WO2006008157A1 - Membran-elektrodeneinheiten und brennstoffzellen mit hoher lebensdauer - Google Patents
Membran-elektrodeneinheiten und brennstoffzellen mit hoher lebensdauer Download PDFInfo
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- WO2006008157A1 WO2006008157A1 PCT/EP2005/007945 EP2005007945W WO2006008157A1 WO 2006008157 A1 WO2006008157 A1 WO 2006008157A1 EP 2005007945 W EP2005007945 W EP 2005007945W WO 2006008157 A1 WO2006008157 A1 WO 2006008157A1
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- H—ELECTRICITY
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- 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
- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
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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
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
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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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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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
- H01M8/1023—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
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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
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
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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
- H01M8/102—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]
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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
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
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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
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
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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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- 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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- 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
- H01M8/1083—Starting from polymer melts other than monomer melts
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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
- H01M2008/1095—Fuel cells with polymeric electrolytes
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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 improved membrane electrode assemblies and high-life fuel cells comprising two electrochemically active electrodes separated by a polymer electrolyte membrane.
- PEM polymer electrolyte membrane
- This document also describes a first method for producing membrane-electrode assemblies.
- two electrodes are pressed onto the membrane, which cover only a part of the two main surfaces of the membrane.
- a PTFE seal is pressed in the cell, so that the gas chambers of anode and cathode are sealed against each other and against the environment.
- a membrane electrode assemblies prepared in this way has a high durability only with very small cell areas of 1 cm 2 . If larger cells, in particular made with an area of at least 10 cm 2 , the shelf life of the cells at temperatures greater than 150 0 C is limited to less than 100 hours.
- Another high-temperature fuel cell is disclosed in JP-A-2001-608282.
- an electrode-membrane unit which is provided with a polyimide seal.
- the problem with this structure is that for sealing two membranes are necessary, between which a sealing ring made of polyimide is provided. Since the thickness of the membrane for technical reasons must be chosen as small as possible, the thickness of the sealing ring between the two membranes described in JP-A-2001 -196082 is extremely limited. In long-term experiments it has been found that such a structure is also not stable over a period of more than 1000 hours.
- a membrane-electrode unit which contains polyimide layers for sealing.
- these layers have a uniform thickness so that the edge region is thinner than the region that is in contact with the membrane.
- the aforementioned membrane-electrode assemblies are generally connected to planar bipolar plates into which channels are milled for gas flow. Since the membrane-electrode assemblies are in part of greater thickness than the seals previously described, a seal is usually placed between the seal of the membrane-electrode assemblies and the bipolar plates, usually made of PTFE.
- the cells should show a long service life at temperatures above 100 ° C.
- the single cells should show consistent or improved performance at temperatures above 100 ° C for a long time.
- the fuel cells should have a high quiescent voltage and a low gas penetration (gas crossover) after a long period of operation.
- the fuel cells should be able to be used in particular at operating temperatures above 100 ° C. and do without additional fuel gas moistening.
- the membrane Electrode units can withstand permanent or alternating pressure differences between anode and cathode.
- the fuel cell should have a high voltage even after a long time and be operated at low stoichiometry.
- the MEE should be robust against different operating conditions (T, p, geometry, etc.) to increase overall reliability.
- the subject of the present invention is a membrane electrode assembly comprising two gas diffusion layers, each in contact with a catalyst layer separated by a polymer electrolyte membrane, the polymer electrolyte membrane having an inner region in contact having a catalyst layer, and having an outer region not provided on the surface of a gas diffusion layer, characterized in that the thickness of all components of the outer region is 50 to 100% based on the thickness of all components of the inner region, wherein the thickness of the outer region at a temperature of 80 0 C and a pressure of 5 N / mm 2 over a period of 5 hours at most by 5%, said decrease in thickness is determined after a first pressing, which at a pressure of 5 N / mm 2 over a period of 1 minute.
- Polymer-electrolyte membranes suitable for the purposes of the present invention are known per se.
- membranes containing phosphonic acid groups which are obtainable by polymerization of monomers comprising phosphonic acid groups are used for this purpose
- Such polymer membranes are obtainable inter alia by a process comprising the steps
- 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. These groups include, among others, hydrogen atoms and halogen atoms, especially 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 in step A) are preferably compounds of the formula
- R represents a bond, a C1-C15 double-alkylene group, C1-C15 double-alkyleneoxy group, for example, ethyleneoxy group, or a C5-C20 double-aryl or heteroaryl group, the above groups themselves being halogen, -OH, COOZ, -CN 1 NZ 2 can be substituted,
- Z independently of one another are hydrogen, C 1 -C 15 -alkyl group, C 1 -C -alkoxy group, for example ethyleneoxy group, or C 5 -C 20 -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
- R represents a bond, a C1-C15 divalent alkylene group, C1-C15 divalent alkylenoxy group, for example ethyleneoxy group, or a divalent C5-C20-aryl or heteroaryl group, the above radicals themselves being in turn halogen, -OH, COOZ, -CN , NZ 2 can be substituted,
- Z is independently of one another hydrogen, C1-C15-alkyl group, C1-C15-alkoxy group, for example ethyleneoxy group or C5-C20-aryl or heteroaryl group, where the above radicals may in turn be substituted by halogen, -OH, -CN, and x is an integer Number 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 means and / or the formula
- 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, for example ethyleneoxy group or C 5 -C 20 aryl or Heteroaryl group, wherein the above radicals may in turn 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 is independently of one another hydrogen, C1-C15-alkyl group, C1-C15-alkoxy group, for example 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 Number 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 having phosphonic acid groups, such as For example, 2-phosphonomethyl-acrylic acid, 2-phosphonomethyl-methacrylic acid, 2-phosphonomethyl-acrylamide and 2-phosphonomethyl-methacrylamide.
- vinylphosphonic acid ethenphosphonic acid
- ethenphosphonic acid such as is obtainable, for example, from Aldrich or Clariant GmbH
- 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 composition prepared 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 composition, of monomers comprising phosphonic acid groups.
- the composition prepared 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 solutions is generally at least 5% by weight, preferably at least 10% by weight, particularly preferably between 10 and 97% by weight.
- ionomer compositions comprising sulfonic acid groups for the preparation of the polymers and / or phosphonic acid groups comprising phosphonic acid groups.
- 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.
- 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
- 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 is independently of one another hydrogen, C1-C15-alkyl group, C1-C15-alkoxy group, for example 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 Number 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 means y is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10
- 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 is independently of one another hydrogen, C1-C15-alkyl group, C1-C15-alkoxy group, for example 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 Number 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, for example ethyleneoxy group or C 5 -C 20 aryl or Heteroaryl group, wherein the above radicals may in turn 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 is independently of one another hydrogen, C1-C15-alkyl group, C1-C15-alkoxy group, for example 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 Number 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.
