WO2003069712A2 - Membranes ceramiques conductrices de protons a base de phosphates de zirconium, procedes de realisation associes et utilisation de ces membranes dans des assemblages membrane-electrode et dans des piles a combustible - Google Patents

Membranes ceramiques conductrices de protons a base de phosphates de zirconium, procedes de realisation associes et utilisation de ces membranes dans des assemblages membrane-electrode et dans des piles a combustible Download PDF

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Publication number
WO2003069712A2
WO2003069712A2 PCT/EP2003/000163 EP0300163W WO03069712A2 WO 2003069712 A2 WO2003069712 A2 WO 2003069712A2 EP 0300163 W EP0300163 W EP 0300163W WO 03069712 A2 WO03069712 A2 WO 03069712A2
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Prior art keywords
proton
membrane
zirconium
acid
substrate
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PCT/EP2003/000163
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German (de)
English (en)
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WO2003069712A3 (fr
Inventor
Volker Hennige
Christian Hying
Gerhard HÖRPEL
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Creavis Gesellschaft Für Technologie Und Innovation Mbh
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Priority to AU2003244864A priority Critical patent/AU2003244864A1/en
Publication of WO2003069712A2 publication Critical patent/WO2003069712A2/fr
Publication of WO2003069712A3 publication Critical patent/WO2003069712A3/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
    • 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 proton-conducting ceramic membranes based on zirconium phosphates, processes for their production and the use thereof in MEAs and fuel cells.
  • Membranes are at the heart of a fuel cell.
  • PEMs proton-exchange membranes
  • polymers modified with an acidic group are essentially used as the electrolyte membranes.
  • Nafion (DuPont, fluorinated backbone with sulfonic acid functionality) or related systems are usually used here.
  • Another example of a purely organic, proton-conducting polymer are the u. a. sulfonated polyether ketones described by Hoechst (EP 0574791 B1).
  • Inorganic proton conductors are also known from the literature (see, for example, in “Proton Conductors”, P. Colomban, Cambridge University Press, 1992), but these mostly show conductivities which are too low or the conductivity only reaches at high temperatures, typically over 500 ° C technically usable values, such as. B. in the defect perovskites.
  • MHSO family another class of purely inorganic proton conductors, the MHSO family, are good proton conductors, but at the same time they are easily soluble in water, so that they are out of the question for fuel cell applications, since water is produced on the cathode side as a product and the membrane thus in the course of Time would be destroyed.
  • zirconium phosphates in the form of the ⁇ - or ⁇ -ZrP, have long been known as proton conductors (Alberti, Solid State Ionics 125 (1999), 91 ff). Since the conductivity of this material is essentially determined by the free OH groups, a large surface area is of great importance.
  • the literature (Glipa et al, Solid State Ionics 97 (1997), 227ff) states a conductivity of 10 "5 to 10 '6 S / cm at medium atmospheric humidity.
  • a composite material as described in WO 99/62620 is not suitable for use in a fuel cell under real conditions either because the electrolyte membrane must be absolutely impermeable to substances for these applications, since otherwise it would lead to a direct reaction of the reactants (hydrogen or Methanol on the anode side and oxygen or air on the cathode side).
  • the openwork carrier has the ion-conducting layers both inside and on both surfaces, since there must be contact between the electrolyte and electrodes in the so-called MEA (membrane electrode assembly) in order to close the circuit in the fuel cell.
  • MEA membrane electrode assembly
  • the steel mesh described in WO 99/62620 as the preferred carrier to be used is absolutely unsuitable for fuel cell applications, since short circuits between the electrodes very easily occur during operation of the fuel cell.
  • the object of the present invention was therefore to provide flexible, inorganic proton-conducting membranes with a conductivity of at least 10 "3 S / cm and a process for their production.
  • nanoscale zirconium phosphates can be produced and can be produced using these thin flexible membranes which have a sufficiently large proton conductivity.
  • a new class of membranes for RFC and DMFC is now available.
  • the present invention therefore relates to a proton-conducting membrane according to claim 1, comprising a flat, flexible, provided with a plurality of openings Substrate with a coating located on and in this substrate, the material of the substrate being selected from woven or non-woven, non-electrically conductive fibers of glass or ceramic or a combination of such materials, which is characterized in that the coating comprises proton-conducting nanoscale particles of zirconium phosphate with a primary particle size smaller than 5000 nm and is impermeable to the reaction components in a fuel cell.
