WO2003073545A2 - Membrane electrolytique souple a base d'un support contenant des fibres polymeres, procedes de realisation et utilisation associes - Google Patents

Membrane electrolytique souple a base d'un support contenant des fibres polymeres, procedes de realisation et utilisation associes Download PDF

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Publication number
WO2003073545A2
WO2003073545A2 PCT/EP2003/000256 EP0300256W WO03073545A2 WO 2003073545 A2 WO2003073545 A2 WO 2003073545A2 EP 0300256 W EP0300256 W EP 0300256W WO 03073545 A2 WO03073545 A2 WO 03073545A2
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Prior art keywords
zirconium
acid
electrolyte membrane
proton
membrane
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PCT/EP2003/000256
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German (de)
English (en)
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WO2003073545A3 (fr
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Volker Hennige
Christian Hying
Gerhard HÖRPEL
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Creavis Gesellschaft Für Technologie Und Innovation Mbh
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Priority to AU2003248341A priority Critical patent/AU2003248341A1/en
Publication of WO2003073545A2 publication Critical patent/WO2003073545A2/fr
Publication of WO2003073545A3 publication Critical patent/WO2003073545A3/fr

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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
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/881—Electrolytic membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8814—Temporary supports, e.g. decal
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8842—Coating using a catalyst salt precursor in solution followed by evaporation and reduction of the precursor
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8857—Casting, e.g. tape casting, vacuum slip casting
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • 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]
    • 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
    • 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 special proton-conductive, flexible electrolyte membranes, in particular for a fuel cell, to a method for producing these electrolyte membranes and to a flexible membrane electrode unit for a fuel cell, which comprises an electrolyte membrane according to the invention.
  • the present invention further relates to special intermediates in the manufacture of the membrane electrode assembly and special uses of the electrolyte membrane and membrane electrode assembly.
  • Fuel cells contain electrolyte membranes which, on the one hand, ensure the proton exchange between the half-cell reactions and, on the other hand, prevent a short circuit between the half-cell reactions.
  • MEAs membrane electrode units
  • electrolyte membranes made from organic polymers that are modified with acidic groups are known, such as Nafion® (DuPont, EP 0 956 604), sulfonated polyether ketones (Höchst, EP 0 574 791) , sulfonated hydrocarbons (Dais, EP 1 049 724) or the phosphoric acid-containing polybenzimidazole membranes (Celanese, WO 99/04445).
  • organic polymers have the disadvantage that the conductivity depends on the water content of the membranes. Therefore, these membranes must be swollen in water before use in the fuel cell and although water is constantly being formed on the cathode, additional water must be added from the outside during operation of the membrane to prevent drying out or a decrease in proton conductivity.
  • organic polymer membranes in a fuel cell must be operated both on the anode and cathode sides in an atmosphere saturated with water vapor. At elevated operating temperatures, electrolyte membranes made from organic polymers cannot be used, because at temperatures of more than about 100 ° C the water content in the membrane at atmospheric pressure can no longer be guaranteed. The use of such membranes in a reformate or direct methanol fuel cell is therefore generally not possible.
  • the polymer membranes show a too high permeability for methanol when used in a direct methanol fuel cell.
  • the so-called cross-over of methanol on the cathode side means that only low power densities can be achieved in the direct methanol fuel cell.
  • Inorganic proton conductors are e.g. B. from “Proton Conductors", P. Colomban, Cambridge University Press, 1992 known.
  • proton-conductive zirconium phosphates known from EP 0 838 258 show conductivities which are too low.
  • a usable proton conductivity is only achieved at temperatures which are above the operating temperatures of a fuel cell that occur in practice.
  • Known proton-conducting MHSO 4 salts are readily soluble in water and are therefore only of limited use for fuel cell applications in which water is formed in the fuel cell reaction (WO 00/45447).
  • Known inorganic proton-conducting materials can also not be produced in the form of thin membrane foils, which are required to provide a low total resistance of the cell. It is therefore not possible to achieve low surface resistances and high power densities in fuel cells for technical applications in automobile construction with the known materials.
  • WO 99/62620 proposes an ion-conducting, permeable composite material and its use as an electrolyte membrane of an MEA in a fuel cell.
  • the electrolyte membrane from the prior art consists of a metal network, which with a porous ceramic material is coated on which a proton conductive material has been applied.
  • This electrolyte membrane has a proton conductivity superior to an organic Nafion membrane at temperatures of more than 80 ° C.
  • the prior art does not contain an embodiment of a fuel cell in which such an electrolyte membrane was used.
  • Electrolyte membrane known from WO 99/62620 has serious disadvantages with regard to the usability of an MEA containing this electrolyte membrane in practice and with regard to the production process which is required for the provision of such MEAs. Due to these disadvantages, the MEA known from WO 99/62620 is unsuitable for use in a fuel cell in practice. It has been shown that the known electrolyte membranes have good proton conductivity at elevated temperatures, but that, under practical conditions of use, short circuits occur in a fuel cell that render the electrolyte membranes unusable. Furthermore, the electrolyte membranes known from WO 99/62620 are problematic with regard to the adhesion of the ceramic material to the metal carrier, so that the ceramic layer has to be expected to detach from the metal network in the event of long standing times.
  • glass fabric based membranes By far the biggest disadvantage of glass fabric based membranes is that glasses used do not have a sufficiently high long-term stability in the very acidic operating conditions of the fuel cell. In addition, although these membranes have comparatively small minimum bending radii, in reality they can easily buckle due to their brittleness. As a result, the membranes for the reaction components of the fuel cell reaction become leaky, that is to say permeable, and can no longer be used in the fuel cell. In the worst case, the entire cell can also explode (as a result of a detonating gas reaction).
  • Polymer membranes, (ii) have a higher proton conductivity than membranes based on composite materials, which in turn have porous ceramics,
  • (iii) enables a low total resistance of a membrane electrode assembly, (iv) has mechanical properties, such as tensile strength and flexibility, which are suitable for use under extreme conditions, such as occur during the operation of a vehicle, (v) increased operating temperatures of more than Tolerated 80 ° C, (vi) avoids short circuits and cross-over problems, and (vii) can be easily manufactured.
  • electrolyte membranes that solve the above-mentioned problems can be easily produced by replacing the MF membranes previously used with glass substrates such as glass.
  • B. glass fabric or nonwoven, such membranes or composites are used as a carrier, which are based on substrates that have polymer fibers, which are then infiltrated with the electrolytes. Since the composite materials based on substrates that have polymer fibers are significantly more flexible, the electrolyte membranes are also significantly more flexible than electrolyte membranes based on membranes based on substrates made of glass fibers. It is important that the carrier is not simply in z. B. mineral acids can be soaked, but the electrolyte immobilized in the form of a gel, glass or crystalline material must ultimately be present in the tissue.
  • the present invention therefore relates to a proton-conductive, flexible electrolyte membrane for a fuel cell, which is impermeable to the reaction components of a fuel cell reaction, comprising a flexible, permeable composite material as a carrier, which has a flat substrate with a plurality of openings and a substrate on and in it Has coating located substrate, wherein the material of the substrate is selected from woven or non-woven polymer fibers and the coating is a porous, ceramic coating, and wherein the carrier is interspersed with a proton-conductive material which is suitable for selectively guiding protons through the membrane.
  • the present invention also relates to a flexible, proton-conductive, flexible electrolyte membrane for a fuel cell which is impervious to the reaction components of a fuel cell reaction and which
  • Networking includes and
  • the present invention also relates to a method for producing an electrolyte membrane according to the invention, which is characterized in that the method comprises the following steps:
  • Substrate is selected from woven or non-woven polymer fibers and the coating is a porous, ceramic coating with
  • the subject of the present invention is a flexible membrane electrode unit for a fuel cell, with an electrically conductive anode and cathode layer, each of which is provided on opposite sides of a proton-conductive, flexible electrolyte membrane for a fuel cell, which is particularly impervious to the reaction components of the fuel cell reaction, the electrolyte membrane a flexible, permeable fabric Composite material comprises as a carrier, which has a flat, provided with a plurality of openings, flexible substrate with a coating on and in this substrate, wherein the material of the substrate is selected from woven or non-woven polymer fibers and the coating is a porous, ceramic coating , and wherein the support is permeated with a proton-conductive material which is suitable for selectively guiding protons through the membrane, and wherein the anode layer and the cathode layer are porous and each have a catalyst for the anode and cathode reaction, a proton-conductive component and optionally one Include catalyst support.