- 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 composition according to step A). In addition, the monomers capable of crosslinking can also be applied to the planar structure according to step C).
- 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 ,
- R ' independently of one another are hydrogen, a C1-C15-alkyl group, C1-C15-
- 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.
- Ebacryl N '
- N-methylenebisacrylamide carbinol, butadiene
- isoprene chloroprene
- divinylbenzene and / or bisphenol A dimethylacrylate.
- crosslinking agents are optional, these compounds customary 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.
- the polymer membranes of the present invention may comprise, in addition to the polymers comprising phosphonic acid groups, further polymers (B) which are not obtainable by polymerization of monomers comprising phosphonic acid groups.
- a further polymer (B) may be added.
- This polymer (B) may be dissolved, dispersed or suspended, inter alia.
- Preferred polymers (B) include, but are not limited to, polyolefins such as poly (chloroprene), polyacetylene, polyphenylene, poly (p-xylylene), polyarylmethylene, polystyrene, polymethylstyrene, polyvinyl alcohol, polyvinyl acetate, polyvinyl ether, polyvinylamine, poly (N-vinylacetamide), Polyvinylimidazole, polyvinylcarbazole, polyvinylpyrrolidone, polyvinylpyridine, polyvinylchloride, polyvinylidene chloride, polytetrafluoroethylene, polyvinyldifluoride, polyhexafluoropropylene, polyethylene tetrafluoroethylene, copolymers of
- Polymers C-S bonds in the main chain for example, polysulfide ethers, polyphenylene sulfide, polyethersulfone, polysulfone, polyether ether sulfone, polyarylene sulfone, polyphenylene sulfone, polyphenylene sulfide sulfone, poly (phenylsulfide-1, 4-phenylene;
- Polymeric CN bonds in the backbone for example polyimines, polyisocyanides, polyetherimine, polyetherimides, poly (trifluoro-methyl-bis (phthalimido) -phenyl, polyaniline, polyaramides, polyamides, polyhydrazides, polyurethanes, polyimides, polyazoles, polyazole ether ketone, polyureas, polyazines; Liquid crystalline polymers, especially Vectra and
- Inorganic polymers for example polysilanes, polycarbosilanes, polysiloxanes, polysilicic acid, polysilicates, silicones, polyphosphazenes and polythiazyl. These polymers can be used singly or as a mixture of two, three or more polymers.
- polymers containing at least one nitrogen atom, oxygen atom and / or sulfur atom in a repeat unit Particular preference is given to polymers which contain at least one aromatic ring having at least one nitrogen, oxygen and / or sulfur heteroatom per repeat unit.
- polymers based on polyazoles are particularly preferred. These basic polyazole polymers contain at least one aromatic ring with at least one nitrogen heteroatom per repeat unit.
- the aromatic ring is preferably a five- or six-membered ring having one to three nitrogen atoms which may be fused to another ring, especially another aromatic ring.
- Polymers based on polyazole generally 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 (XII) 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 (XXII) and / or (XVIII) and / or (XIX) and / or (XX) and / or (XXI) and / or (XXII) and / or (XXII))
- 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 is the same or are 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 is the same or are different and represent a trivalent aromatic or heteroaromatic group which may be mononuclear or polynuclear
- Ar 5 are the same or different and represent a administratige aromatic or heteroaromatic group which may be mononuclear or polynuclear
- Ar 6 same or different and represent a divalent aromatic or heteroaromatic group
- the egg may be mono- or polynuclear
- Amino group which is 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 is identical or different for hydrogen, an alkyl group and an aromatic
- Group is the same or different hydrogen, an alkyl group and an aromatic group is provided with the proviso that R in formula XX is a divalent 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, 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-triazole, 1, 2,3,4-tetrazole, benzo [b] thiophene,
- 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. As 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 polymer containing recurring azole units is a copolymer or a blend containing at least two units of the formulas (I) to (XXII) which differ from each other.
- the polymers can be present as block copolymers (diblock, triblock), random copolymers, periodic copolymers and / or alternating polymers.
- the polymer containing recurring azole units is a polyazole which contains 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 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.
- polyazole polymers are polyimidazoles, polybenzimidazole ether ketone, polybenzothiazoles, polybenzoxazoles, polytriazoles, polyoxadiazoles, polythiadiazoles, polypyrazoles, polyquinoxalines, poly (pyridines), poly (pyrimidines), and poly (tetrazapyrenes).
- Preferred polyazoles are characterized by a high molecular weight. This is especially true for the polybenzimidazoles. Measured as intrinsic viscosity, this is preferably at least 0.2 dl / g, preferably 0.7 to 10 dl / g, in particular 0.8 to 5 dl / g.
- Celazole is particularly preferred from Celanese.
- the properties of the polymer film and polymer membrane can be improved by screening the starting polymer as described in German Patent Application No. 10129458.1.
- Aromatic sulfonic acid groups are groups in which the sulfonic acid group (-SO 3 H) is covalently bonded to an aromatic or heteroaromatic group.
- the aromatic group may be part of the backbone of the polymer or part of a side group, with polymers having aromatic groups in the backbone being preferred.
- the sulfonic acid groups can also be used in many cases in the form of the salts.
- derivatives for example esters, in particular methyl or ethyl esters, or halides of the sulfonic acids, which are converted into the sulfonic acid during operation of the membrane.
- 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, preferably 0.5 to 2.5. This value is determined by the so-called ion exchange capacity (IEC).
- IEC ion exchange capacity
- 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.
- the sulfonated polymer is first treated for 2 hours in boiling water. Excess water is then dabbed off and the sample for 15 hours at 160 0 C in a vacuum drying cabinet at p ⁇ 1 mbar. Then the dry weight of the membrane is determined.
- the thus dried polymer is then dissolved in DMSO at 80 0 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 having sulfonic acid groups covalently bonded to aromatic groups are known in the art.
- polymers containing aromatic 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. In this case, the sulfonation conditions can be selected so that a low degree of sulfonation is formed (DE-A-19959289).
- perfluorinated polymers can be prepared as described in US-A-5422411 by copolymerization of trifluorostyrene and sulfonyl-modified trifuorostyrene.
- high temperature stable thermoplastics which have sulfonic acid groups attached to aromatic groups.
- such polymers have aromatic groups in the main chain.
- sulfonated polyether ketones DE-A-4219077, WO96 / 01177
- sulfonated polysulfones J. Membr. Be. 83 (1993) p.211
- sulfonated polyphenylene sulfide D EA-19527435
- polymers with sulfonic acid groups bound to aromatics described above can be used individually or as a mixture, particular preference being given to mixtures having polymers with aromatics in the main chain.
- Preferred polymers include polysulfones, especially polysulfone having aromatics in the backbone.