  • the present invention also relates to a method for producing a proton-conducting membrane according to at least one of Claims 1 to 15, in which a flat, flexible substrate provided with a multiplicity of openings is provided with a coating in and on this substrate, the material of the Substrate woven or non-woven, non-electrically conductive fibers of glass or ceramic or a combination of such materials, which is characterized in that by applying a suspension or a sol, or the at least nanoscale zirconium phosphate particles, on the substrate and through at least once heating, in which the suspension or the sol is solidified on and in the substrate, a proton-conductive coating is applied.
  • the present invention also relates to the use of a membrane according to at least one of claims 1 to 15 as a proton-exchanging membrane in fuel cells and to fuel cells which have a membrane according to at least one of claims 1 to 15.
  • the membranes according to the invention have the advantage over the membranes based on polymers that they can be used at higher temperatures, the water balance is not critical and there is no methanol crossover. Compared to the known ceramic proton-conducting membranes, the membranes according to the invention have the advantage that they can be manufactured much thinner and more flexibly.
  • 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.
  • a fuel cell such as. B. hydrogen, oxygen, air and / or methanol.
  • gas-tight or impermeable to the reaction components in the Understanding of the present invention understood 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 for methanol is significantly lower than with commercially available Nafion membranes, which are usually also as be called impermeable.
  • the membranes according to the invention show a significantly lower resistance to proton conduction than previously known ceramic membranes, the zirconium phosphates contain.
  • the proton-conducting membranes according to the invention comprise a planar, flexible substrate provided with a multiplicity of openings and having a coating on and in this substrate, the material of the substrate being selected from woven or non-woven, non-electrically conductive fibers of glass or ceramic or a combination Such materials and are characterized in that the coating has proton-conducting nanoscale particles of zirconium phosphate with a primary particle size less than 5 microns and gas-tight or impermeable to the reaction components in a fuel cell, such as. B. is hydrogen, oxygen, air and / or methanol.
  • the membranes according to the invention preferably have a thickness of less than 100 ⁇ m, preferably less than 50 ⁇ m and very particularly preferably less than 30 ⁇ m.
  • Membranes with a thickness of 10 to 50 ⁇ m have proven to be particularly suitable for the use of the membrane according to the invention in fuel cells, although thinner membranes can also be used if they have sufficient stability and gas tightness or tightness with respect to the reaction components in a fuel cell ,
  • the fabrics, fleeces, felts or flexible porous ceramic membranes used as the basis for infiltration with the zirconium phosphate naturally have a very high electrical resistance, since otherwise there would be a risk of a short circuit between the anode and cathode.
  • a membrane according to the invention with electrically insulating properties it preferably has non-electrically conductive fibers as the material for the substrate, selected from glass, aluminum oxide, SiO 2 , SiC, Si 3 N, BN, BN, A1N, Sialone or ZrO 2 on.
  • the material of the substrate can e.g. B. a fabric, fleece or felt made of non-electrically conductive fibers, the substrate also being provided with a porous ceramic coating fabric, fleece or felt made of non-electrically conductive fibers, such as. B. can be a microfiltration membrane.
  • the material of the substrate is very particularly preferably a nonwoven, fabric or felt made of fibers made of glass, which has no porous ceramic coating, since a higher conductivity can be achieved with materials without a porous coating, because the Porosity is significantly higher due to the lower dead volume and therefore more proton-conductive material per area of the membrane is available for proton conduction.
  • nonwovens has the advantage over fabrics that nonwovens again have a higher porosity than fabrics, but fabrics show a higher strength than nonwovens.
  • a woven fabric or a nonwoven made of glass fibers as the substrate in the membrane may be preferred.
  • all glass materials available as fibers such as. B. E, A, ECR, C, D, R, S and M glass can be used for support.
  • E, ECR or S glass fibers are preferably used.
  • the preferred types of glass have a low content of BaO, Na 2 O or K 2 O.
  • the preferred types of glass preferably have a BaO content of less than 5% by weight, very particularly preferably less than 1% by weight, a Na 2 O content of less than 5% by weight, very particularly preferably less than 1% by weight and a K 2 O content of less than 5% by weight, very particularly preferably less than 1% by weight. It may be advantageous if the fibers consist of types of glass which have none of the compounds BaO, Na 2 O or K 2 O, such as, for. B. E-glass, since such glass types are more resistant to chemical influences.
