preferably between 5 and 200 kGy, in particular 10 to 100 kGy. Irradiation can take place in air or under inert gas. This improves the performance properties of the membrane, in particular its durability.
  • the duration of the crosslinking reaction can be in a wide range. In general, this reaction time is in the range from 1 second to 10 hours, preferably 1 minute to 1 hour, without this being intended to impose any restriction.
  • the polymer membrane coated with catalyst according to the invention has improved material properties compared to the previously known doped polymer membranes. In particular, they perform better than known doped polymer membranes. This is due in particular to better contact between the membrane and the catalyst.
  • the membrane according to the invention can be connected to a gas diffusion layer. If the membrane is provided with a catalyst layer on both sides, the gas diffusion layer does not have to have a catalyst before pressing.
  • a membrane-electrode unit according to the invention shows a surprisingly high power density.
  • preferred membrane electrode units have a current density of at least 0.1 A / cm 2 , preferably 0.2 A / cm 2 , particularly preferably 0.3 A / cm 2 . This current density is achieved in operation with pure hydrogen at the anode and air (approx. 20 vol.% Oxygen, approx.
  • the stoichiometry is less than or equal to 2, preferably less than or equal to 1.5, very particularly preferably less than or equal to 1.2.
  • the catalyst layer has a low noble metal content.
  • the noble metal content of a preferred catalyst layer which is comprised by a membrane according to the invention is preferably at most 2 mg / cm 2 , in particular at most 1 mg / cm 2 , very particularly preferably at most 0.5 mg / cm 2 .
  • one side of a membrane has a higher metal content than the opposite side of the membrane. The metal content on one side is preferably at least twice as high as the metal content on the opposite side.
  • a catalytically active layer can be applied to the membrane according to the invention and this can be connected to a gas diffusion layer.
  • a membrane is formed in accordance with steps A) and B) and the catalyst is applied.
  • the catalyst can be applied before or together with the starter solution.
  • the membrane according to steps A) and B) can also be formed on a support or a support film which already has the catalyst. After removing the carrier or the carrier film is the
  • the present invention also relates to a membrane-electrode unit, which may contain at least one polymer membrane according to the invention
  • Combination with another polymer membrane based on polyazoles or a polymer blend membrane contains.
  • Possible areas of application of the polymer membranes according to the invention include use in fuel cells, in electrolysis, in
  • the polymer membranes are preferably used in fuel cells.
  • Examples 1 and 2 A film of high molecular weight polybenzimidazole, which was produced from a PBI-DMAc solution according to DE 10052237.8 and by selecting suitable polymer granules according to DE 10129458.1, is available in a solution consisting of 10 parts by weight of vinylphosphonic acid (97%) from Clariant and one part by weight of an aqueous solution containing 5% by weight of 2,2'-azo-bis- (isobutyric acid amidine) dihydroxychloride at room temperature. After different insertion times, samples are taken and then treated in the oven at 80 ° C for 1 hour. The conductivity at 160 ° C. is determined on the membrane thus obtained by means of impedance spectroscopy.
  • the mechanical properties were determined after the thermal treatment by means of microhardness measurement.
  • the membrane is successively loaded with a Vickers diamond up to a force of 3 mN within 20 s and the depth of penetration is determined. The force is then kept constant at 3 mN for 5 s and the creep is calculated from the penetration depth.
  • the properties of these membranes are summarized in Table 1.
  • Table 1 Properties of PBI films after swelling with a solution containing vinylphosphonic acid at room temperature
  • a film of high molecular weight polybenzimidazole which was produced from a PBI-DMAc solution according to DE 10052237.8 and by selecting suitable polymer granules according to DE 10129458.1, is first washed at 45 ° C. for 30 minutes as described in DE10110752.8. Excess water is then dabbed off the PBI film pretreated in this way with a paper towel. This undoped PBI film is then dissolved in a solution consisting of 10 parts by weight of vinylphosphonic acid (97%) from Clariant and one part by weight of an aqueous solution containing 5% by weight of 2,2'-azobis (isobutyric acid amidine) dihydroxychloride at 45 ° C inserted.
