WO2002080296A2 - Membrane electrolytique, unites d'electrodes membranaires les contenant, procedes permettant de les produire et utilisations particulieres - Google Patents

Membrane electrolytique, unites d'electrodes membranaires les contenant, procedes permettant de les produire et utilisations particulieres Download PDF

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Publication number
WO2002080296A2
WO2002080296A2 PCT/EP2002/001549 EP0201549W WO02080296A2 WO 2002080296 A2 WO2002080296 A2 WO 2002080296A2 EP 0201549 W EP0201549 W EP 0201549W WO 02080296 A2 WO02080296 A2 WO 02080296A2
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WIPO (PCT)
Prior art keywords
zirconium
acid
membrane
electrolyte membrane
proton
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PCT/EP2002/001549
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German (de)
English (en)
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WO2002080296A3 (fr
Inventor
Volker Hennige
Gerhard HÖRPEL
Christian Hying
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Creavis Gesellschaft Für Technologie Und Innovation Mbh
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Priority to AU2002246091A priority Critical patent/AU2002246091A1/en
Publication of WO2002080296A2 publication Critical patent/WO2002080296A2/fr
Publication of WO2002080296A3 publication Critical patent/WO2002080296A3/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
    • 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
    • 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]
    • 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

  • Electrolyte membrane this comprehensive membrane electrode assembly, manufacturing method and special uses
  • the present invention relates to special proton-conductive, flexible electrolyte membranes for a fuel cell, methods for producing these electrolyte membranes and 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 leads
  • fuel cells which consist of an ion-conducting electrolyte membrane and the optionally catalytically active electrodes (anode and cathode) applied to it.
  • Electrolyte membranes made from organic polymers which are modified with acidic groups such as Nafion® (DuPont, EP 0 956 604), sulfonated polyether ketones (Höchst, EP 0 574 791), are known from the prior art as proton-exchanging membranes (PEMs) for fuel cells.
  • PEMs proton-exchanging membranes
  • 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 membrane must be in a fuel cell be operated both on the anode side and on the cathode side in an atmosphere saturated with water vapor.
  • electrolyte membranes made of 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. Low sheet resistances and high power densities of a fuel cell for technical applications in automobile construction are therefore not possible with the known materials.
  • WO99 / 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 is coated with a porous ceramic material to which a proton-conducting material has been applied. This electrolyte membrane has a proton conductivity superior to an organic Nafipn 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 has been used.
  • the electrolyte membrane known from WO99 / 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 WO99 / 62620 is unsuitable for use in a fuel cell in practice. It has in fact shown that the known electrolyte membranes have indeed at elevated temperatures, a good proton conductivity, that "the other hand, occur under practical conditions in a fuel cell shorts that render the electrolyte membranes useless.
  • the use of glass substrates is not excluded, low due to the
  • the long-term stability under the strongly acidic conditions in a fuel cell is problematic in terms of the acid stability of glasses, particularly with regard to the long-term stability in the case of the required service life of more than 5000 hours in a fuel cell on board a vehicle, and the electrolyte membranes known from WO99 / 62620
  • the adhesion of the ceramic material to the metal carrier is problematic, so that the ceramic layer must be separated from the metal net if it is to be left standing for a long time.
  • a high proton conductivity with a significantly reduced air humidity in comparison to polymer membranes (ii) enables a low total resistance of a membrane electrode assembly, (iii) has mechanical properties such as tensile strength and flexibility, which for a
  • Nafion membranes are reached, (vi) short circuits and especially in a direct methanol fuel cell cross-over
  • the present invention provides an electrolyte membrane comprising a combination of a special composite material and a proton conductive material.
  • the present invention therefore proposes a proton-conductive, flexible electrolyte membrane which is impermeable to the reaction components of the fuel cell reaction a fuel cell, comprising a permeable composite material made of a flexible, perforated support comprising a ceramic and a porous ceramic material, the composite material being permeated with a proton-conductive material which is suitable for selectively guiding protons through the membrane.
  • the electrolyte membrane of the present invention 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 all-ceramic carrier also allows the porous ceramic material to adhere firmly to the carrier. In a special embodiment, by using only a single ceramic material, phase boundaries between different materials in the composite material according to the invention can be avoided.
  • the electrolyte membranes according to the invention can be used in a reformate or direct methanol fuel cell, which 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.
  • a 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. Furthermore, it is possible to manufacture the electrolyte membranes of the present invention in a membrane thickness, regardless of the proton conductive material, which is less than that which can be achieved with conventional Nafion membranes. In this way, the conductivity and the sheet resistance can be controlled via the membrane thickness in an area that is not accessible to Nafion membranes, and a large number of proton-conductive materials can be selected at the same time.