  • the present invention also relates to a method for producing a membrane electrode unit according to the invention, the method comprising the following steps,
  • a proton-conductive, flexible electrolyte membrane for a fuel cell in particular one that is impermeable to the reaction components of the fuel cell reaction, the electrolyte membrane comprising a flexible, permeable composite material as a carrier, which has a flat, provided with a plurality of openings, with a flexible substrate and having a coating located in this substrate, the material of the substrate being selected from woven or non-woven polymer fibers and the coating being a porous, ceramic coating, and wherein the support is permeated with a proton-conductive material which is suitable for selectively protons through the membrane to lead
  • Electrode layer gives proton conductivity, (B2) a catalyst which catalyzes the anode reaction or the cathode reaction, or a precursor compound of the catalyst, (B3) optionally a carrier and (B4) optionally a pore former,
  • the present invention also relates to an agent comprising:
  • Tl a condensable component which, after the condensation of an anode layer or a cathode layer, gives a membrane electrode assembly to a fuel cell proton conductivity
  • T2 a catalyst which catalyzes the anode reaction or the cathode reaction in a fuel cell, or a precursor compound of the catalyst
  • (T4) optionally a pore former
  • T5 optionally additives to improve foam behavior, viscosity and adhesion.
  • the subject of the present invention is the use of an electrolyte membrane according to the invention in a fuel cell or for producing a membrane electrode assembly, a fuel cell, or a fuel cell stack.
  • the present invention also relates to the use of a membrane electrode unit according to the invention in a fuel cell and fuel cells with an electrolyte membrane according to the invention or membrane electrode units according to the invention.
  • the membranes of the invention are gas-tight or impermeable to the reaction components in a fuel cell, such as. B. hydrogen, oxygen, air and / or methanol.
  • gas-tight or impermeable to the reaction components is understood to mean that less than 50 liters of hydrogen and less than 25 liters of oxygen per day, bar and square meter pass through the membranes according to the invention and the permeability of the membrane to methanol is significantly less than with commercially available Nafion membranes, which are usually also considered impermeable be designated.
  • the membranes according to the invention have the advantage that they have a high proton conductivity with a significantly reduced air humidity in comparison to conventional polymer membranes.
  • electrolyte membranes according to the invention enable membrane electrode assemblies to be produced which have a low overall resistance, which have good mechanical properties, such as tensile and compressive strength and flexibility, and which are suitable for use under extreme conditions, such as occur when a vehicle is operated, at elevated operating temperatures of Tolerate more than 80 ° C and avoid short circuits and cross-over problems in direct methanol fuel cells.
  • membranes are obtained which also have the advantage that they can be extremely flexible and can have a bending radius of a few mm or even less. This is a further advantage compared to the PEMs based on MF membranes based on glass fiber supports, which are rather brittle and can easily fail catastrophically when sealing or during operation in the fuel cell.
  • the membrane according to the invention based on composite materials comprising polymer fibers show practically the same elasticity but also the same strength as the composite materials themselves or as the polymeric fabrics, knitted fabrics, felts or nonwovens on which these composite materials are based.
  • the electrolyte membrane of the present invention also has the advantage that it does not have to be swollen in water to provide useful conductivity. It is therefore much easier to combine the electrodes and the electrolyte membrane to form a membrane electrode assembly. In particular, it is not necessary to provide a swollen membrane with an electrode layer, as is necessary in the case of a Nafion membrane, in order to prevent the electrode layer from tearing during swelling.
  • the choice of the special carrier also allows the porous ceramic material to adhere firmly to the carrier. This enables a stable MEA to be manufactured that can also withstand high mechanical loads.
  • the electrolyte membrane according to the invention can be used in a reformate or Direct methanol fuel cells are used that provide long service lives and high power densities even at low water partial pressures and high temperatures. It is also possible to control the water balance of the new membrane electrode units by adjusting the hydrophobicity / hydrophilicity of the membrane and electrodes. The effect of capillary condensation can also be exploited through the targeted creation of nanopores in the membrane. Flooding of the electrodes by product water or drying out of the membrane at a higher operating temperature or current density can thus be avoided.
  • diffusion barriers i.e. proton-conductive coatings that are insoluble in water and methanol, also prevents the phenomenon of electrolyte bleeding.
  • the proton-conductive, flexible electrolyte membrane for a fuel cell which is impermeable to the reaction components of a fuel cell reaction, comprises a flexible, permeable composite material as a carrier, which has a flat, provided with a plurality of openings, a flexible substrate with a coating on and in this substrate, wherein the material of the substrate is selected from woven or non-woven polymer fibers and the coating is a porous, ceramic coating, and wherein the carrier is permeated with a proton-conductive material which is suitable for selectively guiding protons through the membrane.
  • the proton-conducting material has a plastic and / or elastic deformability.
  • the proton conductive material preferably comprises
  • Phosphorus as a network former, and / or (iii) zirconium and / or titanium phosphates, phosphonates and / or sulfoaryl phosphonates and optionally an oxide of aluminum, silicon, titanium, zirconium and / or phosphorus as a network former.
  • the inventive for the reaction components of the fuel cell reaction impermeable, proton conductive, flexible electrolyte membranes for a fuel cell are z. B. by
  • Substrate is selected from woven or non-woven polymer fibers and the coating is a porous, ceramic coating with
  • the gel-like structure is ensured by crosslinking the components, the crosslinking being carried out by poly- or oligomerization, in particular hydroxysilylalkyl acids and / or by using the oxides mentioned as network formers.
  • the proton-conducting material can be an organic and / or an inorganic material.
  • the proton-conducting material can only have material that is proton-conducting Has properties or in addition to the material with proton-conducting properties have a non-proton-conducting material, which, for. B. can have support functions or form networks.
  • the proton conductive material of an electrolyte membrane according to the invention preferably comprises a Bronsted acid, an immobilized hydroxysilylalkyl acid of sulfur or phosphorus or a salt thereof. These components give the electrolyte membrane proton conductivity.
  • the proton-conductive material can optionally contain an oxide of aluminum, silicon, titanium, zirconium and / or phosphorus as a network former. Such an oxide is essential when using Bronsted acid.
  • the network can also contain other network-forming oxides such as SiO 2 , Al 2 O 3 , ZrO 2 , or TiO 2 .
  • the Bronsted acid can e.g. B. sulfuric acid, phosphoric acid, perchloric acid, nitric acid, hydrochloric acid, sulfurous acid, phosphorous acid and esters thereof and / or a monomeric or polymeric organic acid.
  • Preferred organic acids are immobilized sulfonic and / or phosphonic acids.
  • the oxides of Al, Zr, Ti and Si are used as network formers. In this case, z. B. ZrO 2 or TiO 2 from a network in which the acid residues z. B. the phosphates or phosphonates are immobilized via Zr-OP or Ti-OP groups.
  • the proton conductive material in the electrolyte membrane according to the invention preferably has an organosilicon compound of the general formulas
  • R 1 is a linear or branched alkyl or alkylene group with 1 to 12 C atoms, a cycloalkyl group with 5 to 8 C atoms or a unit of general formulas
  • n, m each represents an integer from 0 to 6
  • R, R 2 are the same or different and stand for methyl, ethyl, propyl, butyl or H and
  • R 3 represents M or a methyl, ethyl, propyl or butyl radical.
  • the proton-conductive material in the electrolyte membrane according to the invention particularly preferably has trihydroxysilylpropylsulfonic acid, trihydroxysilylpropylmethylphosphonic acid or 4,4-dihydroxy-1, 7-disulfo-4-silaheptane as hydroxysilylalkyl acid of sulfur or phosphorus.
  • the hydroxysilylalkyl acid of sulfur or phosphorus is preferred with a hydrolyzed compound of phosphorus or a hydrolyzed nitrate, oxynitrate, chloride, oxychloride, carbonate, alcoholate, acetate, acetylacetonate of a metal or semimetal or a hydrolyzed compound obtained from diethylphosphite (DEP), diethylethylphosphonate ( DEEP), titanium propylate, titanium ethylate, tetraethyl orthosilicate (TEOS) or tetramethyl orthosilicate (TMOS), zirconium nitrate, zirconium oxynitrate, zirconium propylate, Zirconium acetate, zirconium acetylacetonate, methyl phosphorate or immobilized with precipitated silica.
  • DEP diethylphosphite
  • DEEP diethylethylphosphonate
  • the proton-conductive material of the mixtures (a1) or (a2) can also have zirconium and / or titanium phosphates, phosphonates and / or sulfoaryl phosphonates, the crosslinking or gel formation being carried out by at least one oxide of aluminum, silicon, titanium, Zirconium and / or phosphorus takes place.
  • the proton-conductive material has ceramic particles made from at least one oxide selected from the series Al 2 O, SiO 2 , ZrO 2 or TiO 2 .
  • the proportion of ceramic particles which make no contribution to proton conductivity in the proton conductivity material is preferably less than 40% by volume, particularly preferably less than 30% by volume and very particularly preferably less than 10% by volume.
