EP1716614A1 - Membranes pour piles a combustible, procede pour produire de telles membranes et pour produire des piles a combustibles en utilisant de telles membranes - Google Patents

Membranes pour piles a combustible, procede pour produire de telles membranes et pour produire des piles a combustibles en utilisant de telles membranes

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Publication number
EP1716614A1
EP1716614A1 EP05715219A EP05715219A EP1716614A1 EP 1716614 A1 EP1716614 A1 EP 1716614A1 EP 05715219 A EP05715219 A EP 05715219A EP 05715219 A EP05715219 A EP 05715219A EP 1716614 A1 EP1716614 A1 EP 1716614A1
Authority
EP
European Patent Office
Prior art keywords
membrane
membranes
polymer
oxo acid
fuel cells
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05715219A
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German (de)
English (en)
Inventor
Dieter Melzner
Annette Reiche
Ulrich MÄHR
Suzana Kiel
Stefan Haufe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sartorius Stedim Biotech GmbH
Original Assignee
Sartorius AG
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Filing date
Publication date
Application filed by Sartorius AG filed Critical Sartorius AG
Publication of EP1716614A1 publication Critical patent/EP1716614A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/18—Polybenzimidazoles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/06—Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • Membranes for fuel cells methods of manufacturing the membranes and fuel cells using such membranes.
  • the invention relates to membranes made of organic polymers and derivatives of polybasic inorganic oxo acids, a process for producing the membranes and high-temperature polymer electrolyte membrane fuel cells using such membranes.
  • high-temperature polymer electrolyte membrane fuel cells which contain polymer electrolyte membranes (PEM) based on polybenzimidazole (PBI). These are doped with phosphoric acid. Since the conductivity of these polymer electrolyte membranes is not necessarily linked to the presence of water in the system, these PEM fuel cells can be operated at temperatures between 100 and 200 ° C.
  • the disadvantage of this fuel cell system is the discharge of phosphoric acid by washing it out with product water, in particular at temperatures below 100 ° C. This temperature range is covered in particular in mobile applications, forcibly during startup and shutdown of such fuel cells, which leads to a reduction in the performance of the systems.
  • the thermal stability of PBI is increased by low doping with phosphoric acid.
  • the mechanical stability of the PBI membranes decreases with high levels of doping.
  • It is common to chemically cross-link PBI membranes to increase their mechanical stability (WO 00/44816 AI, DE 101 10 752 AI, DE 101 40 147 AI).
  • Compounds with isocyanate and with epoxy groups which are able to react with the NH groups of the polybenzimidazole are used as crosslinkers.
  • the crosslinker can be added to the polymer solution and reacted during the membrane formation step with simultaneous evaporation of the solvent by increasing the temperature.
  • Criteria for as a networker Suitable compounds are good solubility in the polymer solution, a high crosslinking rate, and chemical and thermal stability of the crosslinking points under operating conditions in the fuel cell.
  • the crosslinking influences the swelling capacity of the membrane with the dopant H 3 PO.
  • the maximum achievable doping level drops.
  • the resulting swelling pressure when the dopant is absorbed can lead to the destruction of the membrane if the doping levels are high.
  • Polybenzimidazole can be crosslinked in this way by reaction with diepoxides or diisocyanates, but this is associated with disadvantages with regard to membrane doping with the dopant.
  • a further disadvantage is that the thermal and chemical stability, in particular of membranes crosslinked with diisocyanates, is insufficient for fuel cell applications.
  • crosslinking with diepoxide compounds Another disadvantage of crosslinking with diepoxide compounds is that the crosslinking takes place relatively slowly at temperatures below 100 ° C, which leads to procedural problems in the manufacturing process: For example, in order to be able to achieve a high degree of crosslinking, the reaction path must be long or Pulling speed in the continuous production of the membranes on a membrane pulling machine must be greatly reduced. At temperatures above 100 ° C the solvent evaporates faster than the crosslinking reaction can take place. The associated decrease in polymer chain mobility can lead to a slightly cross-linked membrane with low mechanical strength and undesirably high swelling capacity. Another disadvantage is that crosslinking with diepoxides or diisocyanates has no influence on the binding of phosphoric acid in the membrane. The disadvantage of the discharge of phosphoric acid in low operating conditions is not overcome.