  • the decoupling according to the invention of the choice of the proton-conductive material from the achievable layer thickness for the creation of electrolyte membranes for fuel cells with desired conductivities and surface resistances is unprecedented in the prior art and enables access to tailored electrolyte membranes.
  • the ceramic of the carrier is preferably a ceramic fleece or a ceramic fabric made of refractory ceramic fibers with a predominantly polycrystalline microstructure.
  • a ceramic fleece is preferred over a ceramic fabric because it has a higher porosity and no mesh.
  • the ceramic is preferably a material that consists to a large extent of aluminum oxide, silicon carbide, silicon nitride or a zirconium oxide. In the event that the fibers contain aluminum oxide, there is a ratio of 0 to 30% silicon oxide in relation to aluminum oxide. Fibers containing alumina are preferred.
  • the carrier must be stable under the operating conditions in a fuel cell. Therefore, the ceramic for the carrier is preferably stable against protons which are passed through the membrane, the proton-conducting material with which the composite material is penetrated and the ceramic material with which the carrier is contacted. Furthermore, the ceramic is preferably also stable with respect to the reaction medium with which the carrier can come into contact if the ceramic coating of the carrier has cracks.
  • the ceramic from which the carrier is produced preferably has a melting / softening point of> 1400 ° C., particularly preferably> 1550 ° C.
  • the flexible, openwork ceramic support may further comprise a material selected from glass, minerals, plastics, amorphous non-conductive substances, natural products, composites, composite materials, or at least a combination of these materials, provided that these materials are useful Do not affect the electrolyte membrane of the invention under the operating conditions in a fuel cell.
  • a carrier which has been made permeable to material by treatment with laser beams or ion beams can also be used as a flexible, openwork carrier comprising a ceramic.
  • the carrier preferably comprises fibers and / or filaments with a diameter of 1 to 150 ⁇ m, preferably 1 to 20 ⁇ m, and / or threads with a diameter of 5 to 150 ⁇ m, preferably 20 to 70 ⁇ m.
  • 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. 5,5-Tex yarns with 10-50 warp or weft threads are particularly preferred, and 20-28 warp and 28-36 weft threads are preferred.
  • the porous ceramic material preferably has pores with an average diameter of at least 20 nm, preferably of at least 100 nm, very particularly preferably more than 500 nm.
  • the ceramic material of the composite material preferably has a porosity of 10% to 60%, preferably 20% to 45%.
  • 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, and / or an ionic liquid. These components impart proton conductivity to the electrolyte membrane.
  • the proton-conductive material can optionally contain an oxide of aluminum, silicon, titanium, zirconium, and / or phosphorus. Such an oxide is essential when using Bronsted acid. In the event that an immobilized hydroxysilylalkyl acid of sulfur or phosphorus or a salt thereof, and / or an ionic liquid are used, the additional oxide can be used to be dispensed with.
  • the Bronsted acid can be sulfuric acid, phosphoric acid, perchloric acid, nitric acid, hydrochloric acid, sulfurous acid, phosphorous acid and also esters thereof and / or a polymeric organic acid.
  • the electrolyte membrane according to the invention is preferably stable at at least 80 ° C., preferably at least 120 ° C., and very particularly preferably at at least 140 ° C.
  • the composite material of the electrolyte membrane preferably has a thickness in the range from 5 to 150 ⁇ m, preferably 5 to 50 ⁇ m, very particularly preferably 5 to 30 ⁇ m, when a ceramic fleece is used as the carrier.
  • the composite material of 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, when a ceramic fabric is used as the carrier.
  • the electrolyte membrane according to the invention preferably tolerates a bending radius of at least 100 mm, in particular of at least 20 mm and very particularly preferably of at least 5 mm.
  • the electrolyte membrane according to the invention preferably has a conductivity of at least 2 mS / cm, preferably at least 20 mS / cm, very particularly preferably 23 mS / cm at room temperature and at a relative atmospheric humidity of 35%.
  • An electrolyte membrane of the present invention is available from
  • the electrolyte membranes of the present invention can contain a special composite material which is known in general terms and for another application from PCT / EP98105939.
  • This composite can be infiltrated with a proton-conducting material or a precursor thereof, whereupon the membrane is dried, solidified and optionally modified in a suitable manner, so that a material-impermeable, ion / proton-conducting and flexible membrane is obtained.