  • the ceramic particles have one or more particle size fractions with particle sizes in the range from 10 to 100 nm and / or from 100 to 1000 nm. Particle fractions with particle sizes of 50 nm to 500 nm are particularly preferred, such as. B.
  • Aerosil 200, Aerosil Ox50 or Aerosil VP 25 (each Degussa AG), or very fine-scaled particles, the z. B. be used directly as a suspension, such as. B. Levasil200E (Bayer AG).
  • the particles used are significantly smaller than the smallest pore diameter of the composite material serving as the carrier.
  • the average particle diameter is typically less than 1/2, preferably less than 1/5 and very particularly preferably less than 1/10 of the average pore diameter of the composite material used.
  • the membranes of the invention In contrast to the conventional proton-conducting microfiltration membranes based on e.g. B. Glass fabrics, the membranes of the invention have a significantly higher proportion of material with proton-conducting properties, since the nonwovens preferably used as a substrate have a significantly higher porosity of up to 90% or even more.
  • the electrolyte membrane according to the invention preferably has a volume ratio of proton-conductive material to carrier of at least 20 to 80.
  • the volume ratio of proton-conductive material to carrier is preferably from 25 to 75 to 45 to 55 and very particularly preferably from 30 to 70 to 40 to 60.
  • the proton-conductive material has further proton-conducting substances.
  • Preferred proton-conducting substances are e.g., selected from the titanium phosphates, Titanphosphonaten, Titansulfoarylphosphonate, zirconium phosphates, zirconium phosphonates, Zirkoniumsulfoarylphosphonate, iso- and heteropoly acids, preferably tungstophosphoric acid or silicotungstic acid, or nano-crystalline metal oxides and Al 2 O 3 - ZrO 2 -, TiO 2 - or SiO 2 Powder are preferred. These can also (if necessary) form the proton-conducting material in combination with the network formers mentioned. In this case, ZrO 2 or TiO 2 form a network in which the phosphates or phosphonates are immobilized via Zr-OP or Ti-OP groups.
  • the electrolyte membrane according to the invention preferably comprises a composite material which is based on a flat, flexible substrate provided with a multiplicity of openings, with a coating located on and in this substrate, the material of the substrate being selected from nonwovens, knitted fabrics, felts or fabrics of polymer fibers, preferably of nonwovens of polymer fibers.
  • the coating of the substrate is preferably a porous, ceramic coating.
  • the substrate of the composite material used particularly preferably has a thickness of 10 to 150 ⁇ m. It can be particularly advantageous if the electrolyte membrane according to the invention has a composite material with a substrate which has a thickness of 30 to 75 ⁇ m, preferably 25 to 50 ⁇ m and particularly preferably 30 to 40 ⁇ m. It can be advantageous if the substrate comprises polymer fibers and / or filaments with a diameter of 1 to 50 ⁇ m, in particular of 1 to 20 ⁇ m. If the polymer fibers are significantly thicker than the areas mentioned, the flexibility of the substrate and thus that of the membrane suffers.
  • the polymer fibers are preferably selected from polyacrylonitrile, polyamides, polyimides, polyacrylates, polytetrafluoroethylene, polyesters, such as, for. B. polyethylene terephthalate and / or Polyolef ⁇ n. But all other known polymer fibers are also conceivable.
  • the membrane according to the invention preferably has polymer fibers which have a softening temperature of greater than 100 ° C., a glass transition temperature of greater than -10 ° C. and a melting temperature of greater than 150 ° C.
  • the ceramic coating located on and in the substrate preferably has an oxide of the metals Al, Zr, Si, Ti and / or Y.
  • the coating on and in the substrate particularly preferably has an oxide of the metals Al, Ti, Zr and / or Si as an inorganic component.
  • the membrane according to the invention has a coating which has at least two grain size fractions of at least one inorganic component. It can also be advantageous if the coating has at least two grain size fractions of at least two inorganic components.
  • the grain size ratio can be from 1: 1 to 1: 10000, 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.
  • adhesion promoters are e.g. B. organofunctional silanes, such as those offered by Degussa under the trade name "Dynasilan”. Pure oxides such as ZrO 2 , TiO 2 , SiO 2 or Al 2 O 3 can also be suitable adhesion promoters for some fiber materials Manufacturing conditions and the adhesion promoter used, the adhesion promoters may still be demonstrably present in the composite materials used according to the invention.
  • such a composite material has a nonwoven, preferably a polymer nonwoven, the fibers of which are provided with a thin layer of an adhesion promoter (such as a metal oxide or an organosilane compound).
  • the porous ceramic material is located in and on the polymeric, pre-coated carrier.
  • the carrier must be stable both in the course of the production of the electrolyte membrane and under the operating conditions in a fuel cell. Therefore, the polymer for the carrier comprising polymer fibers is preferably stable to protons which are passed through the membrane and to the proton-conducting material (gel) with which the membrane is permeated.
  • the carrier is a woven fabric
  • this is preferably a woven fabric made of 11-Tex yarns with 5-50 warp or weft threads and in particular 20-28 warp and 28-36 weft threads.
  • the electrolyte membrane according to the invention is preferably stable at at least 80 ° C., preferably at least 100 ° C., and very particularly preferably at at least 120 ° C.
  • the electrolyte membrane preferably has a thickness in the range from 10 to 150 ⁇ m, preferably 10 to 80 ⁇ m, very particularly preferably 10 to 50 ⁇ m.
  • the electrolyte membrane according to the invention preferably tolerates a bending radius down to 5000 m, preferably 100 m, in particular down to 50 cm, preferably 20 mm and very particularly preferably down to 2 mm.
  • the electrolyte membrane according to the invention preferably has a conductivity of at least 5 mS / cm, preferably at least 20 mS / cm, very particularly preferably at least 50 mS / cm, at room temperature and at a relative atmospheric humidity of at most 80%.
  • the electrolyte membrane according to the invention preferably has a conductivity of at least 5 at room temperature and at a relative atmospheric humidity of at most 50% mS / cm, preferably at least 20 mS / cm and very particularly preferably at least 50 mS / cm.
  • the membrane according to the invention has an additional, outer proton-conducting coating on one side, preferably on both side surfaces, which is insoluble in water and methanol and which serves as a diffusion barrier and prevents leaching of an electrolyte from the electrolyte membrane.
  • This coating preferably has a water- and methanol-insoluble proton-conducting material, such as National®, sulfonated or phosphonated polyphenylsulfones, polyimides, polyoxazoles, polytriazoles, polybenzimidazoles, polyether ether ketones (PEEK), polyether ketones (PEK) or inorganic proton conductors, such as, for. B.
  • immobilized sulfonic or phosphonic acid e.g. hydroxysilylalkyl acids
  • zirconium or titanium phosphates or phosphonates can also contain other oxides, e.g. B. of AI, Zr, Ti or Si, included as a network former.
  • the organic proton-conducting polymers can be applied either as pure materials or in the form of inorganic-organic composite materials. Such composite materials can e.g. B.
  • the presence of a diffusion barrier prevents the membrane from bleeding out and improves the mechanical stability. This results in a higher long-term performance compared to membranes that show bleeding of the electrolyte.
  • the diffusion barrier is made as thin as possible.
  • the diffusion barrier has a thickness of less than 5 ⁇ m, preferably from 10 to 1000 nm and very particularly preferably from 100 to 500 nm. Due to the very thin design of the diffusion barrier, the lower conductivity of the diffusion barrier influences the proton conductivity of the actual membrane only insignificantly.
  • An electrolyte membrane of the present invention is e.g. B. obtainable by the method according to the invention for producing an electrolyte membrane, which, starting from the permeable carrier, comprises in particular the following steps:
  • Networking includes and
  • Bronsted acid z. B sulfuric acid, phosphoric acid, perchloric acid, nitric acid, hydrochloric acid, sulfurous acid, phosphorous acid and esters thereof and / or a monomeric or polymeric organic acid can be used.
  • Preferred organic acids are immobilizable sulfonic and / or phosphonic acids.
  • the oxides of Al, Zr, Ti and Si can be used as additional network formers.
  • organosilicon compounds of the general formulas [ ⁇ (RO) y (R 2 ) z ⁇ a Si ⁇ R 1 -SO 3 - ⁇ a ] x M x + (I) or [( RO) y (R 2 ) z Si ⁇ R 1 -O b -P (O c R 3 ) O 2 - ⁇ a ] x M x + (II), where R 1 is a linear or branched alkyl or alkylene group 1 to 12 carbon atoms, a cycloalkyl group with 5 to 8 carbon atoms or a unit of the general formulas
  • n, m each represents an integer from 0 to 6
  • R, R 2 are the same or different and stand for methyl, ethyl, propyl, butyl or H and
  • R 3 represents M or a methyl, ethyl, propyl or butyl radical.