  • the weight gain, the increase in thickness and the increase in area are then determined after different insertion times. Then the membrane is treated in the oven at 80 ° C for 1 hour. The conductivity at 160 ° C. is determined on the membrane thus obtained by means of impedance spectroscopy. The properties of these membranes are summarized in Table 2.
  • Table 2 Properties of washed doped PBI films after swelling with a solution containing vinylphosphonic acid at elevated temperatures
  • Examples 6 to 9 A film of high molecular weight polybenzimidazole, which according to a PBI-DMAc solution. DE 10052237.8 and by selecting suitable polymer granules according to DE 10129458.1 is first washed as described in DE10110752.8 at 45 ° C for 30 min. Excess water is then dabbed off the PBI film pretreated in this way with a paper towel. This undoped PBI film is then placed in a solution consisting of 1
  • Table 3 Properties of washed, doped PBI films after swelling with a solution containing vinylphosphonic acid and different concentrations of the starter 2,2'-azo-bis- (isobutyric acid amidine) dihydroxychloride
  • the mechanical properties (modulus of elasticity, hardness HU and creep Cr) were determined after the thermal treatment by means of microhardness measurement, the data obtained being set out in Table 3a.
  • a film of high molecular weight polybenzimidazole which was produced from a PBI-DMAc solution according to DE 10052237.8 and by selecting suitable polymer granules according to DE 10129458.1, is first washed at 45 ° C. for 30 minutes as described in DE10110752.8. Excess water is then dabbed off the PBI film pretreated in this way with a paper towel. This undoped PBI film is then placed in a solution consisting of 1 part by weight of water and 10 parts by weight of vinylphosphonic acid (97%) available from Clariant at 80 ° C. for 1.5 to 2.5 hours.
  • the PBI film thus pre-swollen is then 24 hours at room temperature in a solution consisting of 10 parts by weight of vinylphosphonic acid (97%) available from Clariant and one part by weight of an aqueous solution containing 0.1% by weight of 2,2'-azo-bis- (isobutyric acid amidine) dihydroxy chloride. Then the increase in thickness and the increase in area are determined.
  • the membrane is then treated in the oven at 80 ° C. for 1 hour and the weight gain is determined.
  • the conductivity at 160 ° C. is determined on the membrane thus obtained by means of impedance spectroscopy.
  • Table 4 The mechanical properties of these membranes with a weight gain between 500 - 600 wt% vary from 0.4 - 0.7 MPa for the hardness HU, 7-14 MPa for the modulus of elasticity and 2-4% for creep.
  • a film of polybenzimidazole which was produced from a PBI-DMAc solution according to DE 10052237.8 and by adding a crosslinker and a blend component according to DE 10140147.7, is first washed at 45 ° C. for 30 minutes as described in DE10110752.8. Excess water is then dabbed off from the PBI film pretreated in this way using a paper towel. This undoped PBI film is then placed in a solution consisting of 1 Parts by weight of water and 10 parts by weight of vinylphosphonic acid (97%) available from Clariant at 70 ° C. for 3 hours.
  • the PBI film thus pre-swollen is then 24 hours at room temperature in a solution consisting of 10 parts by weight of vinylphosphonic acid (97%) available from Clariant and one part by weight of an aqueous solution containing 0.1% by weight of 2,2'-azo-bis- (Isobutyric acid amidine) Dihydroxychloride inserted. Then the increase in thickness and the increase in area are determined.
  • the membrane is then treated in the oven at 80 ° C. for 1 hour and the weight gain is determined.
  • the conductivity at 160 ° C. on the membrane thus obtained is determined by means of impedance spectroscopy.
  • Table 5 The properties of these membranes are summarized in Table 5.