  • the carrier containing a ceramic is first transferred according to PCT / EP98 / 05939 into a mechanically and thermally stable, permeable ceramic basic membrane which is neither electrically nor ionically conductive. Then this porous, electrically insulating basic membrane is penetrated with the proton-conducting material.
  • a flexible, perforated carrier comprising a ceramic is contacted or infiltrated with a suspension which contains a precursor for the porous ceramic material.
  • a suspension which contains a precursor for the porous ceramic material.
  • the porous ceramic material comes as a preliminary stage for the porous ceramic material at least one inorganic component from a compound of a metal, a semimetal or a mixed metal with one of the elements of the 3rd to 7th main group in question, which are applied as a suspension to the support and can preferably be solidified by heating.
  • Contacting or infiltration can be carried out by printing, pressing, pressing, rolling, knife coating, spreading, dipping, spraying or pouring.
  • the carrier can be treated with a sol before the porous ceramic material is applied.
  • the sol preferably contains precursor compounds of the oxides of aluminum, titanium, zirconium or silicon. By solidifying the sol, the fibers of the ceramic nonwoven are glued together, thereby improving the mechanical stability of the nonwoven.
  • the suspension with which the carrier is contacted preferably contains an inorganic component and a metal oxide sol, a semimetal oxide sol or a mixed metal oxide sol or a mixture of these sols.
  • a preferred suspension can be prepared by suspending an inorganic component in one of these brines.
  • sols such as titanium nitrate sol, zirconium nitrate sol or silica sol can be used.
  • the brine can also be obtained by hydrolysis of a metal compound,
  • a metal nitrate is preferably used as the compound to be hydrolyzed
  • Metal chloride a metal carbonate, a metal alcoholate compound or one
  • Semi-metal alcoholate compound particularly preferably at least one metal alcoholate compound, a metal nitrate, a metal chloride, a metal carbonate or at least one
  • Semi-metal alcoholate compound selected from the compounds of the elements Ti, Zr, Al,
  • Zirconium nitrate hydrolyzed. It may be advantageous to carry out the hydrolysis with at least half the molar ratio of water, based on the hydrolyzable group of the hydrolyzable
  • the hydrolyzed compound may be with an acid, preferably with a 10 to 60% acid, preferably with a mineral acid selected from sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid and nitric acid or a mixture of these acids.
  • An inorganic component with a grain size of 1 to 10,000 nm can be suspended in the sol.
  • At least one inorganic component which comprises at least one compound from the oxides of the subgroup elements or from the elements of the 3rd to 5th main group, preferably oxides, selected from the oxides of the elements Sc, Y, Ti, Zr, Nb, Ce, V , Cr, Mo, W, Mn, Fe, Co, B, AI, In, TI, Si, Ge, Sn, Pb and Bi, such as. B. Y 2 0 3 , Zr0 2 , Fe 2 0 3 , Fe 3 0 4 , Si0 2 , Al 2 O 3 , has suspended.
  • the inorganic component can also be aluminosilicates, aluminum phosphates, zeolites or partially exchanged zeolites, such as, for. B. ZSM-5, Na-ZSM-5 or Fe-ZSM-5 or amorphous microporous mixed oxides, which can contain up to 20% non-hydrolyzable organic compounds, such as. B. vanadium oxide, silicon oxide glass or aluminum oxide-silicon oxide-methyl silicon sesquioxide glasses.
  • the mass fraction of the suspended component is preferably 0.1 to 500 times the hydrolyzed compound used.
  • Cracks in the composite material can be avoided by a suitable choice of the grain size of the suspended compounds depending on the size of the pores, holes or interstices of the carrier, but also by a suitable choice of the layer thickness of the composite material and the proportionate ratio of sol: solvent: metal oxide.
  • 100 microns can preferably be used to increase the freedom from cracks, which has a suspended compound with a grain size of at least 0.7 microns. in the in general, the ratio of grain size to mesh or pore size should be from 1: 1000 to 50: 1000.
  • the composite material can preferably have a thickness of 5 to 1000 ⁇ m, particularly preferably from 10 to 70 ⁇ m and very particularly preferably from 10 to 30 ⁇ m.
  • the suspension of sol and compounds to be suspended preferably has a ratio of solids to the compounds to be suspended from 0.1: 100 to 100: 0.1, preferably from 0.1: 10 to 10: 0.1 parts by weight.
  • the suspension can be solidified by heating the composite of suspension and carrier to 50 to 1000 ° C.
  • the composite is exposed to a temperature of 50 to 100 ° C. for 10 seconds to 1 hour, preferably 10 seconds to 10 minutes.