  • the invention is therefore based on the object of providing membranes for fuel cells which are distinguished by a homogeneous absorption of dopants and their switching back and also ensure high mechanical stability at higher temperatures of up to at least 250 ° C. in the doped state.
  • a method for producing such membranes is also proposed.
  • a Another object of the invention is to provide fuel cells using such membranes for mobile and stationary applications.
  • the membranes according to the invention consist of at least one polymer containing nitrogen atoms, the nitrogen atoms of which are chemically bonded to the central atom of a polybasic inorganic oxo acid or its derivative.
  • the chemical bond can be an amide bond.
  • Polybasic inorganic oxo acids Cotton, Wilkinson, Inorganic Chemistry, Verlag Chemie, Weinheim, Deerfeld Beach, Florida, Basel 1982, 4th edition, pp.
  • Phosphorus, sulfur, molybdenum, tungsten, arsenic, antimony, bismuth, selenium, germanium, tin, lead, boron, chromium or silicon can be used as the central atom.
  • Phosphorus, molybdenum, tungsten and silicon are preferred and phosphorus is particularly preferred.
  • the polymer and the central atom of the oxo acid are preferably crosslinked to form a network which is capable of absorbing dopants, such as, for example, phosphoric acid, with the formation of proton-conducting polyelectrolyte membranes (PEM).
  • PEM proton-conducting polyelectrolyte membranes
  • Membranes which are particularly suitable for use in fuel cells have a degree of crosslinking of at least 70% of the polymer, preferably of more than 80%, particularly preferably of more than 90%.
  • Membranes according to the invention can be produced, for example, by reacting polybenzimidazole with alkoxy compounds or esters, amides or acid chlorides of an oxo acid.
  • the membranes according to the invention do not have proton-conducting properties which would be sufficient for use in fuel cells.
  • the membranes according to the invention excellently contain dopants such as, for example, phosphoric acid. can record and fix. Even at temperatures below 100 ° C., the dopant remains so strongly fixed in the membranes according to the invention that it is not discharged even in the start-up and shut-down area of fuel cells.
  • the membrane according to the invention has a higher hydrophobicity compared to conventional polybenzimidazole membranes, which means that it does not absorb the product water from the fuel cell, as a result of which the discharge of phosphoric acid is prevented, or at least greatly reduced.
  • Polymers selected from the group comprising polybenzimidazole, polypyrridine, polypyrimidine, polyimidazoles, polybenzothiazoles, polybenzoxazoles, polyoxadiazoles, polyquinoxalines, polythiadiazoles, poly (tetrazapyrenes) or a combination of two or more thereof can preferably be used. It is also possible to use polymers which carry reactive groups in the side chain of the polymer which are capable of forming amide bonds and polymers with primary or secondary amino groups and mixtures of these polymers with other polymers. According to the invention, organic derivatives, for example in the form of alkoxy compounds, esters, amides and acid chlorides, are preferably used as oxo acid derivatives.
  • the process according to the invention for producing the membranes is characterized by the following steps: a) preparing an anhydrous homogeneous solution from at least one organic polymer and a derivative of a polybasic inorganic oxo acid, the at least one polymer being capable of forming chemical bonds with the central atom of the oxo acid reactive groups, b) shaping the solution obtained into a membrane mold, c) heating the solution brought into the membrane mold to a temperature in the range from 50 to 90 ° C. until a self-supporting membrane is formed, and d) annealing the membrane at a temperature in the Range of 150 to 400 ° C over a period of 1 minute to 5 hours with removal of the residual solvent.
  • the reaction of the polymers used with the oxo acid derivatives proceeds sufficiently quickly when the solution brought into the membrane form is heated to a temperature in the range from 50 to 90 ° C., preferably from 70 ° C.