- 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 weight ratio of polymer having sulfonic acid groups covalently bonded to aromatic groups to monomers comprising phosphonic acid groups may range from 0.1 to 50, preferably from 0.2 to 20, more preferably from 1 to 10.
- Preferred polymers include polysulfones, especially polysulfone having aromatic and / or heteroaromatic groups in the backbone.
- 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.
- polysulfones having a Vicat softening temperature VST / A / 50 of 180 0 C to 230 0 C are preferred.
- the number average molecular weight of the polysulfones is greater than 30,000 g / mol.
- the polymers based on polysulfone 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 or different, represent an aromatic or heteroaromatic group, these radicals having been explained in more detail above.
- these radicals include in particular 1, 2-phenylene, 1, 3-phenylene, 1, 4-phenylene, 4,4'-biphenyl, pyridine, quinoline, naphthalene, phenanthrene.
- Preferred polysulfones for the purposes of the present invention include homopolymers and copolymers, for example random copolymers.
- Particularly preferred polysulfones comprise recurring units of the formulas H to N:
- the polysulfones described above may under the trade names ® Victrex 200 P, ® Victrex 720 P, ® Ultrason E, ® Ultrason S, ® Mindel, ® Radel A, ® Radel R, ® Victrex HTA, ® Astrel and ® Udel be obtained commercially.
- 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.
- preferred proton-conducting polymer membranes are obtainable by a process comprising the steps
- step II polymerization of at least a portion of the monomers comprising phosphonic acid groups which have been introduced into the polymer film in step I).
- Swelling is understood as meaning a weight increase of the film of at least 3% by weight.
- the swelling is at least 5%, more preferably at least 10%.
- Determination of 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) 1 m 2 .
- the swelling is preferably carried out at a temperature above 0 ° C, in particular between room temperature (20 0 C) and 18O 0 C in a liquid, preferably at least 5 wt .-% monomers comprising phosphonic acid contains. Furthermore, the swelling can also be carried out at elevated pressure. in this connection The limits arise from economic considerations and technical possibilities.
- the polymer film used for swelling generally has a thickness in the range of 5 to 3000 .mu.m, preferably 10 to 1500 .mu.m and particularly preferably 20 to 500 .mu.m.
- the preparation of such films of polymers is generally known, some of which are commercially available.
- 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 10000 mPa * s, in particular from 0.2 to 2000 mPa * s, where these values can be measured, for example, in accordance with DIN 53015.
- the composition prepared in step A) or the liquid used in step I) 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.
- the inorganic solvents include in particular water, phosphoric acid and polyphosphoric acid. These can positively influence the processability. For example, the rheology of the solution can be improved so that it can be more easily extruded or laced.
- fillers in particular proton-conductive fillers, and additional acids.
- additional acids preferably have an intrinsic conductivity at 100 ° C. of at least 10 -6 S / cm, in particular 10 -5 S / cm.
- the addition can be carried out, for example, in step A) and / or step B) or step I).
- these additives if they are in liquid form, can also be added after the polymerization according to step C) or step II).
- Non-limiting examples of proton-conductive fillers are sulfates such as: CsHSO 4 , Fe (SO 4 ) 2 , (NH 4 ) 3 H (SO 4 ) 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 ) 4lZr (HPO 4 ) 2) HZr 2 (PO 4 ) 3 , UO 2 PO 4 .3H 2 O, H 8 UO 2 PO 4 ,
- sulfates such as: CsHSO 4 , Fe (SO 4 ) 2 , (NH 4 ) 3 H (SO 4 ) 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 ) 4lZr (HPO 4 ) 2) H
- HTiTaO 5 , HSbTeO 6 , H 5 Ti 4 O 9 , HSbO 3, H 2 MoO 4 selenites and arsenites such as (NH 4 ) 3 H (SeO 4 ) 2 , UO 2 AsO 4 , (NH 4 ) 3 H (SeO 4 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 after the polymerization according to step C) or step II) comprises at most 80 wt .-%, preferably at most 50 wt .-% and particularly preferably at most 20 wt .-% additives.
- this membrane may also contain perfluorinated sulfonic acid additives (preferably 0.1-20% by weight, preferably 0.2-15% by weight, very preferably 0.2-10% by weight). These additives improve performance near the cathode to increase oxygen solubility and oxygen diffusion and reduce adsorption of the electrolyte on the catalyst surface.
- perfluorinated sulfonic acid additives preferably 0.1-20% by weight, preferably 0.2-15% by weight, very preferably 0.2-10% by weight.
- Nonlimiting examples of perfluorinated sulfonic acid additives are: trifluoromethanesulfonic acid, potassium trifluoromethanesulfonate, Sodium trifluoromethanesulfonate, lithium trifluoromethanesulfonate, ammonium trifluoromethanesulfonate, potassium perfluorohexanesulfonate, sodium perfluorohexanesulfonate, lithium perfluorohexanesulfonate, ammonium perfluorohexanesulfonate, perfluorohexanesulfonic acid, potassium nonafluorobutanesulfonate, sodium nonafluorobutanesulfonate, lithium nonafluorobutanesulfonate, ammonium nonafluorobutanesulfonate, cesium nonafluorobutanesulfonate. Tri ⁇ thylammoniumperfluorohexasulfonat and Perfluros
- Suitable carriers are all suitable carriers under the conditions as inert. These supports include, in particular, films of polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), polyhexafluoropropylene, copolymers of PTFE with hexafluoropropylene, polyimides, polyphenylene sulfides (PPS) and polypropylene (PP).
- PET polyethylene terephthalate
- PTFE polytetrafluoroethylene
- PHS polyphenylene sulfides
- PP polypropylene
- the thickness of the planar structure according to step B) is preferably between 10 and 4000 .mu.m, preferably between 15 and 3500 .mu.m, in particular between 20 and 3000 .mu.m, more preferably between 30 and 1500 .mu.m and very particularly preferably between 50 and 500 .mu.m.
- the polymerization of the monomers comprising phosphonic acid groups in step C) or step II) is preferably carried out free-radically.
- the radical formation can be effected thermally, photochemically, chemically and / or electrochemically.
- a starter solution containing at least one substance capable of forming radicals may be added to the composition after heating the composition according to step A).
- a starter solution can be applied to the flat structure obtained after step B). This can be done by means of per se known means (e.g., spraying, dipping, etc.) known in the art.
- a starter solution may be added to the liquid. This can also be applied after swelling on the planar structure.
- Suitable free-radical formers include azo compounds, peroxy compounds, persulfate compounds or azoamidines.