  • Trihydroxysilylpropylsulfonic acid, trihydroxysilylpropylmethylphosphonic acid or 4,4-dihydroxy-l, 7-disulfo-4-silaheptane are particularly preferably used as hydroxysilylalkyl acid of sulfur or phosphorus in the mixture.
  • the hydroxysilylalkyl acid of sulfur or phosphorus is preferably with a hydrolyzed compound of phosphorus or a hydrolyzed nitrate, oxynitrate, chloride, oxychloride, carbonate, alcoholate, acetate, acetylacetonate of a metal or semimetal or a hydrolyzed compound obtained from diethylphosphite (DEP), diethylethylphosphonate ( DEEP), titanium propylate, titanium ethylate, tetraethyl orthosilicate (TEOS) or tetramethyl orthosilicate (TMOS), zirconium nitrate, zirconium oxynitrate, zirconium propylate, zirconium acetate, zirconium acetylacetonate, phosphoric acid methyl ester or immobilized with precipitated silica.
  • DEP diethylphosphite
  • DEEP diethylethyl
  • the mixture contains further proton-conducting substances selected from the group of iso- or heteropolyacids, such as, for example, tungsten phosphoric acid or silicon tungstic acid, zeolites, mordenites, aluminosilicates, ⁇ -aluminum oxides, zirconium, titanium or cerium phosphates or phosphonates sulfoarylphosphonates, antimonic acids, phosphorus oxides, sulfuric acid, perchloric acid or their salts and / or crystalline metal oxides, preference being given to Al O 3 , ZrO 2 , TiO 2 or SiO powder.
  • iso- or heteropolyacids such as, for example, tungsten phosphoric acid or silicon tungstic acid, zeolites, mordenites, aluminosilicates, ⁇ -aluminum oxides, zirconium, titanium or cerium phosphates or phosphonates sulfoarylphosphonates, antimonic acids
  • the mixture with which the carrier is infiltrated preferably has a sol which can be obtained by hydrolysis of a hydrolyzable compound, preferably in a mixture of water and alcohol, to give a hydrolyzate, the hydrolyzable compound being selected from hydrolyzable alcoholates, acetates, Acetylacetonates, nitrates, oxynitrates, chlorides, oxychlorides, carbonates, of aluminum, silicon, titanium, zirconium, and / or phosphorus or esters, preferably methyl esters, ethyl esters and / or propyl esters of phosphoric acid or phosphorous acid, and peptizing the hydrolyzate to a sol ,
  • hydrolyzable compound carries non-hydrolyzable groups in addition to hydrolyzable groups.
  • An alkyltrialkoxy or dialkyldialkoxy or trialkylalkoxy compound is preferably used as such a compound to be hydrolyzed Silicon used.
  • An acid or base which is soluble in water and / or alcohol can be added to the mixture as the hydrolysis and condensation catalyst.
  • a mineral acid such as. B. H 2 SO 4 , H 3 PO 4 , HNO 3 or HC1 added.
  • the mixture for infiltrating the carrier comprises, in addition to a trialkoxysilane as a network former, acidic or basic compounds and water.
  • acidic or basic compounds preferably comprise at least one Bronsted or Lewis acid or base known to the person skilled in the art.
  • 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 brine or mixtures also contain ceramic particles which can take on the function of fillers or network formers.
  • the oxides, in particular pyrogenic oxides of the elements Si, Al, Zr, Ti, are particularly preferred here. These can be present in several particle size fractions. It can be advantageous if the ceramic particles have one or more particle size fractions with particle sizes in the range from 10 to 100 nm and / or from 100 to 1000 nm. Particle fractions with particle sizes of 50 nm - 500 nm, such as, for. B. Aerosil200, AerosilOx50 or Aerosil VP 25 (all Degussa AG), or very fine-scale particles, which, for. B. be used directly as a suspension, such as. B.
  • Levasil 200E It is important here that the particles added to the sols are significantly smaller than the pore size of the MF membrane used. With a pore size of the MF membrane of 450 nm, the particles should be significantly smaller than 100 nm, better smaller than 50 nm.
  • the mixtures are preferred by suitable measures, such as. B. homogenized by prolonged stirring with a magnetic stirrer or wave stirrer, using an Ultraturrax or attritor mill or using ultrasound before the actual infiltration is carried out.
  • the carrier can be infiltrated by printing, pressing, pressing, rolling, knife coating, spreading, dipping, spraying or pouring the mixture onto the permeable carrier.
  • the infiltration with the mixture can be carried out repeatedly. If appropriate, a drying step, preferably at an elevated temperature in a range from 50 to 200 ° C., preferably from 100 to 150 ° C., can take place between the repeated infiltration.
  • the carrier is infiltrated continuously. It may be advantageous if the carrier is preheated for infiltration.
  • the mixture can be solidified in the carrier by heating to a temperature of 20 to 300 ° C., preferably 50 to 200 ° C., very particularly preferably 80 to 150 ° C., the heating being carried out by heated air, hot air, infrared radiation or microwave radiation can. It can be advantageous if the heating is carried out for 1 second to 60 minutes at a temperature of 20 to 300 ° C.
  • the mixture is particularly preferably heated for solidification for preferably 0.5 to 5 minutes to the temperatures mentioned.
  • the method for producing the electrolyte membrane according to the invention can, for. B. be carried out so that the carrier is unrolled from a roll, at a speed of 1 m / h to 2 m / s, preferably at a speed of 0.5 m / min. up to 20 m / min and very particularly preferably at a speed of 1 m / min to 5 m / min by at least one apparatus which brings the mixture onto and into the carrier and at least one further apparatus which solidifies the mixture on and in enables the carrier by heating, passes through and the electrolyte membrane thus produced is rolled up on a second roll. In this way it is possible to manufacture the electrolyte membrane according to the invention in a continuous process.
  • composite materials are preferably used as described above.
  • the composite material used is particularly preferably flexible and has a correspondingly good tensile strength, preferably a tensile strength of at least 1 N / cm, particularly preferably of at least 3 N / cm.
  • the composite material very particularly preferably has a tensile strength in the machine direction of at least 10 N / cm. The use of composite materials with a high tensile strength ensures that the electrolyte membrane also has a similarly high tensile strength as the composite material.
  • the composite materials are preferably obtainable by a method for producing a membrane, which is characterized in that a flat, flexible substrate provided with a plurality of openings is provided with a coating in and on this substrate, the material of the substrate being selected from woven or non-woven polymer fibers and the coating is a porous, ceramic coating which is applied to the substrate by applying a suspension which comprises at least one oxide of the metals AI, Zr, Si, Ti and / or Y and a sol, and wherein the Suspension on or in or on and in the carrier is solidified by at least one heating.
  • the suspension can have other inorganic components.
  • the suspension can e.g. B. by printing, pressing, pressing, rolling, knife coating, spreading, dipping, spraying or pouring onto and into the substrate.
  • the material of the substrate is preferably a polymer fabric, knitted fabric, felt or non-woven.
  • a substrate, in particular a nonwoven, which has a thickness of 10 to 150 ⁇ m is preferred for producing the composite material.
  • the membrane according to the invention has a substrate which has a thickness of 30 to 75 ⁇ m, preferably 25 to 50 ⁇ m and particularly preferably 30 to 40 ⁇ m.
  • the substrate comprises polymer fibers and / or filaments with a diameter of 1 to 50 ⁇ m, in particular of 1 to 20 ⁇ m. If the polymer fibers are significantly thicker than the areas mentioned, the flexibility of the substrate and thus that of the membrane suffers.
  • the polymer fibers are preferably selected from polyacrylonitrile, polyamides, polyacrylates, polyimides, polytetrafluoroethylene, polyesters, such as, for. B. polyethylene terephthalate and / or Polyolefm such as e.g. B. polypropylene (PP), polyethylene (PE) or mixtures of these. But all other known polymer fibers are also conceivable.
  • the membrane according to the invention preferably has polymer fibers which have a softening temperature of greater than 100 ° C., a glass transition temperature of greater than -10 ° C. and a melting temperature of greater than 150 ° C. The application areas are also reduced for polymer fibers with lower temperatures.
  • the suspension used to produce the coating of the composite material preferably has at least one inorganic oxide of aluminum, silicon, titanium and / or zirconium and at least one sol, at least one semimetal oxide sol or at least one mixed metal oxide sol or a mixture of these sols, and is suspended by suspending at least one inorganic component produced in at least one of these brines.
  • the sols are obtained by hydrolyzing at least one compound, preferably at least one metal compound, at least one semi-metal compound or at least one mixed metal compound. It may also be advantageous to add the compound to be hydrolyzed to alcohol or an acid or a combination of these liquids before the hydrolysis.
  • the compound to be hydrolyzed preferably at least one metal nitrate, one metal chloride, one metal carbonate, one metal alcoholate compound or at least one semi-metal alcoholate compound, particularly preferably at least one metal alcoholate compound, is hydrolyzed.