  • the membrane can then be removed from a molding base (casting base) without mechanical damage and rolled up, for example.
  • parts of the roll can be removed with a time delay.
  • the annealing takes place in a continuous process.
  • the tempering is carried out at temperatures in the range from 200 to 300 ° C., particularly preferably in the range from 230 to 280 ° C. and over a period in the range from 1 minute to 1 hour. But it is also possible to extend the annealing process up to 5 hours.
  • the manufacturing process is carried out under anhydrous conditions, for which purpose the procedure is carried out in anhydrous solvents, with dry reagents and under a dry protective gas atmosphere in the manner familiar to the person skilled in the art.
  • the phosphoric acid ester is used as a salt, preferably a weak, particularly preferably a weak and volatile organic base, such as an amine.
  • Organic oxo acid derivatives with phosphorus, sulfur, molybdenum, tungsten or silicon as the central atom of the oxo acid are preferably used in the process according to the invention.
  • Organic derivatives include, for example, acid chlorides, alkoxy compounds, preferably esters and / or amides of neutralized polybasic inorganic acids.
  • 2- (diethylhexyl) phosphate, molybdaenyl acetylacetonate and / or tetraethoxysilane are used as organic derivatives in the process.
  • the polymers used are those selected from the group comprising polybenzimidazole, polypyrridine, polypyrimidine, Polyimidazoles, polybenzthiazoles, polybenzoxazoles, polyoxadiazoles, polyquinoxalines, polythiadiazoles, poly (tetrazapyrene) or a combination of two or more thereof. It is also possible to use polymers which carry reactive groups in the side chain of the polymer which are capable of forming amide bonds and polymers with primary or secondary amino groups.
  • the solution used to form the solution into a membrane shape contains the polymer or the polymers and the oxo acid derivative.
  • the solvent is preferably selected from the group comprising N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc) and mixtures thereof, with dimethylacetamide being particularly preferred.
  • the concentration of the polymer (s) in the solution is in the range from 4 to 30% by weight, preferably 10 to 25% by weight and more preferably 15 to 25% by weight, based on the weight of the finished product , solution used for membrane production.
  • the concentration depends on the type of polymer (s) and their molecular weight and solubility in the solvent or solvent mixture in question.
  • the proportion of the oxo acid derivative is in the range from 5 to 80% by weight based on the polymer content, preferably from 10 to 40% by weight and more preferably from 15 to 30% by weight.
  • PBI is reacted with 2- (diethylhexyl) phosphate, preferably using PBI whose 1% by weight solution in N, N dimethylacetamide has an intrinsic viscosity or intrinsic viscosity of 0.90 dl / g and higher. Based on these values, the Mark-Houwink relationship can be used to calculate a number-average molar mass of 60,000 g / mol and higher. The use of PBI with molecular weights in the range between 35,000 and 200,000 g / mol is also possible.
  • the process according to the invention for the production of membranes is distinguished by the fact that a chemically stable phosphoric acid amide bond is produced between the PBI and the phosphoric acid derivative.
  • This direct attachment of the phosphoryl group to the nitrogen atom of the polybenzimidazole is extremely stable
  • a further reaction of the phosphoric acid amide to the phosphoric acid diamide takes place, as a result of which the membrane is additionally crosslinked into a network and as a result of which its mechanical properties are further improved.
  • Fuel cells according to the invention consist of at least one membrane electrode unit (MEA), which are assembled from two flat gas diffusion electrodes and a membrane according to the invention arranged in between, and a dopant for the membrane. They are suitable as high-temperature polyelectrolyte membrane fuel cells for a working temperature up to at least 250 ° C.
  • the gas diffusion electrodes are loaded with the dopant in such a way that they represent a dopant reservoir for the membrane, the membrane having become proton-conducting when exposed to pressure and temperature, and being connected to the gas distribution electrodes by proton-conducting.