  • the composite is exposed to a temperature of 100 to 800 ° C. for 5 seconds to 10 minutes, preferably 5 seconds to 5 minutes, particularly preferably for 5 seconds to 1 minute.
  • the composite can be heated with heated air, hot air, infrared radiation, microwave radiation or electrically generated heat.
  • the suspension can be solidified by contacting the suspension with a preheated carrier and thus solidifying immediately after contacting.
  • the carrier is unrolled from a roll at a speed of 1 m / h to 1 m / s, onto an apparatus which contacts the suspension with the carrier and then to another apparatus which solidifies the suspension through Heating is made possible, and the composite material thus produced is rolled up on a second roll. In this way it is possible to manufacture the composite material continuously.
  • the insensitivity to cracks in composite materials with large mesh or pore widths can also be improved by applying suspensions to the carrier which have at least two suspended compounds.
  • Compounds to be suspended are preferably used which have a particle size ratio of 1: 1 to 1:20, particularly preferably 1: 1.5 to 1: 2.5.
  • the weight fraction of the grain size fraction with the smaller grain size should not exceed a proportion of at most 50%, preferably 20% and very particularly preferably 10%, of the total weight of the grain size fraction used.
  • the composite material is penetrated by a proton-conducting material which is suitable for selectively guiding protons through the membrane and which gives the electrolyte membrane proton conductivity.
  • the proton-conducting material can be introduced into the ceramic material after the production of the composite material or also during the production of the composite material.
  • the proton-conductive material can comprise a Bronsted acid, an immobilized hydroxysilylalkyl acid of sulfur or phosphorus or a salt thereof, and / or an ionic liquid and optionally an oxide of aluminum, silicon, titanium, zirconium and / or phosphorus.
  • all the proton-conducting materials described in WO99 / 62620 can be used as a suitable proton-conducting material for producing the electrolyte membrane.
  • the method according to the invention for producing an electrolyte membrane can start on the basis of the permeable composite material include in particular the following steps:
  • Sulfur or phosphorus or a salt thereof and a sol which comprises a precursor for oxides of aluminum, silicon, titanium, zirconium and / or phosphorus and
  • the mixture containing a sol with which the composite material is infiltrated is obtainable 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 phosphoric acid, and peptizing the hydrolyzate to the mixture containing a sol.
  • hydrolyzable compound is non-hydrolyzable groups in addition to hydrolyzable groups.
  • An alkyltrialkoxy or dialkyldialkoxy or trialkylalkoxy compound of the element silicon is preferably used as such a compound to be hydrolyzed.
  • An acid or base soluble in water and / or alcohol can be added to the mixture.
  • An acid or base of the elements Na, Mg, K, Ca, V, Y, Ti, Cr, W, Mo, Zr, Mn, Al, Si, P or S is preferably added.
  • the mixture can also comprise non-stoichiometric metal, semimetal or non-metal oxides or hydroxides which have been produced by changing the oxidation state of the corresponding element.
  • the oxidation level can be changed by reaction with organic compounds or inorganic compounds or by electrochemical reactions.
  • the oxidation stage is preferably changed by reaction with an alcohol, aldehyde, sugar, ether, olefin, peroxide or metal salt.
  • Compounds that change the oxidation state in this way are e.g. B. Cr, Mn, V, Ti, Sn, Fe, Mo, W or Pb.
  • Substances which lead to the formation of inorganic ion-conducting structures can also be added to the mixture.
  • Such substances can e.g. B. zeolite and / or ⁇ -aluminosilicate particles.
  • the permeable composite material can also be given an ionic treatment by treatment with a silane.
  • a silane for this purpose, a 1 to 20% solution of this silane is made up in a water-containing solution and the composite material is immersed.
  • Aromatic and aliphatic alcohols, aromatic and aliphatic hydrocarbons and other common solvents or mixtures can be used as solvents.
  • the use of ethanol, octanol, toluene, hexane, cyclohexane and octane is advantageous.
  • the impregnated composite material is dried at approximately 150 ° C. and can be used either directly or after repeated subsequent coating and drying at 150 ° C. as an ion-conductive, permeable composite material. Both cationic and anionic silane groups are suitable for this. In the case of proton-conducting materials, sulfonic or phosphonic acid groups are preferred.
  • the solution or suspension for treating the composite material also comprises acidic or basic compounds and water in addition to a trialkoxysilane.
  • the acidic or basic compounds preferably comprise at least one Bronsted or Lewis acid or base known to the person skilled in the art.