- Non-limiting examples include dibenzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, Dikaliumpersulfat, ammonium peroxydisulfate, 2,2'-azobis (2-methylpropionitrile) (AIBN), 2,2 'azobis (isobutterklamidin) hydrochloride, benzopinacol, Dib ⁇ nzylderivate, Methylethylenk ⁇ tonperoxid, 1.I-azobiscyclohexanecarbonitrile, methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, didecanoyl peroxide, tert-butyl per-2-ethyl
- free-radical formers which form free radicals upon irradiation.
- Preferred compounds include ⁇ , ⁇ -diethoxyacetophenone (DEAP, Upjon Corp), n-butyl benzoin ether (®Trigonal-14, AKZO), and 2,2-dimethoxy-2-phenylacetophenone (®Igacure 651) and 1-benzoylcyclohexanol ( ®lgacure 184), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (®lgacure 819) and 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-phenylpropan-1-one (®lgacure 2959), each from Ciba Geigy Corp. are commercially available.
- free-radical generator usually between 0.0001 and 5 wt .-%, in particular 0.01 to 3 wt .-% (based on the weight of the monomers comprising phosphonic acid groups) is added to free-radical generator.
- the amount of free radical generator can be varied depending on the desired degree of polymerization.
- IR infra red, ie light with a wavelength of more than 700 nm
- NIR near IR, ie light with a wavelength in the range from about 700 to 2000 nm or an energy in the range of about 0.6 to 1.75 eV).
- the polymerization can also be carried out by the action of UV light having a wavelength of less than 400 nm.
- This polymerization method is known per se and described, for example, in Hans Joerg Elias, Macromolecular Chemistry, ⁇ . Auflage, Volume 1, pp. 492-511; DR Arnold, NC Baird, JR Bolton, JCD Brand, PW M Jacobs, P.de Mayo, WR Ware, Photochemistry-An Introduction, Academic Press, New York and MK Mishra, Radical Photopolymerization of Vinyl Monomers, J. Macromol. Sci.-Revs. Macromol. Chem. Phys. 022 (1982-1983) 409.
- a membrane is irradiated with a radiation dose in the range from 1 to 300 kGy, preferably from 3 to 250 kGy and most preferably from 20 to 200 kGy.
- the polymerization of the monomers comprising phosphonic acid in step C) or step II) is preferably carried out at temperatures above room temperature (20 0 C) and less than 200 0 C, particularly at temperatures between 4O 0 C and 150 0 C, particularly preferably between 50 0 C and 120 0 C.
- the polymerization is preferably carried out under atmospheric pressure, but can also be carried out under the action of pressure.
- the polymerization leads to a solidification of the flat structure, this solidification can be followed by microhardness measurement.
- the increase in hardness caused by the polymerization is preferably at least 20%, based on the hardness of the sheet-like structure obtained in step B).
- the membranes have a high mechanical stability. This size results from the hardness of the membrane, which is determined by means of microhardness measurement according to DIN 50539.
- the membrane is loaded with a Vickers diamond successively within 20 s up to a force of 3 mN and the penetration depth 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 this being a restriction. Subsequently, the force is kept constant at 3 mN for 5 s and the creep is calculated from the penetration depth.
- creep CHU is 0.003 / 20/5 under these conditions less than 20%, preferably less than 10%, and most 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 limit it.
- the hardness of the membrane refers both to a surface which has no catalyst layer and to a side which has a catalyst layer.
- the planar structure obtained after the 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 repeating units, in particular at least 50 repeating units, very particularly preferably at least 100 repeating units. This degree of polymerization is determined by the number average molecular weight M n , which can be determined by GPC methods.
- this value is determined by means of a sample which is carried out by polymerization of monomers comprising phosphonic acid groups without addition of polymer.
- the proportion by weight of monomers comprising phosphonic acid groups and of free-radical initiators is kept constant in comparison with the ratios of preparation of the membrane.
- 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 monomers comprising phosphonic acid groups.
- the polymers comprising phosphonic acid groups contained in the membrane preferably have a broad molecular weight distribution.
- the polymers comprising phosphonic acid groups can have a polydispersity M w / M n in the range from 1 to 20, particularly preferably from 3 to 10.
- the water content of the proton-conducting membrane is preferably at most 15% by weight, more preferably at most 10% by weight and most preferably at most 5% by weight.
- preferred membranes include portions of polymers comprising low molecular weight phosphonic acid groups.
- the proportion of polymers comprising phosphonic acid groups having a degree of polymerization in the range from 2 to 20 is preferably at least 10% by weight, particularly preferably at least 20% by weight, based on the weight of the polymers comprising phosphonic acid groups.
- the polymerization in step C) or step II) can lead to a decrease in the layer thickness.
- the thickness of the self-supporting membrane between 15 and 1000 ⁇ m, preferably between 20 and 500 ⁇ m, in particular between 30 and 250 ⁇ m.
- the membrane obtained according to step C) or step II) is self-supporting, i. It can be detached from the carrier without damage and then optionally further processed directly.
- 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 0 C, preferably at least 200 0 C and more preferably at least 25O 0 C to be heated.
- the thermal crosslinking takes place in the presence of oxygen.
- the oxygen concentration in this process step is usually in the range of 5 to 50% by volume, preferably 10 to 40% by volume, without this being intended to limit it.
- 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
- UV light / or UV light.
- Another method is the irradiation with ß-, ⁇ - and / or electron beams.
- the radiation dose here is preferably between 5 and 250 kGy, in particular 10 to 200 kGy.
- the irradiation can be carried out in air or under inert gas. As a result, the
- the duration of the crosslinking reaction can be in a wide range. In general, this reaction time is in the range of 1 second to 10 hours, preferably 1 minute to 1 hour, without this being a restriction.
- the membrane comprises by elemental analysis at least 3 wt .-%, preferably at least 5 wt .-% and particularly preferably at least 7 wt .-% phosphorus, based on the total weight of the membrane.
- the proportion of phosphorus can be determined by elemental analysis.
- the membrane is dried at 11O 0 C for 3 hours in vacuo (1 mbar).
- the polymers comprising phosphonic acid groups preferably have a content of phosphonic acid groups of at least 5 meq / g, more preferably at least 10 meq / g. This value is determined by the so-called ion exchange capacity (IEC).
- the phosphonic acid groups are converted into the free acid, the measurement being carried out before polymerization of the monomers comprising phosphonic acid groups.
- the sample 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
- 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 1 mS / cm, preferably at least 2 mS / cm, in particular at least 5 mS / cm.
- the membranes show a high conductivity even at a temperature of 70 0 C.
- the conductivity depends on the sulfonic acid group content of the membrane. The higher this proportion, the better the conductivity at low temperatures.
- a membrane according to the invention can be moistened at low temperatures.
- the compound used as an energy source for example hydrogen, be provided with a proportion of water. In many cases, however, the water formed by the reaction is sufficient to achieve humidification.