  • Fig. 1 shows an IR spectrum of a membrane according to the invention
  • Fig. 2 shows a current-voltage characteristic of a fuel cell according to the invention with membranes produced according to Example 1
  • Fig. 3 shows a current-voltage characteristic of a fuel cell according to the invention with membranes produced according to Example 6
  • FIG. 4 shows a current-voltage characteristic of a fuel cell according to the invention with membranes produced according to Example 11.
  • example 1 shows an IR spectrum of a membrane according to the invention
  • Fig. 2 shows a current-voltage characteristic of a fuel cell according to the invention with membranes produced according to Example 1
  • Fig. 3 shows a current-voltage characteristic of a fuel cell according to the invention with membranes produced according to Example 6
  • FIG. 4 shows a current-voltage characteristic of a fuel cell according to the invention with membranes produced according to Example 11.
  • example 1 shows an IR spectrum of a membrane according to the invention
  • Fig. 2 shows a current-voltage characteristic of a fuel cell
  • the solution in the form of a membrane is heated to a temperature of 70 ° C. until a self-supporting membrane has formed.
  • the membrane is then annealed at a temperature of 250 ° C. for 4 hours while removing the residual solvent.
  • the membrane produced in this way has a thickness of approx. 45 ⁇ m and can be used directly for the manufacture of membrane electrode assemblies.
  • a sharp pealc at a wavelength of 1000 cm "1 is observed in an IR spectrum for a phosphoric acid ester.
  • Such a signal can be seen, for example, in a membrane produced according to Example 1 in accordance with DE 101 55 543 C2. As can be seen in FIG.
  • the IR spectrum of the membrane according to the invention produced according to Example 1 does not have such a Pealc, which must be attributed to the fact that the phosphoric acid ester has been completely converted with PBI. Instead, a Pealc now occurs at a wavelength of about 800 cm "1 on which is to be assigned to a phosphorus-nitrogen bond of a phosphoric acid amide.
  • tensile stress measurements are carried out.
  • a membrane sample with a length of 10 cm and a width of 2 cm is clamped in a measuring device Z 2.5 from Zwick GmbH & Co. and at a speed of 5 cm min
  • the viscosity was determined using a 1% by weight solution of PBI in N, N-dimethylacetamide. Using the Mark-Houwink relationship, an average molar mass of the PBF of 60,000 g / mol can be calculated from the intrinsic viscosity. pulled apart.
  • the polymer membrane produced according to Example 1 breaks at a tension of 164 N / mm and an elongation of 5%.
  • the degree of crosslinking of membranes produced according to Example 1 is determined by extraction.
  • a sample is punched out of a polymer membrane piece of 7.5 cm x 7.5 cm edge length with a known starting weight and placed in a round bottom flask. So much dimethylacetamide is added to the round bottom flask until the polymer piece is completely covered with liquid.
  • the round bottom flask is heated to 130 ° C using an oil bath. Non-cross-linked PBI membranes completely dissolve under these conditions. After heating for one hour at 130 ° C. and cooling to room temperature, the solvent is filtered off.
  • the sample is dried in a drying cabinet at 200 ° C. overnight. After drying, the sample is placed in a desiccator filled with dry pearls to cool to room temperature and is evacuated to 100 mbar. It was determined gravimetrically that 93% of the membrane is insoluble and thus crosslinked in a stable manner.
  • the membrane produced according to Example 1 is cut into square pieces measuring approximately 104.04 cm 2 .
  • Commercially available ELAT electrodes with 2.0 mg / cm 2 Pt loading and an area of 50 cm 2 from E-TEK are loaded with 15 mg / cm 2 phosphoric acid.
  • the electrodes thus impregnated are used with the membrane according to the invention -Electrode unit (MEA) installed in a test fuel cell from Fuel Cell Technologies, Inc.
  • the test fuel cell is closed with a contact pressure of 15 bar and conditioned at 160 ° C without pressure in an N stream for 16 h.
  • Example 5 Example 5
  • Fig. 2 shows the course of a current-voltage curve for a fuel cell manufactured according to Example 4 with an MEA at 160 ° C.
  • the gas flow for H 2 was 783 sml / min and for air 2486 sml / min.