  • Table 5 Properties of a high-strength PBI membrane after swelling with a solution containing vinylphosphonic acid
  • the mechanical properties of such a membrane were determined by means of microhardness measurement.
  • the membrane has a hardness HU of 1.2 N / mm 2 , a modulus of elasticity, Y, of 28 MPa and a creep, Cr, of 9.5%.
  • a film of high molecular weight polybenzimidazole which was prepared from a PBI-DMAc solution according to DE 10052237.8 and by selecting appropriate polymer granules according to DE 10129458.1, is first described as shown in DE10110752.8 at 45 C C for 30 min washed. Excess water is then dabbed off from the PBI film pretreated in this way using a paper towel. This undoped PBI film is then placed in a solution consisting of 1 part by weight of water and 10 parts by weight of vinylphosphonic acid (97%) available from Clariant at 70 ° C. for 2 hours. The PBI film thus pre-swollen is then available for 24 hours at room temperature in a solution consisting of 10 parts by weight of vinylphosphonic acid (97%) from the company
  • Examples 20 to 23 A film of high molecular weight polybenzimidazole, which was produced from a PBI-DMAc solution according to DE 10052237.8 and by selecting suitable polymer granules according to DE 10129458.1, is first washed at 45 ° C. for 30 minutes as described in DE10110752.8. Excess water is then dabbed off the PBI film pretreated in this way with a paper towel. This undoped PBI film is then placed in a solution consisting of 1
  • a first step the membranes were added to water at room temperature, stirred for 10 minutes, and the acid released after removal of the membrane was determined by titration from consumption with 0.1 molar sodium hydroxide solution up to the second titration point.
  • the membrane sample is treated in a beaker with boiling water for 30 minutes. The acid released in this way is again determined by titration from the consumption with 0.1 molar sodium hydroxide solution up to the second titration point.
  • the membrane pretreated in this way is boiled again for 30 minutes Treated water and the acid thus released is determined again by titration.
  • Table 7b The results obtained are set out in Table 7b.
  • the consumption of 0.1 molar sodium hydroxide solution up to the second end point is 28-36 ml in the first step, less than 2 ml in the second step and less than 0 in the third step , 2 ml.
  • a membrane electrode assembly is produced by pressing a membrane from Example 11 and 2 electrodes with a Pt content of 1 mg / cm 2 at the anode and 2 mg / cm 2 at the cathode.
  • a temperature of 140 ° C., a pressing time of 30 s and a pressure of 4 N / mm 2 are selected for pressing.
  • a MEA thus produced with an active area of 10 cm 2 is in a single cell at 160 ° C without
  • Humidification operated. After 16 hours of operation with a hydrogen flow of 5.7 l / h and an air flow of 22.5 l / h, the following performance characteristics result at an absolute pressure p a of 1 bar and 2 bar.
  • a membrane electrode assembly is produced by pressing a membrane from Example 21 irradiated with 66 kGy and 2 electrodes with a Pt / Ru content of 1.5 mg / cm 2 at the anode and 4 mg / cm 2 Pt black at the Cathode.
  • a temperature of 120 ° C, a pressing time of 30s and a force of 5 kN are selected for pressing.
  • a MEA thus produced with an active area of 30 cm 2 is first kept at rest potential at 90 ° C. with 0.5 molar methanol solution and a flow of 20 ml / min for 16 hours. The methanol crossover is measured by means of a CO 2 sensor at the cathode outlet.
  • the methanol crossover is 70 mA / cm 2 compared to 100 mA / cm 2 of an identical cell containing a Nafion117 membrane.
  • the cell resistance is 355 mOhm * cm 2 compared to 144 mOhm * cm 2 of an identical cell containing a Nafion 117 membrane.
  • the resting potential is 780 mV compared to 730 mV with 100 mA / cm 2 of an identical cell containing a Nafion117 membrane. The following performance data is then obtained with this direct methanol cell.
