EP1345674A1 - Membrane ceramique conductrice de cations ou de protons a base d'un acide hydroxysilylique, son procede de production et son utilisation - Google Patents

Membrane ceramique conductrice de cations ou de protons a base d'un acide hydroxysilylique, son procede de production et son utilisation

Info

Publication number
EP1345674A1
EP1345674A1 EP01270377A EP01270377A EP1345674A1 EP 1345674 A1 EP1345674 A1 EP 1345674A1 EP 01270377 A EP01270377 A EP 01270377A EP 01270377 A EP01270377 A EP 01270377A EP 1345674 A1 EP1345674 A1 EP 1345674A1
Authority
EP
European Patent Office
Prior art keywords
membrane
acid
conducting
hydroxysilyl
proton
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Withdrawn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
EP01270377A
Other languages
German (de)
English (en)
Inventor
Volker Hennige
Christian Hying
Gerhard HÖRPEL
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.)
Creavis Gesellschaft fuer Technologie und Innovation mbH
Original Assignee
Creavis Gesellschaft fuer Technologie und Innovation mbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Creavis Gesellschaft fuer Technologie und Innovation mbH filed Critical Creavis Gesellschaft fuer Technologie und Innovation mbH
Publication of EP1345674A1 publication Critical patent/EP1345674A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0048—Inorganic membrane manufacture by sol-gel transition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/108—Inorganic support material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/142—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers"
    • 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
    • B01D71/02—Inorganic material
    • 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
    • B01D71/02—Inorganic material
    • B01D71/0215—Silicon carbide; Silicon nitride; Silicon oxycarbide
    • 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
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B01D71/027—Silicium oxide
    • 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
    • B01D71/02—Inorganic material
    • B01D71/04—Glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • 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
    • C08J5/2275—Heterogeneous membranes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/26—Electrical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • 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
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/02—Polysilicates
    • 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
    • H01M2300/0068—Solid electrolytes inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a cation- or proton-conducting membrane which contains an immobilized hydroxysilyl acid or its salt, a ner process for its production and its use.
  • WO99 / 62620 first described the production of an ion-conducting, permeable composite material based on a ceramic and its use.
  • the steel mesh described in WO99 / 62620 as the preferred carrier to be used is, however, absolutely unsuitable for the use of the composite material as a membrane in fuel cells, since short circuits between the electrodes very easily occur during operation of the fuel cell.
  • This composite material also does not appear to be suitable for use in a fuel cell because it is said to be permeable to material.
  • the membrane must at least be impermeable to the reaction gases, ie H 2 , CH 3 OH and O 2 .
  • the ion-conducting membrane according to the invention is substantially more hydrophilic than the fluorinated, hydrophobic polymer membranes currently in use. This allows the water on the cathode side to diffuse back easily to the anode and thus prevents the membrane from drying out, even at higher power densities and operating temperatures.
  • the present invention therefore relates to a cation- / proton-conducting membrane which has immobilized hydroxysilyl acid or salts thereof as the cation- or proton-conducting material.
  • the ammonium, alkali and alkaline earth metal salts are particularly preferably used as salts.
  • the present invention also relates to a method in which a membrane is infiltrated with a hydroxysilyl acid and this is immobilized on and in the membrane.
  • the present invention also relates to the use of such a membrane as a catalyst for acid or base-catalyzed reactions, as a membrane in fuel cells or as a membrane in electrodialysis, membrane electrolysis or electrolysis.
  • the subject of the present invention is a fuel cell which, as the electrolyte membrane, has a cation-z proton-conducting membrane according to the invention or claim 1.
  • the membranes according to the invention are notable for high cation-Z proton conductivity even at low water partial pressures and high temperatures.
  • the membranes according to the invention can also be used at temperatures above 100 ° C., preferably from 100 to 200 ° C.
  • reformate fuel cells are and DMFCs, which are characterized by high power densities even at low water partial pressures and high temperatures.
  • the openwork carrier can e.g. in a first step according to WO 99Z15262 into a mechanically and thermally stable, permeable ceramic composite material which is neither electrically conductive nor ionically conductive.
  • Composites according to WO 99Z15262 have e.g. Carriers made of at least one material, selected from glasses, ceramics, minerals, plastics, amorphous substances, natural products, composite materials or from at least a combination of these materials.
  • the carriers which may have the aforementioned materials, may have been modified by a chemical, thermal or mechanical treatment method or a combination of the treatment methods.
  • the membrane preferably has a carrier which has at least interwoven, bonded, matted or ceramic-bonded fibers or at least sintered or bonded moldings, balls or particles.
  • the composite material used has at least two grain size fractions of at least one inorganic component. It can also be advantageous if the composite material has at least two grain size fractions of at least two inorganic components.