  • the mixture with which the composite material is infiltrated can contain further proton-conducting substances, preferably titanium phosphates, titanium phosphonates, zirconium phosphates, zirconium phosphonates, iso- and heteropolyacids, nanocrystalline and / or crystalline metal oxides, where Al 2 O 3 -, ZrO 2 -, TiO 2 - or SiO 2 powder are preferred.
  • iso- and heteropolyacids are tungsten phosphoric acid and silicon tungstic acid.
  • the infiltration of the composite material can be carried out by printing, pressing, pressing, rolling, knife coating, spreading, dipping, spraying or pouring the mixture onto the permeable composite material.
  • the infiltration with the mixture can be carried out repeatedly. If necessary, a drying step, preferably at an elevated temperature in a range from 50 to 200 ° C., can take place between the repeated infiltration. In a preferred embodiment, the infiltration of the permeable composite material takes place continuously. It may be advantageous to preheat the composite material for infiltration.
  • the mixture can be solidified in the composite material by heating to a temperature of 50 to 800 ° C., preferably 100 to 600 ° C., very particularly preferably 150 to 200 ° C., the heating being carried out by heated air, hot air, infrared radiation or microwave radiation can.
  • the electrolyte membrane can also be formed by using a sol containing an ion-conducting material or a material that is ion-conducting after a further treatment
  • Has properties are obtained in the manufacture of the composite material. Materials are preferably added to the sol, which lead to the formation of inorganic ion-conducting layers on the inner and / or outer surfaces of the particles contained in the composite material.
  • An acidic and / or basic group-containing trialkoxysilane solution or suspension can be used to produce the electrolyte membrane.
  • At least one of the acidic or basic groups is preferably a quaternary ammonium, phosphonium, alkylsulfonic acid, carboxylic acid or phosphonic acid group.
  • the flexible membrane electrode unit for a fuel cell comprises an anode layer and a cathode layer, each of which is 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 being a permeable composite material made of a flexible, perforated, ceramic comprising carrier and a porous ceramic material, wherein the composite material is interspersed with a proton-conductive material which is capable of selectively guiding protons through the membrane, and wherein the anode layer and the cathode layer are porous and a catalyst for the anode and cathode reactions, respectively 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 composite material preferably each comprises (i) an immobilized hydroxysilylalkyl acid of sulfur or phosphorus or a salt thereof, and optionally an oxide of aluminum, silicon, titanium, zirconium and / or phosphorus, and / or (ii) a Bronsted acid and an oxide of aluminum, silicon, titanium, zirconium, and / or phosphorus and optionally (üi) inorganic oxides, phosphates, phosphides, phosphonates, sulfates, sulfonates,
  • the proton conductive material of the composite optionally includes an ionic liquid that may contain Bronsted acid.
  • the hydroxysilylalkyl acid of sulfur or phosphorus or a salt thereof is an organosilicon compound of the general formulas
  • 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 formulas
  • n, m each represents an integer from 0 to 6
  • M represents H, NH 4 or a metal
  • x 1 to 4
  • y 1 to 3
  • z 0 to 2
  • 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 dihydroxysilylpropylsulfondioic acid.
  • the hydroxysilylalkyl acid of sulfur or phosphorus or a salt thereof is immobilized with a hydrolyzed compound of phosphorus or a hydrolyzed nitrate, oxynitrate, chloride, oxychloride, carbonate, alcoholate, acetate, acetylacetonate of a metal or semimetal.
  • TEOS tetraethyl orthosilicate
  • TMOS tetramethyl orthosilicate
  • the composite impregnated with a proton conductive material can additionally contain an ionic liquid which comprises a cation which is selected from the imidazolium ions, pyridinium ions, ammonium ions or phosphonium ions of the following formulas:
  • R and R ' may be the same or different and for alkyl, olefin or aryl groups stand or mean hydrogen
  • the ionic liquid comprises an anion which is selected from the following ions: nitrate, sulfate, hydrogen sulfate, chloroaluminations, BF 4 " , alkyl borate ions, preferably triethylhexyl borate, halogenophosphate ions, preferably PF 6 " .
  • 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 120 ° C, and very particularly preferably at at least 140 ° C.
  • the membrane electrode unit according to the invention preferably tolerates a bending radius of at least 100 mm, in particular of at least 20 mm, very particularly preferably 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 catalyst support is electrically conductive in the anode layer and in the cathode layer.
  • an electrolyte membrane is coated with the optionally catalytically active electrode material by a suitable method.
  • 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 interface gas space / catalyst (electrode) / electrolyte is formed.