  • the metal alcoholate compound or semimetal alcoholate compound an alcoholate compound of the elements Zr,
  • the hydrolysis is preferably carried out in the presence of water, steam, ice, or an acid or a combination of these compounds.
  • particulate sols are produced by hydrolysis of the compounds to be hydrolyzed. These particulate sols are distinguished by the fact that the compounds formed in the sol by hydrolysis are present in particulate form.
  • the particulate sols can be produced as described above or as described in WO 99/15262. These brines usually have a very high water content, which is preferably greater than 50 wt .-%. It may be advantageous to add the compound to be hydrolyzed to alcohol or an acid or a combination of these liquids before the hydrolysis.
  • the hydrolyzed compound can be treated with at least one organic or inorganic acid, preferably with a 10 to 60% organic or inorganic acid, particularly preferably with a mineral acid selected from sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid and nitric acid or a mixture of these acids become.
  • the particulate sols produced in this way can then be used for the production of suspensions, the production of suspensions for application to polymer fiber webs pretreated with polymer sol being preferred.
  • polymeric sols are produced by hydrolysis of the compounds to be hydrolyzed. These polymeric sols are distinguished by the fact that the compounds formed in the sol by hydrolysis are polymeric (ie crosslinked in a chain over a larger space).
  • the polymeric sols usually have less than 50% by weight, preferably very much less than 20% by weight, of water and / or aqueous acid.
  • the hydrolysis is preferably carried out in such a way that the compound to be hydrolyzed is in a 0.5 to 10-fold molar ratio and preferably in half a molar ratio of water, steam or ice, based on the hydrolyzable group, the hydrolyzable compound, is hydrolyzed.
  • the amount of water can be used with very slow hydrolyzing compounds such as e.g. B. be used in tetraethoxysilane.
  • Very quickly hydrolyzing compounds such as zirconium tetraethylate can already form particulate sols under these conditions, which is why 0.5 times the amount of water is preferably used for the hydrolysis of such compounds.
  • Hydrolysis with less than the preferred amount of water, steam, or ice also gives good results. However, falling below the preferred amount of half a molar ratio by more than 50% is possible but not very useful, since if this value is not reached the hydrolysis is no longer complete and coatings based on such brine are not very stable.
  • this polymeric brine with the desired very low proportion of water and / or acid in the sol it can be advantageous if the compound to be hydrolyzed is dissolved in an organic solvent, in particular ethanol, isopropanol, butanol, amyl alcohol, hexane, cyclohexane, ethyl acetate and or mixtures of these compounds, before the actual hydrolysis is carried out.
  • an organic solvent in particular ethanol, isopropanol, butanol, amyl alcohol, hexane, cyclohexane, ethyl acetate and or mixtures of these compounds.
  • a sol produced in this way can be used to produce the suspension or as an adhesion promoter in a pretreatment step.
  • Both the particulate sols and the polymeric sols can be used as sols for the production of the suspension in the production of the composite material used as the carrier.
  • commercially available brines such as e.g. B. zirconium nitrate sol or silica sol can be used.
  • the process for the production of membranes (composite materials) by applying and solidifying a suspension to a carrier in and of itself is known from WO 99/15262, but not all parameters or feedstocks can be used to produce composite materials based on polymeric substrates transfer.
  • a sol system or a suspension which has been adapted to the polymers in terms of wetting behavior completely soaks the nonwoven materials and thus flawless coatings are obtainable.
  • the wetting behavior of the sol or suspension is therefore preferably adjusted in the method according to the invention.
  • This adjustment is preferably carried out by the production of polymeric sols or suspensions from polymeric sols.
  • These sols contain one or more alcohols, such as. B. methanol, ethanol or propanol or mixtures which comprise one or more alcohols and preferably aliphatic hydrocarbons.
  • solvent mixtures are also conceivable which can be added to the sol or the suspension in order to Adapt networking behavior to the substance used.
  • the suspension as an inorganic component, at least one oxide selected from the oxides of the elements Y, Zr, Al, Si, Sn, and Ti is suspended in a sol.
  • An inorganic component which has at least one compound selected from aluminum oxide, titanium dioxide, zirconium oxide and / or silicon dioxide is preferably suspended.
  • the mass fraction of the suspended component is preferably 0.1 to 500 times, particularly preferably 1 to 50 times and very particularly preferably 5 to 25 times the sol used.
  • the use of inorganic components which have an average grain size of 250 to 1250 nm results in a particularly suitable flexibility and porosity of the membrane or of the composite material.
  • adhesion promoters such as e.g. B. organofunctional silanes or pure oxides such as ZrO 2 , TiO 2 , SiO 2 or Al 2 O 3 .
  • adhesion promoters in particular to suspensions based on polymeric sols, is preferred.
  • compounds selected from the octylsilanes, the fluorinated octylsilanes, the vinylsilanes and the amine-functionalized compounds are used as adhesion promoters Silanes and / or the glycidyl-functionalized silanes, such as. B.
  • the Dynasilane from Degussa can be used.
  • Particularly preferred adhesion promoters for polytetrafluoroethylene (PTFE) are e.g. B. fluorinated octylsilanes, for polyethylene (PE) and polypropylene (PP) it is vinyl, methyl and octylsilanes, where the exclusive use of methylsilanes is not optimal, for polyamides and polyamines it is amine-functional silanes, for polyacrylates and polyesters Glycidyl-functionalized silanes and for polyacrylonitrile it is also possible to use glycidyl-functionalized silanes.
  • B. fluorinated octylsilanes for polyethylene (PE) and polypropylene (PP) it is vinyl, methyl and octylsilanes, where the exclusive use of methylsilanes is not optimal, for polyamides and polyamines it is amine-functional silanes,
  • adhesion promoters can also be used, but these have to be matched to the respective polymers.
  • methyltriethoxysilane described in WO 99/15262 to the sol system when coating polymeric carrier materials is a comparatively poor solution to the problem of the adhesive strength of ceramics on polymer fibers.
  • the drying time of 30 to 120 minutes at 60 to 100 ° C is not sufficient for the described sol systems to obtain hydrolysis-resistant ceramic materials. This means that these materials will dissolve or be damaged if stored in water-containing media for a long time.
  • the temperature treatment of over 350 ° C. described in WO 99/15262 would burn the polymer fleece used here and thus destroy the composite material.
  • adhesion promoters must therefore be selected so that the solidification temperature is below the melting or softening point of the polymer and below its decomposition temperature.
  • Suspensions according to the invention preferably have significantly less than 25% by weight, preferably less than 10% by weight, of compounds which can act as adhesion promoters.
  • An optimal proportion of adhesion promoter results from the coating of the fibers and / or particles with a monomolecular layer of the adhesion promoter.
  • the amount of adhesion promoter required in grams can be obtained by multiplying the amount of oxides or fibers used (in g) by the specific surface area of the materials (in m 1 ) and then 1
  • the following table contains an exemplary overview of adhesion promoters that can be used on the basis of organofunctional Si compounds for typical polymers used as nonwoven material.
  • AMEO 3-aminopropyltriethoxysilane
  • DAMO 2-aminoethyl-3-aminopropyltrimethoxysilane
  • GLYMO 3-glycidyloxytrimethoxysilane
  • MEMO 3-methacryloxypropyltrimethoxysilane
  • VTEO vinyl triethoxysilane
  • VTMO vinyltrimethoxysilane
  • VTMOEO vinyltris (2-methoxyethoxy) silane
  • the coatings according to the invention are applied to the substrate by solidifying the suspension in and on the substrate.
  • the suspension present on and in the substrate can be solidified by heating to 50 to 350 ° C. Since the maximum temperature is predetermined by the substrate when using polymeric substrate materials, this must be adjusted accordingly.
  • the suspension present on and in the substrate is solidified by heating to 100 to 350 ° C. and very particularly preferably by heating to 110 to 280 ° C. It can be advantageous if the heating is carried out at a temperature of 100 to 350 ° C. for 1 second to 60 minutes.
  • the suspension is particularly preferably heated for solidification to a temperature of 110 to 300 ° C., very particularly preferably at a temperature of 110 to 280 ° C.
  • the composite can be heated according to the invention by means of heated air, hot air, infrared radiation or by other heating methods according to the prior art.
  • the abovementioned adhesion promoters are applied to the substrate, in particular the polymer fleece, in an upstream step.
  • a suitable solvent such as. B. dissolved ethanol.
  • This solution can also contain a small amount of water, preferably 0.5 to 10 times the amount based on the molar amount of the hydrolyzable group, and small amounts of an acid, such as. B. HC1 or HNO 3 , as a catalyst for the hydrolysis and condensation of the Si-OR groups.
  • an acid such as. B. HC1 or HNO 3
  • adhesion-promoting layers are applied in a pretreatment step in which a polymeric sol is applied and solidified.
