WO2005024988A2 - Protonenleitende polymermembran enthaltend polymere mit an aromatische gruppen kovalent gebundene sulfonsäuregruppen, membran-elektroden-einheit und deren anwendung in brennstoffzellen - Google Patents
Protonenleitende polymermembran enthaltend polymere mit an aromatische gruppen kovalent gebundene sulfonsäuregruppen, membran-elektroden-einheit und deren anwendung in brennstoffzellen Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
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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
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2385/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers
- C08J2385/02—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers containing phosphorus
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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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
- 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
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a proton-conducting polymer membrane containing polymers with sulfonic acid groups covalently bonded to aromatic groups, 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. Furthermore, the present invention relates to membrane-electrode units which comprise the polymer electrolyte membrane.
- 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 permeable to reactive fuels such as hydrogen gas or methanol and oxygen gas.
- a fuel cell generally has several individual cells, so-called MEEs (membrane electrode assemblies), each of which contains an electrolyte and two electrodes separated by the electrolyte.
- MEEs membrane electrode assemblies
- Solids such as polymer electrolyte membranes or liquids such as phosphoric acid are used as the electrolyte for the fuel cell.
- Polymer electrolyte membranes have recently attracted attention as electrolytes for fuel cells. In principle, one can differentiate between two categories of polymer membranes.
- the first category includes cation exchange membranes consisting of a polymer structure which contains covalently bound acid groups, preferably sulfonic 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.
- the operating temperatures of fuel cells containing such 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 National are used.
- PEMBZ polymer electrolyte membrane fuel cells
- perfluorosulfonic acid polymers are used as materials for polymer electrolyte membranes.
- the perfluorosulfonic acid polymer (such as National) 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 sulfonic acid. Methods for sulfonating polymers are described in F. Kucera et. al. Polymer Engineering and Science 1988, Vol. 38, No 5, 783-792.
- cation exchange membranes which have gained commercial importance for use in fuel cells are listed below: The most important representative is the perfluorosulfonic acid polymer National ® (US 3692569). 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 be prepared as described in US5422411 by copolymerization from trifluorostyrene and sulfonyl-modified trifuorostyrene.
- Composite membranes consisting of a porous carrier material, in particular expanded Teflon, filled with ionomers consisting of such sulfonyl-modified trifluorostyrene copolymers are described in US5834523.
- 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 be made by radiation grafting and subsequent sulfonation.
- a grafting reaction is preferably carried out on a previously irradiated polymer film with 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.
- 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.
- Sulfonated polybenzimidazoles are also known from the literature.
- Staiti et al P. Staiti in J. Membr. Sei. 188 (2001) 71 have described the preparation and properties of sulfonated polybenzimidazoles. It was not possible to carry out the sulfonation on the polymer in the solution. When the sulfonating agent is added to the PBI / DMAc solution, the polymer precipitates. For the sulfonation, a PBI film was first produced and this was immersed in a dilute sulfuric acid. For sulfonation, the samples were then treated at temperatures of approx. 475 ° C for 2 minutes.
- the sulfonated PBI membranes only have a maximum conductivity of 7.5 * 10 "5 S / cm at a temperature of 160 ° C.
- the maximum ion exchange capacity is 0.12 meq / g. It has also been shown that such sulfonated PBI membranes are not are suitable for use in a fuel cell.
- polymer membranes are known from WO 00/22684, which have a porous material.
- the water content of the membrane is preferably 20 to 100% by weight, based on the dry weight of the membrane. Accordingly, the proton conductivity is determined by the water content.
- the disadvantage of all of these cation exchange membranes is the fact that the membrane has to be moistened, the operating temperature is limited to 100 ° C. and the membranes have a high methanol permeability.
- the cause of these disadvantages is the conductivity mechanism of the membrane, in which the transport of the protons is coupled to the transport of the water molecule. This is called the "vehicle mechanism" (K.-D. Kreuer, Chem. Mater. 1996, 8, 610-641).
- polymer electrolyte membranes with complexes of basic polymers and strong acids have been developed.
- WO96 / 13872 and the corresponding US Pat. No. 5,525,436 describe a process for producing a proton-conducting polymer electrolyte membrane, in which a basic polymer, such as polybenzimidazole, is treated with a strong acid, such as phosphoric acid, sulfuric acid, etc.
- the mineral acid usually concentrated phosphoric acid
- the polymer serves as a carrier for the electrolyte consisting of the highly concentrated phosphoric acid.
- 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.
- CO arises 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.