  • the performance parameters were determined on an FCATS Advanced Screener from Hydrogenics Inc. At 3 bar abs. a maximum power density of 0.44 W / cm 2 and a current density of 1.3 A / cm 2 are measured. Dry gases were used for this. Under the specified test conditions, the fuel cell shows an impedance of 450 m ⁇ cm 2 at a measuring frequency of 1689 Hz.
  • the viscosity was determined using a 1% by weight solution of PBI in N, N-dimethylacetamide. Using the Mark-Houwink relationship, an average molar mass of the PBF of 60,000 g / mol can be calculated from the intrinsic viscosity. carried out.
  • the membrane produced according to Example 6 tears at a tension of 199 N / mm 2 and an elongation of 5%.
  • the degree of crosslinking of the membranes produced according to Example 6 is as in
  • Example 3 described, determined by extraction.
  • FIG. 3 shows the course of a current-voltage curve for a fuel cell produced according to Example 9 at 160 ° C.
  • the gas flow for H 2 was 783 sml / min and for air 2486 sml / min.
  • the performance parameters were determined on an FCATS Advanced Screener from Hydrogenics Inc. Using dry gases, abs. measured a maximum power density of 0.28 W / cm 2 and a current density of 1.0 A / cm 2 . Under the specified test conditions, the MEA shows an impedance of 950 m ⁇ cm 2 at a measuring frequency of 2664 Hz.
  • a solution of PBI with an intrinsic viscosity or intrinsic viscosity of 0.90 dl / g in dimethylacetamide and a polymer concentration of 23% by weight are mixed with 2.76 g of tetraethoxysilane (silicate TES 28 from Wacker) added.
  • the solution obtained is formed under protective gas on a flat base to form a flat membrane.
  • the solution brought into the membrane form is heated to a temperature of 70 ° C. until a self-supporting membrane has formed. Subsequently, the membrane is removed by removing the residual solvent at a temperature of 250 ° C. over a period of 4 hours and then at 350 ° C. for 30 minutes.
  • the membrane has a thickness of approx. 36 ⁇ m and can be used for the manufacture of membrane electrode units immediately after manufacture.
  • Example 11 The mechanical stability of the membrane produced according to Example 11 was examined, as described in Example 2, with tensile stress measurements.
  • a membrane produced according to Example 11 is cut into square pieces measuring approximately 56.25 cm 2 .
  • Commercially available ELAT electrodes with 2.0 mg / cm 2 Pt loading and an area of 10 cm 2 from E-TEK are loaded with 13 mg / cm 2 phosphoric acid and with the membrane according to the invention as a membrane electrode assembly (MEA) built into a conventional arrangement in the test fuel cell from Fuel Cell Technologies, Inc.
  • MEA membrane electrode assembly
  • Fig. 4 shows the course of a current-voltage curve for a fuel cell manufactured according to Example 14 at 180 ° C.
  • the gas flow for H 2 was 170 sml / min and for air 570 sml / min. Unhumidified gases were used.
  • the performance parameters were determined on an FCATS Advanced Screener from Hydrogenics, Inc. As maximum output at 3 bar abs. was W / cm 2 at a current density of 1.0 A / cm 2 measured 0.34. Under the specified test conditions, the MEA shows an impedance of 280 m ⁇ cm 2 at a measuring frequency of 1314 Hz.

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Abstract

L'invention concerne des membranes pour des piles à combustible, qui se caractérisent par une absorption homogène et par une bonne rétention d'agents de dopage et qui, à l'état dopé, garantissent une stabilité mécanique élevée à hautes températures. Les membranes selon l'invention sont constituées d'au moins un polymère dont les atomes d'azote sont liés chimiquement à un atome central d'un dérivé d'un oxacide inorganique polybasique. Elles sont produites à partir de solutions anhydres de polymères et de dérivés d'oxacides, par chauffage de la solution mise en forme de membrane jusqu'à formation d'une membrane autoporteuse, puis par trempe de cette membrane. Les piles à combustible selon l'invention, constituées d'un ensemble membrane-électrode comprenant une membrane selon l'invention et de l'acide phosphorique comme agent de dopage, présentent, par exemple, une impédance de 0,5 à 1 Ocm2 pour une fréquence de mesure de 1000 Hz, à une température de fonctionnement de 160 °C et pour un flux gazeux de 170 ml/min pour l'hydrogène et de 570 ml/min pour l'air. Ces piles à combustible peuvent être utilisées en tant que piles à combustibles à membrane de type polyélectrolyte haute température, pour une température de travail d'au moins 250 °C.