  • the substrates in particular the polymer nonwovens, are equipped with an oxide of Al, Ti, Zr or Si as an adhesion promoter, which makes the substrate hydrophilic.
  • Substrates equipped in this way can then be provided with a porous coating in accordance with the prior art described in WO 99/15262 or as described above, with the pretreatment allowing a significantly better adhesion of the coating, in particular to polymer nonwovens, to be observed.
  • a typical polymeric sol for a pretreatment is about a 0.1 to 10% by weight, and preferably 0.5 to 2% by weight, alcoholic solution of a metal alcoholate (such as, for example, titanium ethylate or zirconium propylate), which can additionally contain 0.5 to 10 mol parts of water and small amounts of an acid as a catalyst.
  • a metal alcoholate such as, for example, titanium ethylate or zirconium propylate
  • the substrates preferably polymer nonwovens, are treated at a temperature of at most 350 ° C. This creates a dense film of a metal oxide around the substrate fibers, which allows infiltration of the substrate with a suspension or a slip based on a commercial zirconium nitrate sol or silica sol without wetting difficulties.
  • polymer sols tend to form dense films than particulate sols and the particulate sols also have larger and larger amounts of water in the pore structure of the intermediate grain volumes, it is easier to dry polymer sols than particulate sols. Nevertheless, they have to
  • Composite materials are dried at temperatures of over 150 ° C, so that the ceramic material receives a sufficiently good adhesive strength on the carrier. Particularly good ones
  • Adhesive strengths can be achieved at a temperature of at least 200 ° C and very good strengths at a temperature of at least 250 ° C.
  • temperature-stable polymers are absolutely necessary for this, such as
  • PET Polyethylene terephthalate
  • PAN polyacrylonitrile
  • PTFE polytetrafluoroethylene
  • PVDF Polyvinylidene fluoride
  • PA polyamide
  • both types of application of an adhesion promoter before the actual application of the suspension can improve the adhesion behavior of the substrates, in particular with respect to aqueous, particulate sols, which is why substrates pretreated in this way with suspensions based on commercially available sols, such as, for. B. zirconium nitrate sol or silica sol can be coated according to the invention.
  • this procedure of applying an adhesion promoter also means that the manufacturing process for the composite material must be expanded by an intermediate or pretreatment step. This is feasible, however, also more complex than the use of adapted brines to which adhesion promoters have been added, but also has the advantage that better results are also achieved when using suspensions based on commercially available brines.
  • the inventive method can, for. B. be carried out so that the substrate is unrolled from a roll, at a speed of 1 m h to 2 m / s, preferably at a speed of 0.5 m / min. up to 20 m / min and very particularly preferably at a speed of 1 m / min to 5 m / min through at least one apparatus which brings the suspension onto and into the support, such as, for. B. a roller and at least one other apparatus which allows the solidification of the suspension on and in the support by heating, such as. B. an electrically heated oven, and the composite material thus produced is rolled up on a second roll.
  • the pre-treatment steps can also be carried out in a continuous process while maintaining the parameters mentioned.
  • the composite material used is preferably those materials or membranes which have average pore sizes from 5 to 5000 nm, particularly preferably from 10 to 1000 nm and very particularly preferably from 100 to 800 nm.
  • a suitable particle size of the ceramic powder in the sol / slip is used in accordance with the desired pore size.
  • a membrane electrode unit according to the invention is described below.
  • the flexible membrane electrode unit for a fuel cell comprises an anode layer and a cathode layer, which are each provided on opposite sides of a proton-conductive, flexible electrolyte membrane for a fuel cell that is impermeable to the reaction components of the fuel cell reaction, the electrolyte membrane comprising a flexible, permeable composite material as a carrier, which comprises a Flat, provided with a plurality of openings, flexible substrate with a coating located on and in this substrate, wherein the material of the substrate is selected from woven or non-woven polymer fibers and the coating is a porous, ceramic coating, and wherein the carrier with a proton conductive material is penetrated, which is suitable for selectively guiding protons through the membrane, and wherein the anode layer and the cathode layer are porous and a catalyst for the An ode and cathode reaction, a proton conductive component and optionally a catalyst support.
  • the proton-conductive component of the anode and / or cathode layer and / or the proton-conductive material of the electrolyte membrane preferably each comprises
  • the Bronsted acid can e.g. B. sulfuric acid, phosphoric acid, perchloric acid, nitric acid, hydrochloric acid, sulfurous acid, phosphorous acid and esters thereof and / or a monomeric or polymeric organic acid.
  • the hydroxysilylalkyl acid of sulfur or phosphorus or a salt thereof is an organosilicon compound of the general formulas [ ⁇ (RO) y () z ⁇ aSi ⁇ R 1 -S ⁇ 3- ⁇ a ] ⁇ w - (I) or
  • R 1 is a linear or branched alkyl or alkylene group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms or a unit of the general formula n
  • n, m each represents an integer from 0 to 6
  • R, R 2 are the same or different and represent methyl, ethyl, propyl, butyl or H and R 3 represents M or a methyl, ethyl, propyl or butyl radical.
  • the hydroxysilylalkyl acid of sulfur or phosphorus is preferably trihydroxysilylpropylsulfonic acid, trihydroxysilylpropylmethylphosphonic acid or 4,4-dihydroxy-l, 7-disulfo-4-silaheptane.
  • TEOS tetraethyl orthosilicate
  • TMOS tetramethyl orthosilicate
  • the protonenleitfahige component of the anode and / or cathode layer may also include proton-conducting materials selected from titanium phosphates, Titanphosphonaten, zirconium phosphates, Zirkoniumphosphonaten, iso- and heteropoly acids, preferably tungstophosphoric acid or silicotungstic acid, or nano-crystalline metal oxides and Al 2 O 3 - ZrO 2 -, TiO 2 or SiO 2 powder are preferred.
  • the membrane electrode assembly according to the invention can preferably be operated in a fuel cell at a temperature of at least 80 ° C, preferably at least 100 ° C, and very particularly preferably at least 120 ° C.
  • the membrane electrode unit according to the invention preferably tolerates a bending radius of at least 5000 mm, preferably 100 mm, in particular of at least 50 mm and particularly preferably of at least 20 mm.
  • the membrane electrode unit according to the invention very particularly preferably tolerates a bending radius of at least 5 mm.
  • the proton-conductive component of the anode layer and cathode layer and the proton-conductive material of the electrolyte membrane have the same composition.
  • the proton-conductive component of the anode layer and / or the cathode layer and / or the membrane it is also possible for the proton-conductive component of the anode layer and / or the cathode layer and / or the membrane to be different.
  • the catalyst can be the same on the anode and cathode side, but in the preferred embodiment it is different.
  • the catalyst support is electrically conductive in the anode layer and in the cathode layer.
  • the electrolyte membrane can be provided with the electrode in various ways.
  • the manner and the sequence in which the electrically conductive material, catalyst, electrolyte and possibly further additives are applied to the membrane are at the discretion of the person skilled in the art. It is only necessary to ensure that the gas chamber catalyst (electrode) / electrolyte interface is formed.
  • the electrically conductive material as a catalyst carrier is dispensed with; in this case, the electrically conductive catalyst directly removes the electrons from the membrane electrode assembly.
  • the method according to the invention for producing a membrane electrode unit according to the invention comprises the following steps: (A) Provision of a proton-conductive, flexible electrolyte membrane which is impermeable to the reaction components of the fuel cell reaction, for a fuel cell, in particular an electrolyte membrane according to the invention, the electrolyte membrane comprising a flexible, permeable composite material as a carrier , Which has a flat, with a plurality of openings, flexible substrate with a coating on and in this substrate, the material of the substrate is selected from woven or non-woven polymer fibers and the coating is a porous, ceramic coating and wherein the carrier is permeated with a proton-conductive material which is suitable for selectively passing protons through the membrane, (B) providing in each case a means for producing an anode icht and a cathode layer, wherein the agent each comprises: (B1) a condensable component, which after the condensation of the
  • the application of the agent in step (C) can, for. B. by printing, pressing, pressing, rolling, knife coating, spreading, dipping, spraying or pouring.
  • the agent according to step (B) for producing an anode layer or a cathode layer is preferably a suspension which is obtainable from
  • TMOS zirconium nitrate, zirconium oxynitrate, zirconium propylate, zirconium acetate or zirconium acetylacetonate
  • the agent according to step (B) for producing an anode layer or a cathode layer is very particularly preferably a suspension which is obtainable by
  • hydrolysis of a hydrolyzable compound to a hydrolyzate the hydrolyzable compound being selected from a hydrolyzable compound of phosphorus or hydrolyzable nitrates, oxynitrates, chlorides, oxychlorides, carbonates, alcoholates, acetates, acetylacetonates of a metal or semimetal, preferably Aluminum alcoholates, vanadium alcoholates, titanium propylate, titanium ethylate,
  • Silicotungstic acid is preferred, (H2) peptizing the hydrolyzate with an acid to form a dispersion, (H3) mixing the dispersion with a nanocrystalline proton-conducting metal oxide, preferably Al O 3 , ZrO 2 , TiO 2 or SiO 2 powder, (H4 ) Dispersing the catalyst and optionally the carrier and pore former.