- the CO content of the fuel must be less than 100 ppm at temperatures ⁇ 100 ° C. At temperatures in the range of 150-200 °, however, 10,000 ppm CO or more can also be tolerated (NJ Bjerrum et. Al. Journal of Applied Electrochemistry, 2001, 31, 773-779).
- a great 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. Water forms as a reaction product on the cathode. Heat is therefore a by-product of the electrochemical reaction.
- 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 used efficiently using existing technologies such as heat exchangers.
- 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 will be possible to cool the fuel cell system more efficiently or to use small cooling surfaces and to dispense with additional devices compared to fuel cells which, due to the membrane humidification, are below 100 ° C must be operated.
- DMBZ direct methanol fuel cell
- the present invention is therefore based on the object of providing a novel polymer electrolyte membrane which achieves the objects set out above.
- a membrane according to the invention should be able to be produced inexpensively and simply.
- the conductivity should be achieved without additional humidification, especially at high temperatures.
- the membrane should have a high mechanical stability in relation to its performance.
- a polymer electrolyte membrane should be made available that can be used in many different fuel cells.
- the membrane is said to be particularly suitable for fuel cells that use pure hydrogen and numerous carbon-containing fuels, in particular natural gas, gasoline, methanol and biomass, as energy sources.
- the membrane should be able to be used in a hydrogen fuel cell and in a direct methanol fuel cell (DMBZ).
- DMBZ direct methanol fuel cell
- the operating temperature should be able to be extended from ⁇ 20 ° C to 200 ° C without reducing the service life of the fuel cell very much.
- a polymer electrolyte membrane should be created which has a high mechanical stability, for example a high modulus of elasticity, a high tensile strength and a high fracture toughness.
- the present invention relates to a proton-conducting polymer membrane containing polymers with sulfonic acid groups covalently bonded to aromatic groups and polymers comprising phosphonic acid groups obtainable by polymerizing monomers comprising phosphonic acid groups
- preferred proton-conducting polymer membranes can be obtained by a process comprising the steps
- step B) applying a layer using the mixture according to step A) on a support
- step B Polymerization of the monomers comprising phosphonic acid groups present in the sheet-like structure obtainable according to step B).
- preferred proton-conducting polymer membranes are obtainable by a process comprising the steps I) swelling of a polymer film, the polymer film comprising polymer with aromatic sulfonic acid groups, with a liquid containing monomers comprising phosphonic acid groups, and
- 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 ) / m 0 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 which preferably contains monomers comprising at least 5% by weight of phosphonic acid groups. Furthermore, 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 with aromatic sulfonic acid groups, wherein this film can contain further generally customary additives.
- the liquid containing monomers comprising phosphonic acid groups can be a solution, wherein the liquid can also contain suspended and / or dispersed constituents.
- the viscosity of the liquid which contains monomers comprising phosphonic acid groups can be in a wide range, solvents being added or the temperature being increased in order to adjust the viscosity.
- the dynamic viscosity is preferably in the range from 0.1 to 10000 mPa * s, in particular 0.2 to 2000 mPa * s, these values being able to be measured, for example, in accordance with DIN 53015.
- a membrane according to the invention exhibits a high temperature over a wide temperature range
- a membrane according to the invention shows a relatively high mechanical stability.
- a membrane according to the invention can be produced simply and inexpensively. Furthermore, these membranes have a surprisingly long service life. Furthermore, a fuel cell that is equipped with a membrane according to the invention can also be operated at low temperatures, for example at 20 ° C., without the service life of the fuel cell being greatly reduced thereby.
- 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.
- 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 of the present invention show high mechanical stability, in particular high modulus of elasticity, high tensile strength and high fracture toughness. Furthermore, these membranes have a surprisingly long service life.
- 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.
- the two carbon atoms which form the carbon-carbon double bond preferably have at least two, preferably 3, bonds to groups which lead to a slight steric hindrance of the double bond.
- These groups include hydrogen atoms and halogen atoms, especially fluorine atoms.
- the polymer comprising phosphonic acid groups results from the polymerization product which is obtained by polymerizing the monomer comprising phosphonic acid groups alone or with further monomers and / or crosslinking agents.
- the monomer comprising phosphonic acid groups can comprise one, two, three or more carbon-carbon double bonds. Furthermore, the monomer comprising phosphonic acid groups may contain one, two, three or more phosphonic acid groups.
- the monomer comprising phosphonic acid groups contains 2 to 20, preferably 2 to 10, carbon atoms.