  • the electrically conductive material as a catalyst carrier is dispensed with, in which case the electrically conductive catalyst directly for the discharge of the electrons from the membrane electrode assembly.
  • the catalytically active (gas diffusion) electrodes are built up on the electrolyte membrane to produce the membrane electrode unit.
  • an ink is produced from a soot 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, scraping, spraying, rolling or by dipping.
  • the ink can contain any ion-conducting material that is also used to infiltrate the composite.
  • the ink can contain an acid or its salt, which is immobilized by a chemical reaction in the course of a nerfixation 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, 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 composite material, 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 of the catalyst and electrolyte without inhibiting mass transfer 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 proportion of solvent in the ink.
  • an agent can be used which comprises the following components: (TI) 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, lead, tin, vanadium
  • TEOS tetraethyl orthosilicate
  • TMOS tetramethyl orthosilicate
  • 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 or a platinum alloy and optionally a cocatalyst, the cocatalyst being a transition metal complex of phthalocyanine or substituted phthalocyanines.
  • the catalyst precursor preferably comprises platinum, palladium and / or ruthenium.
  • the transition metal complex of the cocatalyst preferably comprises nickel and / or cobalt.
  • 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 600 ° C and preferably between 100 and 250 ° 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 contains carbon black, metal powder, metal oxide powder, carbon or carbon.
  • a prefabricated gas distributor which contains the gas diffusion electrode, consisting of an electrically conductive material (for example a porous carbon fleece), catalyst and electrolyte, can be applied directly to the membrane.
  • the gas distributor and membrane are fixed using a pressing process.
  • the gas distributor can also be fixed on the membrane by an adhesive.
  • This adhesive must be ion-conductive Have properties and can in principle consist of the material classes already mentioned above.
  • a metal oxide sol that additionally contains a hydroxysilyl acid can be used as the adhesive.
  • the gas distributor can also be applied "in situ" in the last stage of membrane or gas diffusion electrode production. 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 cases by gelling the sol with subsequent drying / solidification.
  • 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 can additionally contain a compound that is already proton-conductive or at least ion-conductive at the end of the manufacturing process. Suitable ionic materials are the ionic 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 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.
  • Production example 1.4 50 g of titanium tetraethoxylate were hydrolyzed with 270 g of water and peptized with 30 g of nitric acid (25%). 100 g of ethanol and 350 g of CT 2000 SG from Alcoa were then added and stirred. This suspension can then be used to manufacture a composite or as a precursor for a proton conductive material.
  • Production Example 1.8 80 g of titanium tetraisopropylate are hydrolyzed with 40 g of water and the resulting precipitate is peptized with 120 g of 25% hydrochloric acid. This solution will last until Stirring is clear and after adding 200 g of titanium dioxide from Bayer, the mixture is stirred until the agglomerates have dissolved. This suspension can then be used to manufacture a composite or as a precursor for a proton conductive material.
  • S500-300 test product from Rhone-Poulenc
  • Production Example 112 100 g of silica sol (Levasil 200, from Bayer AG) were stirred with 180 g of AA07 aluminum oxide from Sumitomo Chemical until the agglomerates dissolved. This suspension can then used to manufacture a composite or as a precursor for a proton conductive material.
  • Precipitation is after adding 10 g of zirconium dioxide from Degussa (particle size 50 run) until the agglomerates are completely dissolved. This suspension can then be used to manufacture a composite or as a precursor for a proton conductive material.
  • a ceramic fleece with a thickness of about 10 microns made of Al 2 O 3 fibers is with a
  • Zikonnitratsol containing 30 wt .-% ZrO 2 , treated and annealed at 200 ° C to bond the ceramic fibers.
  • a suspension according to Example 1.9 is knife-coated onto the treated ceramic fleece and dried within 10 seconds by blowing with hot air which had a temperature of 550 ° C.
  • a flat composite material was obtained which can be used as a composite material with a pore size of 0.2 to 0.4 ⁇ m. The composite material can be bent to a radius of 5 mm without the composite material being destroyed.
  • the composite material can be used to produce an electrolyte membrane according to the invention.
  • a suspension according to production example 1.2 was applied to a composite material as described in example 2.1 by rolling it up with a layer thickness of 5 ⁇ m. The suspension was solidified again by blowing the composite with hot air at 550 ° C. for about 5 seconds. A composite material was obtained which had a pore size of 30-60 nm and is suitable for producing an electrolyte membrane according to the invention.
  • the suspensions of preparation examples 1.3 to 1.19 are each applied to the carrier described in preparation example 2.1 and dried by blowing with air at a temperature of 450-550 ° C. for a few seconds.