- 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 spectrum obtained is evaluated using a simple model consisting of a parallel arrangement of an ohmic resistance 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 membrane-electrode assembly according to the invention has two gas diffusion layers separated by the polymer electrolyte membrane.
- Usually flat, electrically conductive and acid-resistant structures are used for this purpose. These include, for example, graphite fiber papers, carbon fiber papers, graphite fabrics and / or papers rendered conductive by the addition of carbon black. Through these layers, a fine distribution of the gas and / or liquid streams is achieved.
- This layer generally has a thickness in the range from 80 ⁇ m to 2000 ⁇ m, in particular 100 ⁇ m to 1000 ⁇ m and particularly preferably 150 ⁇ m to 500 ⁇ m.
- At least one of the gas diffusion layers may consist of a compressible material.
- a compressible material is characterized by the property that the gas diffusion layer can be pressed by half the pressure, in particular to one third of its original thickness, without losing its integrity.
- This property generally comprises a gas diffusion layer of graphite fabric and / or paper rendered conductive by the addition of carbon black.
- the catalyst layer or catalyst layers contain or contain catalytically active substances. These include, but are not limited to, noble metals of the platinum group, i. Pt, Pd, Ir, Rh, Os, Ru, or the precious metals Au and Ag. Furthermore, it is also possible to use alloys of all the aforementioned metals. Further, at least one catalyst layer may contain alloys of the platinum group elements with base metals such as Fe, Co, Ni, Cr, Mn, Zr, Ti, Ga, V, etc. In addition, the oxides of the aforementioned noble metals and / or non-noble metals can also be used.
- the catalytically active particles which comprise the abovementioned substances can be used as metal powder, so-called black noble metal, in particular platinum and / or platinum alloys.
- Such particles generally have a size in the range of 5 nm to 200 nm, preferably in the range of 7 nm to 100 nm.
- the metals can also be used on a carrier material.
- this carrier comprises carbon, in particular in the form of carbon black, graphite or graphitized carbon black.
- electrically conductive metal oxides such as, for example, SnO x , TiO x , or phosphates, such as, for example, FePO x , NbPO x , Zr y (PO x ) z as carrier material.
- the indices x, y and z denote the oxygen or metal content of the individual compounds, which may be in a known range, since the transition metals can assume different oxidation states.
- the content of these supported metal particles is generally in the range of 1 to 80 wt .-%, preferably 5 to 60 wt .-% and particularly preferably 10 to 50 wt. %, without this being a limitation.
- the particle size of the carrier in particular the size of the carbon particles, is preferably in the range of 20 to 1000 nm, in particular 30 to 100 nm.
- the size of the metal particles present thereon is preferably in the range of 1 to 20 nm, in particular 1 to 10 nm and more preferably 2 to 6 nm.
- the sizes of the different particles represent mean values and can be determined by transmission electron microscopy or powder X-ray diffractometry.
- the catalytically active particles set forth above can generally be obtained commercially.
- the catalytically active layer may contain conventional additives. These include, but are not limited to, fluoropolymers, e.g. Polytetrafluoroethylene (PTFE), proton-conducting ionomers and surface-active substances.
- fluoropolymers e.g. Polytetrafluoroethylene (PTFE)
- PTFE Polytetrafluoroethylene
- the weight ratio of fluoropolymer to catalyst material comprising at least one noble metal and optionally one or more support materials, greater than 0.1, wherein this ratio is preferably in the range of 0.2 to 0.6.
- the catalyst layer has a thickness in the range from 1 to 1000 .mu.m, in particular from 5 to 500, preferably from 10 to 300 .mu.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 more preferably 0.3 to 3.0 mg / cm 2 . These values can be determined by elemental analysis of a flat sample.
- the electrochemically active area of the catalyst layer designates the area which is in contact with the polymer electrolyte membrane and at which the above-described redox reactions can take place.
- the present invention enables the formation of particularly large electrochemically active areas.
- the size of this electrochemically active surface is at least 2 cm 2 , in particular at least 5 cm 2 and preferably at least 10 cm 2 , without this being a restriction.
- electrode means that the material has electron conductivity, the electrode designating the electrochemically active region.
- the polymer electrolyte membrane has an inner portion that is in contact with a catalyst layer and an outer portion that is not provided on the surface of a gas diffusion layer.
- the inner region has no overlapping region with a gas diffusion layer, if a view perpendicular to the surface of a gas diffusion layer or the outer region of the polymer electrolyte membrane is made so that only after contacting the polymer electrolyte Membrane with the gas diffusion layer an assignment can be made.
- the outer region of the polymer electrolyte membrane may have a single-layered construction.
- the outer portion of the polymer electrolyte membrane is generally made of the same material as the inner portion of the polymer electrolyte membrane.
- the outer region of the polymer electrolyte membrane may in particular comprise at least one further layer, preferably at least two have further layers.
- the outer region of the polymer electrolyte membrane has at least two or at least three components.
- the thickness of all components of the outer region of the polymer electrolyte membrane is greater than the thickness of the inner region of the polymer electrolyte membrane.
- the thickness of the outer area refers to the sum of the thicknesses of all components of the outer area.
- the components of the outer region result from the vector parallel to the surface of the outer region of the polymer electrolyte membrane, wherein the layers that intersect this vector are to be counted among the components of the outer region.
- the outer region preferably has a thickness in the range from 80 ⁇ m to 4000 ⁇ m, in particular in the range from 120 ⁇ m to 2000 ⁇ m and particularly preferably in the range from 150 ⁇ m to 800 ⁇ m.
- the thickness of all components of the outer region is 50% to 100%, preferably 65% to 95% and particularly preferably 75% to 85%, based on the sum of the thickness of all components of the inner region.
- the thickness of the components of the outer region in this case refers to the thickness of these components after a first pressing, which takes place at a pressure of 5 N / mm 2 , preferably 10 N / mm 2 over a period of 1 minute.
- the thickness of the components of the inner region refer to the thicknesses of the layers used, without this having to be pressed.
- the thickness of all components of the inner region generally results from the sum of the thicknesses of the membrane, the catalyst layers and the gas diffusion layers of anode and cathode.
- the thickness of the layers is determined using a digital thickness gauge from Mitutoyo.
- the contact pressure of the two circular flat contact surfaces during the measurement is 1 PSI, the diameter of the contact surface is 1 cm.
- the catalyst layer is generally not self-supporting but is commonly applied to the gas diffusion layer and / or the membrane. In this case, part of the catalyst layer can diffuse, for example, into the gas diffusion layer and / or the membrane, whereby transition layers form. This can also lead to the fact that the catalyst layer can be regarded as part of the gas diffusion layer.
- the thickness of the catalyst layer results from the measurement of the thickness of the layer to which the catalyst layer has been applied, for example the gas diffusion layer or the membrane, this measurement being the sum of the Catalyst layer and the corresponding layer results, for example, the sum of gas diffusion layer and catalyst layer.