- the monomer comprising phosphonic acid groups used to prepare the polymers comprising phosphonic acid groups is preferably a compound of the formula
- R denotes 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, the above radicals in turn being halogen, -OH, COOZ, -CN, NZ 2 can be substituted,
- Z independently of one another is hydrogen, C1-C15-al yl group, C1-C15-alkoxy group, ethyleneoxy group or C5-C20-aryl or heteroaryl group, it being possible for the above radicals in turn to be substituted with halogen, -OH, -CN, and x is a whole Number 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 means y an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 and / or of the formula x (Z 2 0 3 P) -R- "R— (P0 3 Z 2 ) x where
- 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 C1-C15-alkyl group, C1-C15-alkoxy group, ethyleneoxy group or C5-C20-aryl or heteroaryl group means, where the above radicals may in turn be substituted with 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 can 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
- the preferred monomers comprising phosphonic acid groups 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, for example, 2-phosphonomethyl-acrylic acid, 2-phosphonomethyl-methacrylic acid, 2-phosphonomethyl-acrylic acid amide and 2-phosphonomethyl-methacrylic acid amide.
- vinylphosphonic acid ethenephosphonic acid
- Aldrich or Clahant GmbH is particularly preferably used.
- 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 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 monomers comprising phosphonic acid groups.
- the mixture produced in step A) or the liquid used in step I) preferably comprises at least 20% by weight, in particular at least 30% by weight and particularly preferably at least 50% by weight, based on the total weight of the mixture, comprising phosphonic acid groups monomers.
- the mixture produced in step A) or the liquid used in step I) can 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.
- the solubility of polymers which are formed, for example, in step B) can be improved by adding the organic solvent.
- 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.
- compositions containing monomers comprising sulfonic acid groups can be used to prepare the polymers 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 which form the carbon-carbon double bond preferably have at least two, preferably 3, bonds to groups which lead to a slight steric hindrance of the double bond.
- These groups include 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 crosslinking agents.
- the monomer comprising sulfonic acid groups can comprise one, two, three or more carbon-carbon double bonds. Furthermore, 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 is preferably a compound of the formula wherein
- R denotes 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, the above radicals in turn being halogen, -OH, COOZ, -CN, NZ 2 can be substituted,
- Z independently of one another denotes hydrogen, C1-C15-alkyl group, C1-C15-alkoxy group, ethyleneoxy group or C5-C20-aryl or heteroaryl group, it being possible for the above radicals themselves to be substituted by halogen, -OH, -CN, and x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 means y an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10
- R denotes 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, the above radicals in turn being halogen, -OH, COOZ, -CN, NZ 2 can be substituted,
- Z independently of one another denotes hydrogen, C1-C15-alkyl group, C1-C15-alkoxy group, ethyleneoxy group or C5-C20-aryl or heteroaryl group, it being possible for the above radicals themselves to be substituted by halogen, -OH, -CN, and x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 means
- A represents a group of the formulas COOR 2 , CN, CONR 2 2 , OR 2 and / or R 2 , wherein R 2 is hydrogen, a C1-C15-alkyl group, C1-C15-alkoxy group, ethyleneoxy group or C5-C20-aryl or heteroaryl group means, where the above radicals in turn can be substituted with 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 can 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
- the preferred monomers comprising sulfonic acid groups include alkenes which have sulfonic acid groups, such as ethene sulfonic acid, propene sulfonic acid, butene sulfonic acid; Acrylic acid and / or methacrylic acid compounds that have sulfonic acid groups, such as 2-sulfonomethyl-acrylic acid, 2-sulfonomethyl-methacrylic acid, 2-sulfonomethyl-acrylic acid amide and 2-sulfonomethyl-methacrylic acid amide.
- vinyl sulfonic acid ethene sulfonic acid
- Aldrich or Clariant GmbH is particularly preferably used.
- a preferred vinyl sulfonic 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 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 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 particularly preferably 2: 1 to 1: 2.
- monomers capable of crosslinking can be used in the production of the polymer membrane. 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 flat structure according to step B). Furthermore, these monomers can be added to the liquid in accordance with step l).
- the monomers capable of crosslinking 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 , where the above radicals can in turn be substituted, R ' independently of one another 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, carboxy, 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, trimethylolpropane 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 usually being in the range between 0.05 to 30% by weight, preferably 0.1 to 20% by weight, particularly preferably 1 and 10% by weight, based on the weight of the Monomers comprising phosphonic acid groups can be used.
- the composition produced according to step A) or the polymer film used in step I) comprises at least one polymer with aromatic sulfonic acid groups.
- Aromatic sulfonic acid groups are groups in which the sulfonic acid group (-S0 3 H) is covalently bound 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 main chain being preferred.