  • the grain size ratio can be from 1: 1 to 1: 10,000, preferably from 1: 1 to 1: 100.
  • the quantitative ratio of the grain size fractions in the composite material can preferably be from 0.01: 1 to 1: 0.01.
  • the hydroxysilyl acid can be used directly or in the form of a precursor, ie a derivative (e.g. Alcoholate) can be used.
  • a derivative e.g. Alcoholate
  • R 1 is a linear or branched alkyl or alkylene group with 1 to 12 carbon atoms, a cycloalkyl group with 5 to 8 carbon atoms or a unit of the general formulas
  • Preferred hydroxysilyl acids or their precursors are trihydroxysilylpropylsulfonic acid, trihydroxysilylpropylmethylphosphonic acid, or dihydroxysilylpropylsulfonic acid or salts thereof.
  • the existing hydroxyl groups or those generated by hydrolysis serve to bind the silylic acids to the inorganic composite material. This connection immobilizes the acid or its salt, ie makes it insoluble.
  • the structure of the ion-conducting material to be built up can be precisely adjusted by a suitable choice of the tri- (network former), di- (chain former) and monohydroxysilyl acid (chain link) as well as by the addition of further sol former.
  • Suitable sol formers are, for example, the hydrolyzed precursors of SiO 2 , Al 2 O 3 , P 2 O 5 , TiO 2 or ZrO 2 .
  • Trihydroxysilyl acids are known from EP 0 771 589, EP 0 765 897 and EP 0 582 879. In these publications, the production of shaped acid catalysts based on trihydroxysilylpropylsulfonic acid and trihydroxysilylpropylmercaptan has been described.
  • the membrane according to the invention has at least one further ion-conducting compound from the group of iso- or heteropolyacids, zeolites, mordenites, aluminosilicates, ⁇ -aluminum oxides, zirconium, titanium or cerium phosphates, phosphonates or sulfoaryl phosphonates, antimonic acids, Has phosphorus oxides, sulfuric acid, perchloric acid or their salts.
  • the membrane also contains nanoscale powders from the SiO 2 , Al 2 O 3 , ZrO 2 or TiO 2 series .
  • the membrane of the invention is at a temperature of -40 ° C to 300 ° C, preferably from - 10 to 200 ° C cation or proton conductive.
  • the membrane according to the invention is also flexible and, depending on the composite material used, can be bent to a minimum radius of 25 mm, preferably 10 mm, very particularly preferably 5 mm.
  • the membrane is infiltrated with a solution or suspension which, in addition to the hydroxysilyl acid, its salts or precursors, also contains at least one further proton- or cation-conducting material.
  • the composite material can be infiltrated with a solution, a sol or a suspension which, in addition to the hydroxysilylic acid, its salts or precursors contains at least one further material based on a hydrolyzed or hydrolyzable compound of a metal or semimetal which contributes to immobilization of the hydroxysilyl acid.
  • the membrane has a thickness of less than 200 ⁇ m, preferably less than 100 ⁇ m and very particularly preferably less than 50 or 20 ⁇ m.
  • hydroxysilyl acid To immobilize the hydroxysilyl acid in and on the membrane, it is infiltrated or treated at least with the hydroxysilyl acid, if appropriate in aqueous or alcoholic solution.
  • the ion-conducting compounds already mentioned can also be introduced. These can be in dissolved form or suspended in the solution used for the coating.
  • hydroxysilyl acid must be immobilized in and on a membrane. This can be done thermally according to the method of the invention, the membrane infiltrated with hydroxysilyl acid first being treated at a temperature of 0 to 50 ° C. and the hydroxysilyl acid being subsequently immobilized at a temperature of 20 to 250 ° C.
  • brine that has been produced as described above, but also commercially available brine, such as Titanium or zirconium nitrate sol, zirconium acetate sol or silica sol.
  • At least one inorganic proton-conducting component selected from the group of iso- or heteropolyacids, such as, for example, 12-tungsten phosphoric acid (WPA), silicon tungstic acid, zirconium, titanium or cerium phosphates, phosphonates or sulfoaryl phosphonates, antimonic acids, phosphorus oxides, aerosil ( SiO 2 ), nanoscale Al 2 O 3 , TiO 2 or ZrO 2 powder, zeolites, mordenites, aluminosilicates, ⁇ -aluminum oxides, suspended in the sol.
  • WPA 12-tungsten phosphoric acid
  • silicon tungstic acid silicon tungstic acid
  • zirconium titanium or cerium phosphates
  • phosphonates or sulfoaryl phosphonates antimonic acids
  • phosphorus oxides aerosil ( SiO 2 )
  • nanoscale Al 2 O 3 TiO 2 or ZrO 2 powder
  • zeolites morden
  • the freedom from cracks in the membrane according to the invention can be optimized by a suitable choice of the grain size of the suspended compounds depending on the size of the pores, holes or interspaces of the porous ceramic composite material.
  • the membrane according to the invention is therefore also suitable as a catalyst for acid or base-catalyzed reactions.
  • the membrane filled with the gel is dried at a temperature of 200 ° C. for 60 minutes, so that the gel has solidified and has been rendered water-insoluble. In this way a dense membrane is obtained which has a proton conductivity at room temperature and normal ambient air of approx. 2-10 "3 SZcm.
  • Example 2 25 g of tungsten phosphoric acid are dissolved in 50 ml of the sol from Example 2. The composite material from Example 1 is immersed in this sol for 15 minutes. Then proceed as in Example 2.
  • Trihydroxysilylmethylphosphonic acid dissolved in a little water is diluted with ethanol.
  • the same amount of TEOS is added to this solution and stirring is continued briefly.
  • the composite material from Example 1 is immersed in this sol for 15 minutes. Then proceed as in Example 2.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Sustainable Development (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Sustainable Energy (AREA)
  • Metallurgy (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Fuel Cell (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Conductive Materials (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