EP05715219A 2004-02-04 2005-01-28 Membranes pour piles a combustible, procede pour produire de telles membranes et pour produire des piles a combustibles en utilisant de telles membranes Withdrawn EP1716614A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004005389A DE102004005389A1 (de) 2004-02-04 2004-02-04 Membranen für Brennstoffzellen, Verfahren zur Herstellung der Membranen und Brennstoffzellen unter Verwendung derartiger Membranen
PCT/EP2005/000838 WO2005076401A1 (fr) 2004-02-04 2005-01-28 Membranes pour piles a combustible, procede pour produire de telles membranes et pour produire des piles a combustibles en utilisant de telles membranes

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EP1716614A1 true EP1716614A1 (fr) 2006-11-02

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US (1) US7682723B2 (fr)
EP (1) EP1716614A1 (fr)
JP (1) JP2007522615A (fr)
CN (1) CN1918739A (fr)
DE (2) DE102004005389A1 (fr)
WO (1) WO2005076401A1 (fr)

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DE102005058578A1 (de) * 2005-12-08 2007-06-28 Sartorius Ag Membranen aus Polyazolen, Verfahren zu ihrer Herstellung und Brennstoffzellen unter Verwendung derartiger Membranen
JP4753201B2 (ja) * 2006-02-15 2011-08-24 綜研化学株式会社 Ｏｈ変性ポリベンゾイミダゾール樹脂及びその製造方法
DE102006010705A1 (de) * 2006-03-08 2007-09-13 Sartorius Ag Hybridmembranen, Verfahren zur Herstellung der Hybridmembranen und Brennstoffzellen unter Verwendung derartiger Hybridmembranen
US8039166B2 (en) * 2006-12-20 2011-10-18 Samsung Sdi Co., Ltd. Polymer electrolyte membrane for fuel cell, method of manufacturing the same, and fuel cell employing the same
US20120148936A1 (en) 2009-08-21 2012-06-14 Basf Se Inorganic and/or organic acid-containing catalyst ink and use thereof in the production of electrodes, catalyst-coated membranes, gas diffusion electrodes and membrane electrode units
DE102010029990A1 (de) 2010-06-11 2011-12-15 Wacker Chemie Ag Polymerfilme auf der Basis von Polyazolen
US20130206694A1 (en) * 2012-02-13 2013-08-15 King Abdullah University Of Science And Technology Membrane for water purification
US9283523B2 (en) * 2012-05-25 2016-03-15 Pbi Performance Products, Inc. Acid resistant PBI membrane for pervaporation dehydration of acidic solvents
CN103880121B (zh) 2012-12-20 2016-12-28 通用电气公司 水处理系统与方法
WO2015088579A1 (fr) 2013-12-09 2015-06-18 General Electric Company Dispositif électrochimique à base d'électrode composite polymère/métallique pour générer des oxydants
CN106967217A (zh) * 2016-01-14 2017-07-21 华南理工大学 聚咪唑类化合物及其原位制备方法和应用
CN108539235A (zh) * 2018-03-19 2018-09-14 同济大学 一种具有双网络结构的聚苯并咪唑质子导电膜及其制备方法

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US20070003808A1 (en) 2007-01-04
JP2007522615A (ja) 2007-08-09
CN1918739A (zh) 2007-02-21
DE102004005389A1 (de) 2005-08-25
WO2005076401A1 (fr) 2005-08-18
DE202005001541U1 (de) 2005-03-31
US7682723B2 (en) 2010-03-23

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