- the sulfonic acid groups can often also be used 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.
- 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-thazole, 1, 2,3,4-tetrazole, benzo [b] thiophene
- substitution pattern is arbitrary, in the case of phenylene, for example, 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.
- the polymers modified with sulfonic acid groups preferably have a sulfonic acid group content in the range from 0.5 to 3 meq / g, preferably 0.5 to 2 meq / g. This value is determined via 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 with acid in a known manner, excess acid being removed by washing.
- the sulfonated polymer is first treated in boiling water for 2 hours. Excess water is then dabbed off and the sample is dried for 15 hours at 160 ° C. in a vacuum drying cabinet at p ⁇ 1 mbar. Then the dry weight of the membrane is determined.
- the polymer dried in this way is then dissolved in DMSO at 80 ° C. for 1 hour. The solution is then titrated with 0.1 M NaOH.
- the ion exchange capacity (IEC) is then calculated from the consumption of the acid up to the equivalent point and the dry weight.
- Polymers with sulfonic acid groups covalently bonded to aromatic groups are known in the art.
- polymers with aromatic sulfonic acid groups can be produced by sulfonation of polymers. Methods for sulfonating polymers are described in F. Kucera et. al. Polymer Engineering and Science 1988, Vol. 38, No 5, 783-792. The sulfonation conditions can be selected so that a low degree of sulfonation is produced (DE-A-19959289).
- polystyrene derivatives With regard to polymers with aromatic sulfonic acid groups, the aromatic radicals of which are part of the side group, reference is made in particular to polystyrene derivatives.
- US-A-6110616 describes copolymers of butadiene and styrene and their subsequent sulfonation for use in fuel cells.
- perfluorinated polymers as described in US-A-5422411 can be prepared by copolymerization from trifluorostyrene and sulfonyl-modified trifuorostyrene.
- abile thermoplastics are ADtemperaturst 'used 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. Sei. 83 (1993) p.211
- sulfonated polyphenylene sulfide DE-A-19527435
- polymers set out above with sulfonic acid groups bonded to aromatics can be used individually or as a mixture, with particular preference being given to mixtures which have polymers with aromatics in the main chain.
- the molecular weight of the polymers with sulfonic acid groups bonded to aromatics can, depending on the type of polymer and its processability, be in wide ranges.
- the weight average molecular weight M w is preferably in the range from 5,000 to 10,000,000, in particular 10,000 to 1,000,000, particularly preferably 15,000 to 50,000.
- polymers having sulfonic acid groups bonded to aromatics and having a low polydispersity index M w / M n have.
- the polydispersity index is preferably in the range 1 to 5, in particular 1 to 4.
- the weight ratio of polymer with monomers covalently bonded to aromatic groups to monomers comprising phosphonic acid groups is in the range from 0.1 to 50, preferably from 0.2 to 20, particularly preferably from 1 to 10.
- a further polymer can be added to the composition produced in step A) or the liquid used in step I) which does not comprise any sulfonic acid groups bound to aromatics.
- This polymer can be dissolved, dispersed or suspended, among other things.
- the preferred polymers include polyolefins such as poly (chloroprene),
- Polyacetylene polyphenylene, poly (p-xylylene), polyarylmethylene, polystyrene, polymethylstyrene,
- Polyvinyl alcohol polyvinyl acetate, polyvinyl ether, polyvinylamine, poly (N-vinylacetamide),
- Polyvinylimidazole Polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl pyridine, polyvinyl chloride,
- Polyvinylidene chloride polytetrafluoroethylene, polyvinyl difluoride, polyhexafluoropropylene,
- Polychlorotrifluoroethylene polyvinyl fluoride, polyvinylidene fluoride, polyacrolein, polyacrylamide,
- Polyacetal polyoxymethylene, polyether, polypropylene oxide, polyepichlorohydrin,
- Polyester in particular polyhydroxyacetic acid, polyethylene terephthalate,
- Polymeric C-S bonds in the main chain for example polysulfide ether,
- Polyphenylene sulfide polyether sulfone, polysulfone, polyether ether sulfone, polyaryl ether sulfone,
- Polyphenylene sulfone polyphenylene sulfide sulfone, poly (phenylisulfide-1,4-phenylene;
- Polyimines polyisocyanides, polyether brain.
- Polyetherimides poly (trifluoromethyl bis (phthalimide) phenyl, polyaniline, polyaramides, polyamides, polyhydrazides, polyurethanes,
- Liquid crystalline polymers especially Vectra as well
- Inorganic polymers for example polysilanes, polycarbosilanes, polysiloxanes,
- Polysilicic acid Polysilicates, silicones, polyphosphazenes and polythiazyl.