  • step (C) it can be advantageous if the means for producing an anode layer and a cathode layer are printed on in step (C) and to create a firm bond between the coatings and the electrolyte membrane, forming a porous, proton-conductive anode layer or cathode layer in step (D) on one Temperature of 20 to 300 ° C, preferably 50 to 200 ° C, most preferably 80 to 150 ° C is heated.
  • the method according to the invention can also include the steps: (Ml) applying the agent for producing an anode layer or cathode layer to a support membrane, preferably made of polytetrafluoroethylene, (M2) drying the coating obtained under (Ml),
  • Temperature range from room temperature to 300 ° C, preferably 50 to 200 ° C, most preferably 80 to 150 ° C.
  • the agent (i) comprises a catalyst metal salt, preferably hexachloroplatinic acid (ii) after application of the agent by step (C) the catalyst metal salt is reduced to a catalyst which catalyzes the anode reaction or the cathode reaction, (iii) in step (D) an open-pore gas diffusion electrode, preferably an open-pore one
  • Carbon paper pressed onto the catalyst or with an electrically conductive
  • Glue is glued to the catalyst.
  • the method according to the invention can be carried out in such a way that the application of the agent for producing an anode layer or cathode layer is carried out repeatedly and optionally a drying step, preferably at an elevated temperature in a range from 50 to 200 ° C., preferably from 60 to 150 ° C. and is most preferably carried out at an elevated temperature of 80 to 120 ° C between repeated application of the application.
  • the agent for producing an anode layer or cathode layer is applied to a flexible electrolyte membrane or flexible support membrane rolled off a first roll.
  • the agent for producing an anode layer or cathode layer is applied continuously. It can be particularly advantageous if the agent for producing an anode layer or cathode layer is applied to a heated electrolyte or support membrane.
  • the bond is preferably at a temperature of 20 to 300 ° C. preferably 50 to 200 ° C, most preferably 80 to 150 ° C heated.
  • the heating can take place by means of heated air, hot air, infrared radiation or microwave radiation.
  • the catalytically active (gas diffusion) electrodes are built up on the electrolyte membrane according to the invention in a special embodiment.
  • an ink is produced from a carbon black catalyst powder and at least one proton-conducting material.
  • the ink can also contain other additives that improve the properties of the membrane electrode assembly.
  • the carbon black can also be replaced by other electrically conductive materials (such as metal powder, metal oxide powder, carbon, coal).
  • a metal or semimetal oxide powder such as Aerosil is used as the catalyst support instead of carbon black.
  • This ink is then applied to the membrane, for example by screen printing, knife coating, spraying on, rolling on or by dipping.
  • the ink can contain all proton-conducting materials that are also used to infiltrate the carrier.
  • the ink can thus contain an acid or its salt, which is immobilized by a chemical reaction in the course of a solidification process after the ink has been applied to the membrane.
  • this acid can e.g. B. simple Bronsted acid, such as sulfuric or phosphoric acid, or a silylsulfonic or silylphosphonic acid.
  • materials that support the solidification of the acid for. B. Al 2 O 3 , SiO 2 , ZrO 2 , TiO 2 are used, which are also added via molecular precursors of the ink.
  • both the cathode and the anode In contrast to the proton-conductive material of the electrolyte membrane, which must be impermeable to the reaction components of the fuel cell reaction, both the cathode and the anode must have a large porosity so that the reaction gases, such as hydrogen and oxygen, are brought to the interface between the catalyst and the electrolyte without inhibiting the transport of substances can.
  • This porosity can be influenced, for example, by using metal oxide particles with a suitable particle size and by organic pore formers in the ink or by a suitable solvent content in the ink.
  • an agent can be used which comprises the following components: (Tl) a condensable component which, after the condensation of an anode layer or a cathode layer of a membrane electrode assembly of a fuel cell
  • T2 Proton conductivity gives (T2) a catalyst that the anode reaction or the cathode reaction in one
  • T5 optionally additives to improve foam behavior, viscosity and adhesion.
  • the condensable component which imparts proton conductivity to the anode layer or the cathode layer after the condensation is preferably selected from
  • Alcoholates, acetates, acetylacetonates of a metal or semimetal preferably aluminum alcoholates, vanadium alcoholates, titanium propylate, titanium ethylate, zirconium nitrate, zirconium oxynitrate, zirconium propylate, zirconium acetate or zirconium acetylacetonate, and / or metal acids of aluminum, titanium, tin, vanadium, chromium, lead, tin, vanadium,
  • TEOS tetramethyl orthosilicate
  • TMOS tetramethyl orthosilicate
  • zirconium nitrate zirconium oxynitrate
  • zirconium propylate zirconium acetate or zirconium acetylacetonate
  • the ink can also be used to increase the proton conductivity, nanoscale oxides such.
  • the catalyst or the precursor compound of the catalyst preferably comprises platinum, palladium and / or ruthenium or an alloy which contains one or more of these metals.
  • the pore former which is optionally contained in the ink, can be an organic and / or inorganic substance which decomposes at a temperature between 50 and 300 ° C and preferably between 100 and 200 ° C.
  • the inorganic pore former can be ammonium carbonate or ammonium bicarbonate.
  • the catalyst support which is optionally contained in the ink, is preferably electrically conductive and preferably comprises carbon black, metal powder, metal oxide powder, carbon or carbon.
  • a prefabricated gas distributor which comprises the gas diffusion electrode, consisting of an electrically conductive material (e.g. a porous one)
  • Carbon fleece Carbon fleece
  • catalyst and electrolyte contains are applied directly to the membrane.
  • the gas distributor and membrane are fixed by a
  • the gas distributor can also be fixed on the membrane with an adhesive. This adhesive must be ion-conductive
  • the gas distributor can also be applied “in situ” in the last stage of membrane or gas diffusion electrode manufacture. At this stage, the proton-conducting material in the gas distributor or in the membrane has not yet hardened and can be used as an adhesive. The gluing process takes place in both
  • Precipitation by gelation of the sol followed by drying / solidification it is also possible to deposit the catalyst directly on the membrane and to provide it with an open-pore gas diffusion electrode (such as an open-pore carbon paper).
  • an open-pore gas diffusion electrode such as an open-pore carbon paper.
  • a metal salt or an acid applied to the surface and reduced to metal in a second step.
  • platinum can be applied via hexachloroplatinic acid and reduced to metal.
  • the lead electrode is fixed using a pressing process or an electrically conductive adhesive.
  • the solution containing the metal precursor may additionally contain a compound that is already proton-conductive or at least ion-conductive at the end of the manufacturing process. Suitable proton materials are the proton-conducting substances mentioned above.
  • a membrane electrode unit which can be used in a fuel cell, in particular in a direct methanol fuel cell or a reformate fuel cell.
  • the electrolyte membranes according to the invention can, for. B. in a fuel cell, in particular in a direct methanol fuel cell or a reformate fuel cell.
  • the electrolyte membrane according to the invention can be used to produce a membrane electrode assembly, a fuel cell, or a fuel cell stack.
  • the electrolyte membrane according to the invention and the membrane electrode assembly according to the invention can be used in particular for producing a fuel cell or a fuel cell stack, the fuel cell being in particular a direct methanol fuel cell or a reformate fuel cell which is used in a vehicle.
  • fuel cells with an electrolyte membrane according to the invention and / or a membrane electrode unit according to the invention are also the subject of the present invention and thus also a mobile or stationary system with a membrane electrode unit, a fuel cell or a fuel cell stack containing an electrolyte membrane according to the invention or a membrane electrode unit according to the invention.
  • a mobile or stationary system with a membrane electrode unit, a fuel cell or a fuel cell stack containing an electrolyte membrane according to the invention or a membrane electrode unit according to the invention.
  • the mobile or stationary systems vehicles or home energy systems.
  • Examples A-D Production of polymer-supported microfiltration membranes as supports
  • Example A Production of an MF membrane S100PET
  • the slip is rolled onto the fleece with a roller that moves in the opposite direction to the belt direction (direction of movement of the fleece).
  • the fleece then runs through an oven at the specified temperature.
  • the same method or arrangement is used in the subsequent experiments.
  • a microfiltration membrane with an average pore size of approximately 80 to 100 nm is obtained.