L'invention concerne une membrane conductrice de cations ou de protons, son procédé de production et son utilisation. La membrane selon l'invention représente une nouvelle classe de membranes solides conductrices de protons. La base de cette invention est une membrane céramique souple et poreuse, décrite dans le dépôt de brevet PCT/EP98/05939. Cette membrane est infiltrée avec une substance conductrice de protons, puis elle est séchée et consolidée de sorte qu'on obtient finalement une membrane imperméable, conductrice de cations ou de protons. La substance conductrice de protons est un acide hydroxysilylsulfonique ou un acide hydroxysilylphosphonique, intégré dans un réseau inorganique, par exemple SiO>2<. Ce faisant, la membrane céramique reste souple et peut être utilisée sans problème en tant que membrane dans une pile à combustible.
EP01270377A 2000-12-13 2001-10-27 Membrane ceramique conductrice de cations ou de protons a base d'un acide hydroxysilylique, son procede de production et son utilisation Withdrawn EP1345674A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10061920A DE10061920A1 (de) 2000-12-13 2000-12-13 Kationen-/protonenleitende keramische Membran auf Basis einer Hydroxysilylsäure, Verfahren zu deren Herstellung und die Verwendung der Membran
DE10061920 2000-12-13
PCT/EP2001/012466 WO2002047801A1 (fr) 2000-12-13 2001-10-27 Membrane ceramique conductrice de cations ou de protons a base d'un acide hydroxysilylique, son procede de production et son utilisation

Publications (1)

Publication Number Publication Date
EP1345674A1 true EP1345674A1 (fr) 2003-09-24

Family

ID=7666866

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01270377A Withdrawn EP1345674A1 (fr) 2000-12-13 2001-10-27 Membrane ceramique conductrice de cations ou de protons a base d'un acide hydroxysilylique, son procede de production et son utilisation

Country Status (9)

Country Link
US (1) US20040028913A1 (fr)
EP (1) EP1345674A1 (fr)
JP (1) JP2004515896A (fr)
AU (1) AU2002221771A1 (fr)
CA (1) CA2431055A1 (fr)
DE (1) DE10061920A1 (fr)
NO (1) NO20032719D0 (fr)
PL (1) PL361860A1 (fr)
WO (1) WO2002047801A1 (fr)

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AU2002221771A1 (en) 2002-06-24
CA2431055A1 (fr) 2002-06-20
US20040028913A1 (en) 2004-02-12
JP2004515896A (ja) 2004-05-27
DE10061920A1 (de) 2002-06-20
NO20032719L (no) 2003-06-13
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