- polymers can be used individually or as a mixture of two, three or more polymers.
- Polymers which contain at least one nitrogen atom, oxygen atom and / or sulfur atom in a repeating unit are particularly preferred.
- Particularly preferred are polymers which contain at least one aromatic ring with at least one nitrogen, oxygen and / or sulfur heteroatom per repeating unit.
- Polymers based on polyazoles are particularly preferred within this group. 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 with one to three nitrogen atoms, which can be fused to another ring, in particular 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 (XXI) 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 for a tetra-bonded aromatic or heteroaromatic group, which can be mono- or polynuclear
- Ar 1 are the same or different and for a divalent aromatic or heteroaromatic group, which can be mono- or polynuclear
- Ar 2 are the same or different
- Ar 3 are the same or different for a two or three-membered aromatic or heteroaromatic group, which may be mono- or polynuclear, and for a tridentic aromatic or heteroaromatic group, which may be single 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 tetra-aromatic or heteroaromatic group which may be mono- or polynuclear
- Ar 6 are the same or different and for a divalent aromatic or heteroaromatic group, which can be mononuclear or polynuclear
- 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, 3,4-oxazole, pyrazole , 2,5-diphenyl-1, 3,4-oxadiazoI, 1, 3,4-thiadiazole, 1, 3,4-triazole, 2,5-diphenyI-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] thioph
- 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 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, hydroxyl 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.
- polyazole polymers are polyimidazoles, polybenzthiazoles, polybenzoxazoles, polyoxadiazoles, polyquinoxaiines, polythiadiazoles poly (pyridines), poly (pyrimidines), and poly (tetrazapyrenes).
- 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 present as block copolymers (diblock, triblock), statistical 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 00 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.
- polyazole polymers are polyimidazoles, polybenzimidazole ether ketone, polybenzthiazoles, polybenzoxazoles, polytriazoles, polyoxadiazoles, polythiadiazoles, polypyrazoles, polyquinoxalines, poly (pyridines), poly (pyrimidines), and poly (tetrazapyrenes).
- Preferred polyazoles are distinguished by a high molecular weight. This applies in particular to 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 from Celanese is particularly preferred.
- the properties of the polymer film and polymer membrane can be improved by sieving the starting polymer, as described in German patent application No. 10129458.1.
- the mixture produced in step A) or the liquid used in step I) can 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 have a positive impact on processability. For example, the rheology of the solution can be improved; so that it can be extruded or crocheted more easily.
- fillers in particular proton-conducting fillers, and additional acids can also be added to the membrane.
- Such substances preferably have an intrinsic conductivity at 100 ° C. of at least 10 "6 S / cm, in particular 10 " 5 S / cm.
- the addition can take place, 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 in step C) or step II).
- 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 like 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 4 , Ce (HP0 4 ) 2 ,.
- 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 4 -analyses, NH 4 -sodalites, NH 4 -galates, H-montmorillonites, acids such as HCI0 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 polyazoles.
- additives can be present in the proton-conducting polymer membrane in customary amounts, but the positive properties, such as high conductivity, long service life and high mechanical stability of the membrane, should not be adversely affected by the addition of too large amounts of additives, generally including Membrane after the polymerization in step C) or step II) 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% by weight). These additives improve performance, increase proximity to the cathode to increase oxygen solubility and diffusion, and decrease the absorption 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% by weight.
- Non-limiting examples of perfluorinated suifonic acid additives are: trifluomethanesulfonic acid, Kaliumtrifluormethansuifonat, sodium trifluoromethanesulfonate, lithium, Ammoniumtrifluormethansulfonat, Kaliumperfluorohexansulfonat, Natriumperfluorohexansulfonat perfluorohexanesulphonate, lithium, ammonium perfluorohexanesulphonate, perfluorohexanesulphonic acid, potassium nonafluorobutanesulphonate, Natriumnonafluorbutansulfonat, Lithiumnonafluorbutansulfonat, Ammoniumnonafluorbutansulfonat, Cäsiumnonafluorbutansulf onate, triethylammonium perfluorohexasulfonate and perflurosulfoimide.
- Suitable carriers are all carriers which are inert under the conditions. These carriers include, in particular, films made from polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), polyhexafluoropropylene, copolymers of PTFE with hexafluoropropylene, polyimides, polyphenylene sulfides (PPS) and polypropylene (PP).