  • Example B Production of an MF membrane S240PO
  • Example C Production of an MF membrane S450PAN
  • Example D Production of an MF membrane Z450PAN
  • a microfiltration membrane with an average pore size of approximately 450 nm is obtained, which has very good adhesive strength and is very stable even in very alkaline media (pH> 10).
  • Example la Preparation of a cPEM based on trihydroxysilylpropylsulfonic acid / Levasil
  • the membrane from example lc is coated again with the Aerosil®-free sol from lc on the back under otherwise identical test conditions.
  • This membrane has an LF of 50 mS / cm at 35% relative humidity RH. and 140 mS / cm at 85% RH Due to the very good flexibility, it can be installed very well in the fuel cell and shows good performance.
  • Example 2 Coating a cPEM with diffusion barriers
  • Example 2a Coating with a pure nation
  • a membrane according to example la is coated in a continuous rolling process with a commercial, aqueous / alcoholic 5% by weight Nafion® solution (from Aldrich) and dried at 100 ° C.
  • the LF of the overall membrane decreases somewhat, but the membrane is suitable for the DMFC.
  • Example 2b Coating with Nafion / TEOS 10 ml of Dynasil A ® are added to 10 ml of a commercial, aqueous / alcoholic 5% by weight Nafion® solution (Aldrich) with vigorous stirring and stirring is continued until only a clear phase is present.
  • a membrane according to Example 1c is coated with this solution in a continuous rolling process and dried at 100.degree.
  • Example 2c Coating with Nafion / TEOS / ethanol
  • Example 2d Coating with trihydroxysilylpropylsulfonic acid / Levasil
  • Example 2e Coating with trihydroxysilylpropylsulfonic acid / TEOS
  • Example 2f Coating with zirconium phosphate
  • a membrane produced according to Example 1c is first coated with a thin layer of zirconium propylate using a doctor blade.
  • the alcoholate is hydrolyzed in the presence of air humidity.
  • the freshly precipitated zirconium hydroxide 7 oxide is then reacted with H 3 PO 4 and the membrane briefly dried at 200 ° C. in order to solidify the zirconium phosphate formed.
  • This thin layer is then water-insoluble and prevents the electrolyte from bleeding out.
  • Example 8 Production of a membrane electrode unit
  • Example 8a Production of a membrane electrode unit
  • a membrane according to Example 2e is first printed with the ink according to Example 3 by screen printing on the front. This side serves as an anode in the later membrane electrode assembly.
  • the printed membrane is dried at a temperature of 150 ° C.
  • the silylpropylsulfonic acid is also immobilized.
  • the membrane on the back which will later serve as the cathode, is printed with the ink from Example 6. Even now the printed membrane is again dried at a temperature of 150 ° C., whereby the solvent escapes and at the same time the silylpropylsulfonic acid is immobilized. Since the cathode is hydrophobic, the product water can easily escape when the membrane electrode unit is operated in the fuel cell.
  • This membrane electrode assembly can be installed in a direct methanol fuel cell or a reformate fuel cell.
  • both the anode ink according to Example 4 and the cathode ink according to Example 7 are each applied to an electrically conductive carbon paper.
  • a heat treatment at a temperature of 150 ° C removes the solvent and immobilizes the proton-conductive component.
  • These two gas diffusion electrodes are pressed with a proton-conductive membrane according to Example 2e to form a membrane electrode unit, which can then be installed in the fuel cell.
  • Example 9 Production of a Fuel Cell
  • the electrodes are first manufactured.
  • a ceramic fleece is coated with a carbon black / platinum mixture (40%).
  • These electrodes are pressed onto the electrolyte membrane according to Example 2c.
  • the pressure is applied via a graphitic gas distribution plate, which also serves for electrical contacting. Pure hydrogen is used on the anode side and pure oxygen is used on the cathode side. Both gases are moistened via water vapor saturators (so-called "bubblers").
  • a fuel cell was fabricated as described in Example 9, except that a conventional National® 117 membrane was used as the proton conductive membrane. It was found that the proton conductivity dropped drastically when using a Nafion membrane at a relative air humidity of less than 100%, and the surface resistance increased significantly, so that the fuel cell could no longer be operated. In contrast, the membrane according to the invention could also be operated at a relative atmospheric humidity which was approximately 50% at the anode side and at most 0 to 50% on the cathode side, without the function of the fuel cell being significantly impaired.

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Abstract

L'invention concerne une membrane électrolytique souple, conductrice de protons et imperméable aux éléments réactionnels d'une pile à combustible. Destinée à une pile à combustible, cette membrane est composée d'un support perméable, souple, ajouré et contenant des fibres polymères et une matière pouvant conduire des protons de manière sélective à travers la membrane. Cette invention concerne une membrane conductrice de protons, un procédé de fabrication associé et son utilisation. La membrane selon l'invention représente une nouvelle catégorie de membranes solides conductrices de protons, dont la base est un support souple et poreux contenant des fibres polymères, de préférence un non-tissé polymère. Ce support est d'abord infiltré d'une matière conductrice de protons, puis la membrane est séchée et la matière conductrice de protons se solidifie en un gel ou en une matière cristalline pour former une membrane conductrice de protons imperméable. La membrane électrolytique selon l'invention reste souple et peut être facilement utilisée dans une pile à combustible.
PCT/EP2003/000256 2002-02-26 2003-01-14 Membrane electrolytique souple a base d'un support contenant des fibres polymeres, procedes de realisation et utilisation associes WO2003073545A2 (fr)

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AU2003248341A AU2003248341A1 (en) 2002-02-26 2003-01-14 Flexible electrolyte membrane based on a carrier comprising polymer fibres, methods for the production thereof and use of the same

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DE10208275A DE10208275A1 (de) 2002-02-26 2002-02-26 Flexible Elektrolytmembran auf Basis eines Polymerfasern umfassenden Trägers, Verfahren zu deren Herstellung und die Verwendung derselben
DE10208275.8 2002-02-26

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Publication number Priority date Publication date Assignee Title
CN104592541A (zh) * 2015-01-20 2015-05-06 浙江大学 微孔聚苯并咪唑膜及改性聚苯并咪唑为隔膜的锂硫电池
US9680141B2 (en) 2012-01-30 2017-06-13 Litarion GmbH Separator comprising an organic-inorganic adhesion promoter

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113629281B (zh) * 2021-06-30 2022-07-15 嘉寓氢能源科技(辽宁)有限公司 一种燃料电池膜电极制备方法

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EP0875524A2 (fr) * 1997-04-25 1998-11-04 Johnson Matthey Public Limited Company Membranes composites
WO1999057769A1 (fr) * 1998-05-06 1999-11-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Separateur electrique a base d'un substrat revetu de ceramique
WO1999060650A1 (fr) * 1998-05-18 1999-11-25 Firma Carl Freudenberg Unite membrane-electrodes pour pile a combustible
DE19821976A1 (de) * 1998-05-18 1999-11-25 Freudenberg Carl Fa Brennstoffzelle
WO1999062620A1 (fr) * 1998-06-03 1999-12-09 Creavis Gesellschaft Für Technologie Und Innovation Mbh Materiau composite conducteur d'ions permeable aux substances, procede permettant de le produire et son utilisation
EP1166860A2 (fr) * 2000-06-27 2002-01-02 Creavis Gesellschaft für Technologie und Innovation mbH Matériau composite perméable revêtu d'un polyélectrolyte, son procédé de fabrication et son utilisation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0875524A2 (fr) * 1997-04-25 1998-11-04 Johnson Matthey Public Limited Company Membranes composites
WO1999057769A1 (fr) * 1998-05-06 1999-11-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Separateur electrique a base d'un substrat revetu de ceramique
WO1999060650A1 (fr) * 1998-05-18 1999-11-25 Firma Carl Freudenberg Unite membrane-electrodes pour pile a combustible
DE19821976A1 (de) * 1998-05-18 1999-11-25 Freudenberg Carl Fa Brennstoffzelle
WO1999062620A1 (fr) * 1998-06-03 1999-12-09 Creavis Gesellschaft Für Technologie Und Innovation Mbh Materiau composite conducteur d'ions permeable aux substances, procede permettant de le produire et son utilisation
EP1166860A2 (fr) * 2000-06-27 2002-01-02 Creavis Gesellschaft für Technologie und Innovation mbH Matériau composite perméable revêtu d'un polyélectrolyte, son procédé de fabrication et son utilisation

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9680141B2 (en) 2012-01-30 2017-06-13 Litarion GmbH Separator comprising an organic-inorganic adhesion promoter
CN104592541A (zh) * 2015-01-20 2015-05-06 浙江大学 微孔聚苯并咪唑膜及改性聚苯并咪唑为隔膜的锂硫电池

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TW200306032A (en) 2003-11-01
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WO2003073545A3 (fr) 2005-01-06
AU2003248341A1 (en) 2003-09-09

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