- the thickness of the components of the outer region decreases at a temperature of 8O 0 C and a pressure of 5 N / mm 2 over a period of 5 hours at most by 5%, this decrease in thickness is determined after a first pressing, which at a pressure of 5 N / mm 2 , preferably 10 N / mm 2 over a period of 1 minute.
- the measurement of the pressure and temperature-dependent deformation parallel to the surface vector of the components of the outer region, in particular of the outer region of the polymer electrolyte membrane is carried out by a hydraulic press with heatable press plates.
- the hydraulic press has the following technical data:
- the press has a force range of 50-50000 N with a maximum pressing surface of 220 x 220 mm 2 .
- the resolution of the pressure sensor is ⁇ 1 N.
- An inductive displacement sensor with a measuring range of 10 mm is attached to the press plates.
- the resolution of the displacement sensor is ⁇ 1 ⁇ m.
- the press plates can be operated in a temperature range of RT - 200 ° C.
- the press is power-controlled by means of a PC with appropriate software
- the data from the force and displacement sensors are recorded and displayed in real time at a data rate of up to 100 measured data / second.
- the material to be tested is cut to an area of 55 x 55 mm 2 and placed between the pre-heated to 80 °, 12O 0 C and 16O 0 C press platens.
- the press plates are closed and an initial force of 120N applied, so that the control loop of the press is closed.
- the position sensor is set to 0 at this point.
- a previously programmed pressure ramp is traversed.
- the pressure is increased at a rate of 2 N / mm 2 s to a predetermined value, for example, 5, 10, 15 or 20 N / mm 2 and held at this value for at least 5 hours.
- the pressure is reduced to 0 N / mm 2 with a ramp of 2 N / mm 2 s and the press is opened.
- the relative and / or absolute change in thickness can be read from a deformation curve recorded during the pressure test or measured by a standard thickness gauge measurement after the pressure test.
- the outer region components is generally achieved through the use of polymers having high pressure stability.
- the polymer electrolyte membrane in the outer region may have a particularly high degree of crosslinking, which can be achieved by a specific irradiation, which was previously described.
- the outer region membrane is irradiated with a dose of at least 100 kGy, preferably at least 132 kGy and more preferably at least 200 kGy.
- the inner region of the membrane is preferably irradiated with at most 130 kGy, preferably at most 99 kGy and particularly preferably at most 80 kGy.
- the ratio of the irradiation power of the outer region to the irradiation power of the inner region is preferably at least 1.5, more preferably at least 2, and most preferably at least 2.5.
- the irradiation of the outer region may furthermore preferably take place with a UV lamp having a power of at least 5OW, in particular 100W, and particularly preferably 200W.
- the duration can be within a wide range. Preference is given to irradiating for at least one minute, in particular at least 30 minutes and more preferably at least 5 hours, in many cases irradiation of up to 30 hours, in particular up to 10 hours, being sufficient.
- the ratio of the irradiation time of the outer region to the irradiation time of the inner region is preferably at least 1.5, more preferably at least 2, and most preferably at least 2.5
- these materials generally exhibit high pressure stability.
- the thickness of the components of the outer region at a temperature of 120 0 C, more preferably 16O 0 C and a pressure of 5 N / mm 2 , preferably 10 N / mm 2 , in particular 15 N / mm 2 and particularly preferably 20 N. / mm 2 over a period of 5 hours, more preferably 10 hours at the most by 5%, in particular at most 2%, preferably at most by 1% from.
- the outer region comprises at least one, preferably at least two polymer layers having a thickness greater than or equal to 10 ⁇ m, the polymers of these layers each having an E modulus of at least 6 N / mm 2 , preferably at least 7 N / mm 2 , measured at 80 0 C, preferably at 16O 0 C and an elongation of 100%.
- the measurement of these values is carried out in accordance with DIN EN ISO 527-1.
- a layer may be applied by thermoplastic methods, for example injection molding or extrusion. Accordingly, a layer is preferably made of a meltable polymer.
- polymers used preferably have a continuous use temperature of at least 19O 0 C, preferably at least 220 0 C and most preferably at least 250 ° C measured according to MIL-P-46112B, paragraph 4.4.5.
- the preferred meltable polymers include, in particular, fluoropolymers such as poly (tetrafluoroethylene-co-hexafluoropropylene) FEP, polyvinylidene fluoride PVDF, perfluoroalkoxy polymer PFA, poly (tetrafluoroethylene-co-perfluoro (methylvinyl ether)) MFA.
- fluoropolymers such as poly (tetrafluoroethylene-co-hexafluoropropylene) FEP, polyvinylidene fluoride PVDF, perfluoroalkoxy polymer PFA, poly (tetrafluoroethylene-co-perfluoro (methylvinyl ether)) MFA.
- fluoropolymers such as poly (tetrafluoroethylene-co-hexafluoropropylene) FEP, polyvinylidene fluoride PVDF, perfluoroalkoxy polymer PFA, poly (tetrafluoroethylene-co-
- One or both layers may include, but are not limited to, polyphenylenes, phenolic resins, phenoxy resins, polysulfide ethers, polyphenylene sulfides, polyethersulfones, polyimines, polyetherimines, polyazoles, polybenzimidazoles, polybenzoxazoles, polybenzothiazoles, polybenzoxadiazoles, polybenzotriazoles, polyphosphazenes, polyetherketones, polyketones, polyetheretherketones, polyetherketone ketones, polyphenyleneamides, Polyphenyleneoxide, polyimides and mixtures of two or more of these polymers are produced.
- the polyimides also include polymers which in addition to imide also amide (polyamide), ester (polyester) u. Ether groups (polyetherimides) as constituents of the main chain.
- the various layers can be bonded together using suitable polymers. These include in particular fluoropolymers. Suitable fluoropolymers are known in the art. These include, but are not limited to, polyfluorotetraethylene (PTFE) and poly (tetrafluoroethylene-co-polymer). hexafluoropropylene) (FEP).
- the layer of fluoropolymers present on the layers described above generally has a thickness of at least 0.5 ⁇ m, in particular of at least 2.5 ⁇ m. This layer may be provided between the polymer electrolyte membrane and further layers. Furthermore, the layer can also be applied to the side facing away from the polymer electrolyte membrane side. In addition, both surfaces of the layers to be laminated may be provided with a layer of fluoropolymers. This can surprisingly improve the long-term stability of the MEUs.
- At least one component of the outer region of the polymer electrolyte membrane is commonly in contact with electrically conductive separator plates, typically provided with flow field troughs on the sides facing the gas diffusion layers, to facilitate the distribution of reactant fluids.
- the separator plates are usually made of graphite or of conductive, heat-resistant plastic.