- PET polyethylene terephthalate
- PTFE polytetrafluoroethylene
- PTFE polyhexafluoropropylene
- copolymers of PTFE with hexafluoropropylene polyimides
- PPS polyphenylene sulfides
- PP polypropylene
- the thickness of the flat structure according to step B) is preferably between 10 and 4000 ⁇ m, preferably between 15 and 3500 ⁇ m, in particular between 20 and 3000 ⁇ m, particularly preferably between 30 and 1500 ⁇ m and very particularly preferably between 50 and 1200 ⁇ m.
- the polymerization of the monomers comprising phosphonic acid groups in step C) or step II) is preferably carried out by free radicals.
- the radical formation can take place thermally, photochemically, chemically and / or electrochemically.
- a starter solution containing at least one substance capable of forming radicals can be added to the mixture after the mixture has been heated in accordance with step A). Furthermore, a starter solution can be applied to the flat structure obtained after step B). This can be done by means of measures known per se (e.g. spraying, dipping, etc.) which are known from the prior art. If the membrane is made by swelling, a starter solution can be added to the liquid. This can also be applied to the flat structure after swelling.
- Suitable 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, benzpinakoi, dibenzyl derivatives, methyl ethylene ketone peroxide, 1, 1-azobiscyclohexane carbonitrile, methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, didecanoyiperoxide, tert-butyl per-2-ethylhexanoate,
- 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 ( ⁇ Igacure 184), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (®lrgacure 819) and 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-phenylpropan-1-one ( ⁇ Irgacure 2959), each from Ciba Geigy Corp. are commercially available.
- Free radical generator added.
- the amount of radical generator can be varied depending on the desired degree of polymerization.
- IR InfraRot, ie light with a wavelength of more than 700 nm
- NIR Near IR, ie light with a wavelength in the range from approx. 700 to 2000 nm or an energy in the range of approx. 0.6 to 1.75 eV).
- 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.492-511; 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. Sci.-Revs. Macromol. Chem. Phys. C22 (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 very particularly preferably from 20 to 200 kGy.
- the polymerization of the monomers comprising phosphonic acid groups in step C) or step II) is preferably carried out at temperatures above room temperature (20 ° C.) and below 200 ° C., in particular at temperatures between 40 ° C. and 150 ° C., particularly preferably between 50 ° C. and 120 ° C.
- the polymerization is preferably carried out under normal pressure, but can also be carried out under the action of pressure.
- the polymerization leads to a solidification of the flat structure, 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 sheet-like structure obtained in step B).
- the membranes have 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 successively loaded with a Vickers diamond within 20 s up to a force of 3 mN 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 this being intended to 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 YHU is at least 0.5 MPa, in particular at least 5 MPa and very particularly preferably at least 10 MPa, without any intention that this should impose a restriction.
- the flat structure which is 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 repeat units, in particular at least 50 repeat units, very particularly preferably at least 100 repeat units.
- M n the number average molecular weight
- the proportion by weight of monomers comprising phosphonic acid groups and of radical initiators is kept constant in comparison with the ratios of the manufacture 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 used.
- 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, particularly preferably at most 10% by weight and very particularly preferably at most 5% by weight.
- preferred membranes comprise portions of polymers comprising low molecular weight 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 is preferably between 15 and 1000 ⁇ m, preferably between 20 and 500 ⁇ m, in particular between 30 and 250 ⁇ m.
- the membrane obtained in step C) or step II) is preferably self-supporting, ie it can be detached from the support without damage and then, if necessary, processed further 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 ° 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 250 kGy, in particular 10 to 200 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 membrane comprises at least 3% by weight, preferably at least 5% by weight and particularly preferably at least 7% by weight, of phosphorus (as an element), based on the total weight of the membrane.
- the proportion of phosphorus can be determined using an elementary analysis.
- the membrane is dried at 110 ° C. for 3 hours in a vacuum (1 mbar).
- the polymers comprising phosphonic acid groups preferably have a phosphonic acid group content of at least 5 meq / g, particularly preferably at least 10 meq / g. This value is determined via the so-called ion exchange capacity (IEC).
- IEC ion exchange capacity
- the phosphonic acid groups are converted into the free acid, the measurement being carried out before polymerization of the monomers comprising phosphonic acid groups he follows.
- the sample is then titrated with 0.1 M NaOH.
- the ion exchange capacity (IEC) is then calculated from the consumption of the acid up to the equivalent point and the dry weight.
- 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 the presence of polymers containing phosphonic acid groups.
- the polymer membrane 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 an improved proton conductivity. At temperatures of 120 ° C., this is at least 1 mS / cm, preferably at least 2 mS / cm, in particular at least 5 mS / cm, preferably measured without humidification.