  • the composite material obtained can be used to produce a composite membrane according to the invention.
  • the suspension produced according to production example 1.20 is applied in a thin layer to a ceramic fleece and solidified at 550 ° C. within 5 seconds.
  • the composite material obtained can be used to produce a composite membrane according to the invention.
  • An inorganic, permeable composite material which was produced by applying a thin layer of the suspension from preparation example 1.1 on a ceramic carrier according to preparation example 2.1, was immersed in a solution which consisted of the following components: 5% Degussa silane 285 (a propylsulfonic acid triethoxysilane), 20% deionized (VE) water in 75% ethanol. The solution had to be stirred at room temperature for 1 h before use.
  • the composite was dried at 80 to 150 ° C to provide an electrolyte membrane of the present invention.
  • Example 5 An additional 25 g of tungsten phosphoric acid are dissolved in 50 ml of the sol from Example 5.
  • the composite material from production example 2.1 is immersed in this sol for 15 minutes. Then proceed as in Example 5.
  • a porous electrolyte membrane according to Examples 5 to 9 is sprayed with [EMIM] CF 3 SO 3 (EMIM: 1-ethyl-3-methylimidazolium) as the ionic liquid.
  • [EMIM] CF 3 SO 3 EMIM: 1-ethyl-3-methylimidazolium
  • Spraying is carried out from one side of the composite material until the opposite side of the composite material is also wetted by the ionic liquid which has passed through the composite material. In this way it is achieved that the air contained in the porous ion-conducting composite material is displaced by the ionically conductive liquid.
  • This membrane can be allowed to air dry after wiping off excess ionic liquid.
  • the ionic liquid is retained in the membrane according to the invention by capillary forces. Because ionic
  • Liquids do not have a measurable vapor pressure, even after prolonged storage of the membrane produced according to the invention, a reduction in the ionic liquid in the membrane is not to be expected.
  • EMIM 1-ethyl-3-methylimidazolium ion
  • BMIM 1-butyl-3-methylimidazolium ion
  • MMIM 1-methyl-3-methylimidazolium ion
  • Ts H 3 CC 6 H 4 SO 2 (tosyl)
  • Oc octyl
  • Et ethyl
  • Me methyl
  • Bu n-butyl
  • CF 3 SO 3 triflate anion
  • Ph phenyl can be used.
  • Example 75 An electrolyte membrane was produced as in Example 75, H 2 SO 4 (98% strength) being added to the sol instead of HClO 4 as acid. Under the same measurement conditions (room temperature and approx. 35% RH), the conductivity is about 23 mS / cm after a thermal treatment of 100 ° C (1 h).
  • Example 77
  • a TEOS sol consisting of TEOS (11 ml), diethyl phosphite (19 ml), ethanol (11 ml) and H 3 PO 4 (10 ml) is precondensed for one hour and then a basic membrane, which was produced according to Preparation Example 2.20 , infiltrated by doctor blade.
  • the membrane is dried at 150 ° C for 1 h.
  • the conductivity of the membrane at room temperature and approx. 35% rh is around. 2.9 mS / cm.
  • a membrane according to Example 1 is first screen-printed with the ink according to Example 79 by screen printing. This side serves as an anode in the later membrane electrode assembly. The printed membrane is dried at a temperature of 150 ° C. In addition to the escape of the solvent, 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 82. 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 80 and the cathode ink according to Example 83 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 to form a membrane electrode unit, which can then be installed in the fuel cell.
  • the electrodes are first manufactured. For this, a ceramic fleece is coated with a carbon black / platinum mixture (40%). These electrodes are pressed onto the electrolyte membrane according to Example 77. 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 made as described in Example 86, except that a conventional Nafion®117 membrane was used as the MEA. 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 sharply, so that the fuel cell could no longer be operated. On the other hand, a membrane according to the invention can also be operated at a relative atmospheric humidity which was approximately 10% on the anode side and approximately 5% on the cathode side without the function of the fuel cell being significantly impaired.

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  • Sustainable Energy (AREA)
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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne une membrane électrolytique souple, imperméable aux constituants de la réaction des cellules électrochimiques, qui conduit les protons. Ladite membrane comprend un matériau composite perméable aux substances, à base d'un support souple ajouré comprenant une céramique, ainsi que d'un matériau céramique. Le matériau composite est chargé avec un matériau conduisant les protons, approprié pour conduire des protons de manière sélective à travers la membrane.