- the components of the outer area In combination with the separator plates, the components of the outer area generally seal the gas spaces to the outside. In addition, the components of the outer region in combination with the inner region of the polymer electrolyte membrane generally also seal the gas spaces between the anode and the cathode. Surprisingly, it has thus been found that an improved sealing concept can lead to a fuel cell with a prolonged service life.
- Electrode unit wherein the catalyst layer has been applied to the gas diffusion layer
- FIG. 2 shows a schematic cross section of a second membrane-electrode unit according to the invention, wherein the catalyst layer has been applied to the gas diffusion layer.
- Figure 1 shows a side view of a membrane-electrode assembly according to the invention in a sectional view. It is a schema, where the description describes the state before pressing and the distances between the layers should improve understanding.
- the polymer Electrolyte membrane 1 a layer which has a substantially constant thickness.
- the outer region is formed by two layers 2 and 3, so that the outer region has a greater thickness than the inner region of the polymer electrolyte membrane.
- the inner region of the polymer electrolyte membrane is in contact with the catalyst layers 4 and 4a.
- a gas diffusion layer 5, 6 is provided, which has a catalyst layer 4 and 4a, respectively.
- a gas diffusion layer 5 provided with a catalyst layer 4 forms the anode or cathode
- the second gas diffusion layer 6 provided with a catalyst layer 4a forms the cathode or anode.
- the thickness of the sum of the layers 1 + 2 + 3 is in the range of 50 to 100%, preferably 65 to 95% and particularly preferably 75 to 85% of the thickness of the layers 1 + 4 + 4a + 5 + 6.
- Figure 2 shows a side view of a membrane-electrode assembly according to the invention in a sectional view. It is a schema, where the description describes the state before pressing and the distances between the layers should improve understanding.
- the polymer electrolyte membrane 1 has an inner region 1a and an outer region 1b. The inner region of the polymer electrolyte membrane is in contact with the catalyst layers 4 and 4a.
- a gas diffusion layer 5, 6 is provided, which has a catalyst layer 4 and 4a, respectively.
- a gas diffusion layer 5 provided with a catalyst layer 4 forms the anode or cathode
- the second gas diffusion layer 6 provided with a catalyst layer 4a forms the cathode or anode.
- the thickness of the outer region 1b is in the range of 50 to 100%, preferably 65 to 95% and particularly preferably 75 to 85% of the thickness of the layers 1a + 4 + 4a + 5 + 6
- membrane electrode assembly The production of membrane electrode assembly according to the invention will be apparent to those skilled in the art.
- the various components of the membrane-electrode assembly are superimposed and bonded together by pressure and temperature.
- pressure and temperature In general, at a temperature in the range of 10 to 300 0 C, in particular 20 0 C to 200 ° and at a pressure in the range of 1 to 1000 bar, in particular from 3 to 300 bar laminated.
- the outer region of the polymer electrolyte membrane can be thickened by a second polymer layer.
- This second layer can be laminated, for example.
- the second layer may also be through thermoplastisch ⁇ method, for example, extrusion or injection molding can be applied.
- the finished membrane-electrode unit (MEU) is ready for operation after cooling and can be used in a fuel cell.
- membrane electrode units according to the invention can easily be stored or shipped due to their dimensional stability under fluctuating ambient temperatures and humidity. Even after prolonged storage or after shipment to locations with significantly different climatic conditions, the dimensions of the MEE are easily suitable for installation in fuel cell stacks. The MEE does not have to be conditioned on site for external installation, which simplifies the production of the fuel cell and saves time and costs.
- An advantage of preferred MEEs is that they allow the operation of the fuel cell at temperatures above 120 0 C. This applies to gaseous and liquid fuels, such as hydrogen-containing gases, which are prepared for example in an upstream reforming step from hydrocarbons. For example, oxygen or air can be used as the oxidant.
- MEEs have a high tolerance to carbon monoxide in operation above 120 0 C with pure platinum catalysts, ie without a further alloying ingredient. At temperatures of 160 0 C, for example, more than 1% CO may be contained in the fuel gas, without this leading to a significant reduction in the performance of the fuel cell.
- Preferred MEUs can be operated in fuel cells without the need to humidify the fuel gases and the oxidants despite the possible high operating temperatures.
- the fuel cell is still stable and the membrane does not lose its conductivity. This simplifies the entire fuel cell system and brings additional cost savings, since the management of the water cycle is simplified. Furthermore, this also improves the behavior at temperatures below 0 ° C. of the fuel cell system.
- preferred MEEs allow the fuel cell to be cooled to room temperature and below, and then put back into service without sacrificing performance. Furthermore, the preferred MEEs of the present invention show very high long-term stability. It has been found that a fuel cell according to the invention can be operated continuously for long periods, for example more than 5000 hours at temperatures of more than 120 0 C with dry reaction gases, without a noticeable performance degradation is detected. The achievable power densities are very high even after such a long time.
- the fuel cells according to the invention show a high quiescent voltage, even after a long time, for example more than 5000 hours, which after this time preferably at least 900 mV, more preferably at least 920 mV.
- a fuel cell is operated with a hydrogen flow on the anode and an air flow on the cathode de-energized. The measurement is made by the fuel cell is switched from a current of 0.2 A / cm 2 to the de-energized state and then there 2 minutes, the quiescent voltage is recorded. The value after 5 minutes is the corresponding rest potential.
- the measured values of open circuit voltage apply for a temperature of 160 0 C.
- the fuel cell according to this time is preferably a small gas passage (gas cross-over).
- the anode side of the fuel cell is operated with hydrogen (5 L / h), the cathode with nitrogen (5 L / h).
- the anode serves as a reference and counter electrode.
- the cathode as a working electrode.
- the cathode is set to a potential of 0.5 V and oxidized through the membrane diffusing hydrogen at the cathode mass transport-limited.
- the resulting current is a measure of the hydrogen permeation rate.
- the current is ⁇ 3 mA / cm 2, preferably ⁇ 2 mA / cm 2, particularly preferably ⁇ 1 mA / cm 2 in a 50 cm 2 cell.
- the measured values of H2-cross-overs are valid for a temperature of 16O 0 C.
- the MEUs according to the invention can be produced inexpensively and easily.
- a PBI film with a thickness of 50 ⁇ m was produced.
- the film was washed in H2O at 80 ° C. three times.
- the film was doped with the vinylphosphonic acid / H 2 O mixture (9/1) at 50 ° C.
- the membrane was then irradiated with the electron irradiation 99 kGy.
- the thickness of the membrane after irradiation was 120 ⁇ m.
- the membrane thus obtained was used to prepare a membrane-electrode assembly.