- the membranes show a high conductivity even at a temperature of 70 ° C.
- the conductivity depends, among other things, 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
- the water formed by the reaction is sufficient to achieve 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 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 before the sample assembly. To measure the temperature dependency, 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 temperature, the sample is kept at this temperature for 10 minutes before starting the measurement.
- the passage current density when operating with 0.5 M methanol solution and 90 ° C. in a so-called liquid direct methanol fuel cell 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 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 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 CO 2 sensor. From the value of the C0 2 amount thus obtained, as from P. Zelenay, SC Thomas, S. Gottesfeld in S. Gottesfeld, TF filler "Proton Conducting Membrane Fuel Cells II" ECS Proc. Vol. 98-27 p. 300 -308, the passage current density is calculated.
- the intrinsically conductive polymer membranes according to the invention include use in fuel cells, in electrolysis, in capacitors and in battery systems. Because of their property profile, the polymer membranes can preferably be used in fuel cells, in particular in DMBZ fuel cells (direct methanol fuel cell).
- the present invention also relates to a membrane electrode unit 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.
- gas diffusion layers provided with a catalytically active layer can be 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 papers, carbon fiber fabrics, graphitized carbon fiber fabrics and / or flat structures which have been made conductive by adding carbon black.
- the catalytically active layer contains a catalytically active substance.
- a catalytically active substance include noble 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 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.
- PTFE polytetrafluoroethylene
- the weight ratio of fluoropolymer to catalyst material is greater than 0.1, this ratio preferably being in the range from 0.2 to 0.6.
- 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 noble metal content of the catalyst layer is 0.1 to 10.0 mg / cm 2 , preferably 0.2 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 catalytically active layer can be applied to the membrane according to the invention and this can be connected to a gas diffusion layer.
- the membrane formation can also take place directly on the electrode instead of on a support.
- a membrane is also the subject of the present invention.
- Another object of the present invention is an electrode with a proton-conducting polymer coating containing polymers with sulfonic acid residues which are bonded to aromatic groups, obtainable by a process comprising the steps
- step B) Polymerization of the monomers comprising phosphonic acid groups present in the sheet-like structure obtainable according to step B)
- all preferred embodiments of a self-supporting membrane also apply accordingly to a membrane applied directly to the electrode.
- the coating has a thickness between 2 and 3000 ⁇ m, preferably between 2 and 2000 ⁇ m, in particular between 3 and 1500 ⁇ m, particularly preferably 5 to 500 ⁇ m and very particularly preferably between 10 to 200 ⁇ m, without this there should be a restriction.
- the polymerization in step C) leads to a hardening of the coating.
- the treatment is carried out until the coating has sufficient hardness to be able to be pressed into a membrane electrode assembly.
- the hardness is sufficient if a membrane treated accordingly is self-supporting. In many cases, however, a lower hardness is sufficient.
- the hardness determined in accordance with DIN 50539 is generally at least 1 mN / mm 2 , preferably at least 5 mN / mm 2 and very particularly preferably at least 50 mN / mm 2 , without any intention that this should impose a restriction.
- An electrode coated in this way can be installed in a membrane-electrode unit, which may have at least one polymer membrane according to the invention.
- 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) to C) and the catalyst is applied.
- the membrane according to steps A) to C) can also be formed on a support or a support film which already has the catalyst. After removing the carrier or the carrier film, the catalyst is on the membrane according to the invention.