  • Example 26 A membrane electrode unit is produced by pressing a membrane from Example 11 and 2 electrodes with a Pt content of 1 mg / cm 2 at the anode and 2 mg / cm 2 at the cathode. A temperature of 140 ° C., a pressing time of 30 s and a pressure of 4 N / mm 2 are selected for pressing. The active area is 30 cm 2 . A MEA produced in this way is then treated with electron radiation and a radiation dose of 99 kGy. A MEA produced in this way with an active area of 30 cm 2 is first kept at rest potential at 90 ° C. with 0.5 molar methanol solution and a flow of 20 ml / min for 16 hours.
  • the methanol crossover is measured using a CO 2 sensor at the cathode outlet.
  • the methanol crossover is 9 mA / cm 2 .
  • the cell resistance is 944 mOhm * cm 2 .
  • the resting potential is 750 mV. After 1 hour of operation at
  • Example 27 A film made of high molecular weight polybenzimidazole, which consists of a PBI-DMAc solution according to DE 10052237.8 and by selection of suitable polymer granules was produced according to DE 10129458.1, is first washed as described in DE10110752.8 at 45 ° C for 30 min. Excess water is then dabbed off from the PBI film pretreated in this way using a paper towel.
  • This undoped PBI film is then dissolved in a solution consisting of 50 g vinylphosphonic acid (97%) from Clariant, 4,463 g bisphenol-A epoxy diacrylate (CN-120 from Sartomer Inc.) and 2 g 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 from Ciba-Geigy) for 2 hours at 70 ° C. in a dark chamber.
  • the membrane so swollen is placed between 2 paper towels and unrolled 10 times with a 250 g cylinder.
  • the film is then placed between 2 transparent films made of oriented polypropylene and excess air is removed by rolling it several times as described above.
  • This laminate is then transferred to a chamber and there each side is irradiated for 1 minute with a 300 W mercury arc lamp of the H3T7 type from General Electric and this process is repeated once.
  • the polypropylene film is carefully removed from the membrane. This process is facilitated by gentle heating with a hot air dryer. A typical weight gain after this treatment is 500 wt%.

Abstract

Membrane électrolytique conductrice de protons qui peut être obtenue par un procédé consistant (A) à faire gonfler une feuille polymère à l'aide d'un liquide contenant de l'acide phosphonique renfermant du vinyle et (B) à polymériser l'acide phosphonique renfermant du vinyle présent dans le liquide utilisé à l'étape (A). En raison de ses excellentes propriétés chimiques et thermiques, la membrane selon la présente invention peut être utilisée dans de nombreuses applications et convient particulièrement en tant que membrane polymère (PEM) dans les piles à combustibles PEM.
EP03711950A 2002-03-05 2003-03-04 Membrane electrolytique conductrice de protons pour des applications a hautes temperatures et utilisation desdites membranes dans des piles a combustible Withdrawn EP1483314A1 (fr)

Applications Claiming Priority (3)

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DE10209419A DE10209419A1 (de) 2002-03-05 2002-03-05 Verfahren zur Herstellung einer Polymerelektrolytmembran und deren Anwendung in Brennstoffzellen
DE10209419 2002-03-05
PCT/EP2003/002399 WO2003074596A1 (fr) 2002-03-05 2003-03-04 Membrane electrolytique conductrice de protons pour des applications a hautes temperatures et utilisation desdites membranes dans des piles a combustible

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US20050084727A1 (en) 2005-04-21
JP2005527073A (ja) 2005-09-08
WO2003074596A1 (fr) 2003-09-12
KR20100065402A (ko) 2010-06-16
CN100408616C (zh) 2008-08-06
US7846983B2 (en) 2010-12-07
DE10209419A1 (de) 2003-09-25
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CN1649944A (zh) 2005-08-03
KR101016931B1 (ko) 2011-02-25

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