PCT/EP2002/001549 2001-03-30 2002-02-14 Membrane electrolytique, unites d'electrodes membranaires les contenant, procedes permettant de les produire et utilisations particulieres WO2002080296A2 (fr)

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AU2002246091A AU2002246091A1 (en) 2001-03-30 2002-02-14 Electrolyte membrane, membrane electrode units comprising the same, method for the production thereof and specific uses therefor

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DE10115927A DE10115927A1 (de) 2001-03-30 2001-03-30 Elektrolytmembran, diese umfassende Membranelektrodeneinheiten, Verfahren zur Herstellung und spezielle Verwendungen
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WO2003073543A2 (fr) * 2002-02-26 2003-09-04 Creavis Gesellschaft Für Technologie Und Innovation Mbh Membrane electrolyte souple a base d'un support comprenant des fibres polymeres, procede de production et utilisation de cette membrane
WO2007104477A1 (fr) * 2006-03-10 2007-09-20 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Barbotines et matériau composite céramique qu'elles permettent de produire
CN100405644C (zh) * 2004-07-21 2008-07-23 株式会社东芝 质子导电固体电解质以及使用该电解质的燃料电池
CN100422112C (zh) * 2005-07-08 2008-10-01 中国科学院物理研究所 一种具有球形核壳结构的碳硅复合材料及其制法和用途
US9365020B2 (en) 2011-09-15 2016-06-14 Siemens Aktiengesellschaft Method for the dry production of a membrane electrode unit, membrane electrode unit, and roller arrangement
US9680141B2 (en) 2012-01-30 2017-06-13 Litarion GmbH Separator comprising an organic-inorganic adhesion promoter
CN110878441A (zh) * 2019-11-05 2020-03-13 杭州师范大学 一种高效重金属吸附、抗菌的纳米纤维膜及其制备方法
CN114804492A (zh) * 2022-06-01 2022-07-29 苏州仕净科技股份有限公司 一种高氨氮废水处理系统及工艺

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DE10255122A1 (de) 2002-11-26 2004-06-03 Creavis Gesellschaft Für Technologie Und Innovation Mbh Langzeitstabiler Separator für eine elektrochemische Zelle
DE10255121B4 (de) * 2002-11-26 2017-09-14 Evonik Degussa Gmbh Separator mit asymmetrischem Porengefüge für eine elektrochemische Zelle
DE102006061779A1 (de) * 2006-12-21 2008-06-26 Volkswagen Ag Membran-Elektroden-Einheit mit elektrolytdotierter Elektrode für Brennstoffzelle und Verfahren zu ihrer Herstellung
JP2020049429A (ja) * 2018-09-27 2020-04-02 トヨタ自動車株式会社 車両用排ガス浄化装置

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WO1999038896A1 (fr) * 1998-01-30 1999-08-05 Dais Corporation Membrane conductrice d'ions pour pile a combustible
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
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WO2003073543A2 (fr) * 2002-02-26 2003-09-04 Creavis Gesellschaft Für Technologie Und Innovation Mbh Membrane electrolyte souple a base d'un support comprenant des fibres polymeres, procede de production et utilisation de cette membrane
WO2003073543A3 (fr) * 2002-02-26 2004-01-08 Creavis Tech & Innovation Gmbh Membrane electrolyte souple a base d'un support comprenant des fibres polymeres, procede de production et utilisation de cette membrane
CN100405644C (zh) * 2004-07-21 2008-07-23 株式会社东芝 质子导电固体电解质以及使用该电解质的燃料电池
CN100422112C (zh) * 2005-07-08 2008-10-01 中国科学院物理研究所 一种具有球形核壳结构的碳硅复合材料及其制法和用途
WO2007104477A1 (fr) * 2006-03-10 2007-09-20 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Barbotines et matériau composite céramique qu'elles permettent de produire
US9365020B2 (en) 2011-09-15 2016-06-14 Siemens Aktiengesellschaft Method for the dry production of a membrane electrode unit, membrane electrode unit, and roller arrangement
US9680141B2 (en) 2012-01-30 2017-06-13 Litarion GmbH Separator comprising an organic-inorganic adhesion promoter
CN110878441A (zh) * 2019-11-05 2020-03-13 杭州师范大学 一种高效重金属吸附、抗菌的纳米纤维膜及其制备方法
CN114804492A (zh) * 2022-06-01 2022-07-29 苏州仕净科技股份有限公司 一种高氨氮废水处理系统及工艺
CN114804492B (zh) * 2022-06-01 2024-02-27 苏州仕净科技股份有限公司 一种高氨氮废水处理系统及工艺

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