- the present invention also relates to a membrane-electrode unit which has at least one coated electrode and / or at least one polymer membrane according to the invention.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Fuel Cell (AREA)
- Conductive Materials (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Inert Electrodes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006525126A JP2007504616A (ja) | 2003-09-04 | 2004-09-04 | 芳香族基へ共有結合されているスルホン酸基を有するポリマーを含むプロトン伝導性高分子膜、膜電極ユニット、および燃料電池におけるそれらの使用 |
EP04764851A EP1678778A2 (de) | 2003-09-04 | 2004-09-04 | Protonenleitende polymermembran enthaltend polymere mit an aromatische gruppen kovalent gebundene sulfonsäuregruppen, membran -elektroden-einheit und deren anwendung in brennstoffzellen |
US10/570,637 US20070055045A1 (en) | 2003-09-04 | 2004-09-04 | Proton-conducting polymer membrane containing polymers with sulfonic acid groups that are covalently bonded to aromatic groups, membrane electrode unit, and use thereof in fuel cells |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10340927.0 | 2003-09-04 | ||
DE10340927A DE10340927A1 (de) | 2003-09-04 | 2003-09-04 | Protonenleitende Polymermembran enthaltend Polymere mit an aromatische Gruppen kovalent gebundene Sulfonsäuregruppen, Membran-Elektoden-Einheit und deren Anwendung in Brennstoffzellen |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2005024988A2 true WO2005024988A2 (de) | 2005-03-17 |
WO2005024988A3 WO2005024988A3 (de) | 2005-11-03 |
Family
ID=34223365
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2004/009900 WO2005024988A2 (de) | 2003-09-04 | 2004-09-04 | Protonenleitende polymermembran enthaltend polymere mit an aromatische gruppen kovalent gebundene sulfonsäuregruppen, membran-elektroden-einheit und deren anwendung in brennstoffzellen |
Country Status (5)
Country | Link |
---|---|
US (1) | US20070055045A1 (de) |
EP (1) | EP1678778A2 (de) |
JP (1) | JP2007504616A (de) |
DE (1) | DE10340927A1 (de) |
WO (1) | WO2005024988A2 (de) |
Cited By (4)
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WO2006117199A1 (de) * | 2005-05-03 | 2006-11-09 | Basf Fuel Cell Gmbh | Brennstoffzellen mit geringerem gewicht und volumen |
WO2008142570A2 (en) * | 2007-03-21 | 2008-11-27 | Advent Technologies | Proton conductors based on aromatic polyethers and their use as electrolytes in high temperature pem fuel cells |
JP2009513756A (ja) * | 2005-10-31 | 2009-04-02 | ビーエーエスエフ、フューエル、セル、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング | 改良された膜電極アセンブリ及び耐用年数が長い燃料電池 |
JP2009524205A (ja) * | 2006-01-23 | 2009-06-25 | トーマス ヘーリング | ホスホン酸含有電解液 |
Families Citing this family (5)
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DE10361832A1 (de) * | 2003-12-30 | 2005-07-28 | Celanese Ventures Gmbh | Protonenleitende Membran und deren Verwendung |
DE10361932A1 (de) | 2003-12-30 | 2005-07-28 | Celanese Ventures Gmbh | Protonenleitende Membran und deren Verwendung |
US20080317946A1 (en) * | 2007-06-21 | 2008-12-25 | Clearedge Power, Inc. | Fuel cell membranes, gels, and methods of fabrication |
US8119294B2 (en) * | 2007-11-19 | 2012-02-21 | Clearedge Power, Inc. | System and method for operating a high temperature fuel cell as a back-up power supply with reduced performance decay |
CN107431223B (zh) * | 2015-04-14 | 2021-05-07 | 洛克希德马丁能量有限公司 | 具有双极膜的液流电池平衡电池单元及其使用方法 |
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- 2004-09-04 JP JP2006525126A patent/JP2007504616A/ja active Pending
- 2004-09-04 US US10/570,637 patent/US20070055045A1/en not_active Abandoned
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006117199A1 (de) * | 2005-05-03 | 2006-11-09 | Basf Fuel Cell Gmbh | Brennstoffzellen mit geringerem gewicht und volumen |
JP2009513756A (ja) * | 2005-10-31 | 2009-04-02 | ビーエーエスエフ、フューエル、セル、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング | 改良された膜電極アセンブリ及び耐用年数が長い燃料電池 |
JP2009524205A (ja) * | 2006-01-23 | 2009-06-25 | トーマス ヘーリング | ホスホン酸含有電解液 |
US20100047655A1 (en) * | 2006-01-23 | 2010-02-25 | Haering Thomas | Electrolyte containing phosphonic acid |
US9023557B2 (en) * | 2006-01-23 | 2015-05-05 | Between Lizenz Gmbh | Method for preparing a solution of a sulfonated polymer and an amino-phosphonic acid in an aprotic solvent |
WO2008142570A2 (en) * | 2007-03-21 | 2008-11-27 | Advent Technologies | Proton conductors based on aromatic polyethers and their use as electrolytes in high temperature pem fuel cells |
WO2008142570A3 (en) * | 2007-03-21 | 2009-02-05 | Advent Technologies | Proton conductors based on aromatic polyethers and their use as electrolytes in high temperature pem fuel cells |
Also Published As
Publication number | Publication date |
---|---|
DE10340927A1 (de) | 2005-03-31 |
WO2005024988A3 (de) | 2005-11-03 |
EP1678778A2 (de) | 2006-07-12 |
JP2007504616A (ja) | 2007-03-01 |
US20070055045A1 (en) | 2007-03-08 |
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