- the area of the membrane was 80mm * 80mm, the membrane was placed (54mm * 54mm) between an anode (54mm * 54mm) and a cathode, and microns pressed at 120 0 C to a total thickness of the 720th
- the anode used was a catalyst-coated and ionomer-containing diffusion layer.
- the catalyst loading was 1.5 mgpt / RU / cm 2
- the anode used was a catalyst-coated and ionomer-containing diffusion layer.
- the catalyst loading was 4 mg Pt / cm 2
- the active MEA area is 29.26 cm 2 and the total area of the membrane is 64 cm 2 .
- the thickness of the membrane in the interior was on average 70 microns, in the outdoor area on average 100 microns.
- the methanol penetration was 70mA / cm 2 and the cell resistance was 200mOhmcm 2
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Sustainable Development (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE502005008337T DE502005008337D1 (de) | 2004-07-21 | 2005-07-21 | Membran-elektrodeneinheiten und brennstoffzellen mit hoher lebensdauer |
DK05773445.1T DK1771911T3 (da) | 2004-07-21 | 2005-07-21 | Membran-elektrode-enheder og brændstofceller med lang levetid |
JP2007521901A JP5004794B2 (ja) | 2004-07-21 | 2005-07-21 | 改良された膜電極接合体及び高耐久性燃料電池 |
US11/572,323 US20070281204A1 (en) | 2004-07-21 | 2005-07-21 | Membrane Electrode Assemblies and Highly Durable Fuel Cells |
AT05773445T ATE445919T1 (de) | 2004-07-21 | 2005-07-21 | Membran-elektrodeneinheiten und brennstoffzellen mit hoher lebensdauer |
EP05773445A EP1771911B1 (de) | 2004-07-21 | 2005-07-21 | Membran-elektrodeneinheiten und brennstoffzellen mit hoher lebensdauer |
US13/349,613 US20120141909A1 (en) | 2004-07-21 | 2012-01-13 | Membrane electrode assemblies and highly durable fuel cells |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102004035305A DE102004035305A1 (de) | 2004-07-21 | 2004-07-21 | Verbesserte Membran-Elektrodeneinheiten und Brennstoffzellen mit hoher Lebensdauer |
DE102004035305.0 | 2004-07-21 |
Related Child Applications (1)
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US13/349,613 Division US20120141909A1 (en) | 2004-07-21 | 2012-01-13 | Membrane electrode assemblies and highly durable fuel cells |
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WO2006008157A1 true WO2006008157A1 (de) | 2006-01-26 |
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ID=35079231
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PCT/EP2005/007945 WO2006008157A1 (de) | 2004-07-21 | 2005-07-21 | Membran-elektrodeneinheiten und brennstoffzellen mit hoher lebensdauer |
Country Status (7)
Country | Link |
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US (2) | US20070281204A1 (de) |
EP (1) | EP1771911B1 (de) |
JP (1) | JP5004794B2 (de) |
AT (1) | ATE445919T1 (de) |
DE (2) | DE102004035305A1 (de) |
DK (1) | DK1771911T3 (de) |
WO (1) | WO2006008157A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007019978A1 (de) * | 2005-08-12 | 2007-02-22 | Basf Fuel Cell Gmbh | Verbesserte membran-elektrodeneinheiten und brennstoffzellen mit langer lebensdauer |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US8968967B2 (en) * | 2008-09-17 | 2015-03-03 | Ballard Power Systems Inc. | Fuel cell catalyst support with fluoride-doped metal oxides/phosphates and method of manufacturing same |
WO2010033121A1 (en) * | 2008-09-19 | 2010-03-25 | Utc Power Corporation | Fuel cell catalyst support with boron carbide-coated metal oxides/phosphates and method of manufacturing same |
EP2396843A1 (de) | 2009-02-10 | 2011-12-21 | UTC Power Corporation | Brennstoffzellenkatalysator mit einer metalloxid-/phosphat-haltestruktur und herstellungsverfahren dafür |
JP2010257669A (ja) * | 2009-04-23 | 2010-11-11 | Toppan Printing Co Ltd | 膜電極接合体及びその製造方法並びに固体高分子形燃料電池 |
US20150190760A1 (en) * | 2014-01-06 | 2015-07-09 | Pall Corporation | Membrane with plurality of charges |
BE1030539B1 (nl) * | 2022-05-18 | 2023-12-19 | Vaneflon Nv | Werkwijze voor het persen van een fluorpolymeer en/of polyether ether keton product |
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JPH06333582A (ja) * | 1993-05-25 | 1994-12-02 | Fuji Electric Co Ltd | 固体高分子電解質型燃料電池 |
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EP1341251A1 (de) * | 2002-02-28 | 2003-09-03 | OMG AG & Co. KG | PEM-Brennstoffzellenstapel |
CA2496589A1 (en) * | 2002-08-29 | 2004-03-25 | Pemeas Gmbh | Process for producing proton-conducting polymer membranes, improved polymer membranes and thier use in fuel cells |
-
2004
- 2004-07-21 DE DE102004035305A patent/DE102004035305A1/de not_active Withdrawn
-
2005
- 2005-07-21 WO PCT/EP2005/007945 patent/WO2006008157A1/de active Application Filing
- 2005-07-21 JP JP2007521901A patent/JP5004794B2/ja not_active Expired - Fee Related
- 2005-07-21 US US11/572,323 patent/US20070281204A1/en not_active Abandoned
- 2005-07-21 DE DE502005008337T patent/DE502005008337D1/de active Active
- 2005-07-21 EP EP05773445A patent/EP1771911B1/de not_active Not-in-force
- 2005-07-21 AT AT05773445T patent/ATE445919T1/de not_active IP Right Cessation
- 2005-07-21 DK DK05773445.1T patent/DK1771911T3/da active
-
2012
- 2012-01-13 US US13/349,613 patent/US20120141909A1/en not_active Abandoned
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US20030091885A1 (en) * | 2001-01-31 | 2003-05-15 | Matsushita Electric Industrial Co., Ltd. | High polymer electrolyte fuel cell and electrolyte film-gasket assembly for the fuel cell |
US20030078157A1 (en) * | 2001-03-15 | 2003-04-24 | Hiroaki Matsuoka | Method of manufacturing electrolytic film electrode connection body for fuel cell |
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Also Published As
Publication number | Publication date |
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JP2008507106A (ja) | 2008-03-06 |
ATE445919T1 (de) | 2009-10-15 |
EP1771911B1 (de) | 2009-10-14 |
DK1771911T3 (da) | 2010-02-08 |
JP5004794B2 (ja) | 2012-08-22 |
DE502005008337D1 (de) | 2009-11-26 |
US20120141909A1 (en) | 2012-06-07 |
EP1771911A1 (de) | 2007-04-11 |
US20070281204A1 (en) | 2007-12-06 |
DE102004035305A1 (de) | 2006-02-16 |
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