  • the fibers are the substrate with a thin film made of SiO 2 , ZrO, TiO 2 or Al 2 O 3 or with mixtures of these oxides are coated.
  • the oxidic coatings are particularly preferred for types of glass that have low acid stability, such as. B. E-glass.
  • the weight ratio of oxidic coating to glass in the carrier is preferably less than 15 to 85, more preferably less than 10 to 90 and very particularly preferably less than 5 to 95.
  • the membrane according to the invention has a glass fiber textile, such as. B. a glass fiber fabric, felt or nonwoven, these are preferably made of fibers with a maximum thickness of 20 tex (mg / m), preferably from fibers with a maximum thickness of 10 tex and very particularly preferably from fibers with a thickness of a maximum of 5.5 tex was produced.
  • the substrate very particularly preferably has a glass fiber fabric which was produced from fibers with a thickness of 5.5 or 11 tex.
  • the individual filaments of such fibers have z. B. a diameter of 5 to 7 microns.
  • the glass fiber fabric preferably used as support has from 5 to 30 weft threads / cm and from 5 to 30 warp threads / cm, preferably from 10 to 30 weft threads / cm and from 10 to 30 warp threads / cm and very particularly preferably from 15 to 25 weft threads / cm and from 15 to 25 warps / cm.
  • the coating of the membrane according to the invention preferably has nanoscale zirconium phosphate particles with a primary particle size of 1 to 1000 nm, preferably nanoscale zirconium phosphate particles with a primary particle size 1 to 100 nm and very particularly preferably nanoscale zirconium phosphate particles with a primary particle size 10 to 100 nm.
  • the coating according to the invention can also have agglomerates of zirconium phosphate primary particles with a size of 1 ⁇ m or more, preferably from 1 to 100 ⁇ m, particularly preferably from 1 to 25 ⁇ m.
  • the coating of the proton-conducting membrane has at least one oxide of the metals Al, Zr, Si or Ti in addition to the nanoscale zirconium phosphate particles.
  • These oxides can be in the coating as z. B. particles present by gluing, sintering or similar processes. This is particularly the case when a carrier provided with a ceramic coating is used to produce the proton-conducting membrane.
  • the oxides can also be present as isolated ceramic particles. This is particularly the case if the coating is produced by applying and solidifying oxide particles together with the zirconium phosphate primary particles as a sol or suspension on the carrier.
  • isolated oxide particles are present when the weight ratio of oxide to zirconium phosphate is significantly less than 1: 1.
  • the oxide particles preferably have a particle size of 5 ⁇ m or less, particularly preferably a particle size of 0.01 to 1 ⁇ m or 0.01 to 0.1 ⁇ m, it being possible for the particles to be primary particles or agglomerates.
  • the membranes according to the invention are distinguished by the fact that they have a conductivity greater than 1 mS / cm.
  • the membranes according to the invention preferably have a proton conductivity of 1 to 100 mS / cm and very particularly preferably of 1 to 10 mS / cm at room temperature and a relative humidity of 80 to 90%.
  • the membranes according to the invention can preferably be bent down to a radius of 250 m, preferably 10 cm and very particularly preferably 5 mm without damage.
  • the high conductivity and the good flexibility of the membranes according to the invention has the advantage that the membranes according to the invention can be used in fuel cells of almost any geometry.
  • the membranes are insoluble in water and methanol and show, e.g. B. compared to Nafion, only a very low permeability (practically no permeability) for methanol. These membranes are therefore preferably suitable for DMFCs.
  • the membranes according to the invention are preferably obtainable by a process for producing a proton-conducting membrane, in which a flat, flexible substrate provided with a multiplicity of openings is provided with a coating in and on this substrate, the material of the substrate being woven or non-woven, not electrically Has conductive fibers of glass or ceramic or a combination of such materials, which is characterized in that on the substrate by applying a suspension which has at least nanoscale zirconium phosphate particles to the substrate and by at least one heating, in which the suspension and is solidified in the substrate, a coating is applied.
  • 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 selected from glass, aluminum oxide, SiO 2 , SiC, Si 3 N, BN, B 4 N, A1N, sialone or ZrO 2 , in particular from high-temperature and / or acid-proof glass, quartz glass or ceramic
  • the material of the substrate can consist of non-electrically conductive fibers of the aforementioned materials as a fabric, fleece or felt.
  • a glass fiber fleece made of non-woven fibers made of glass is preferably used as the material of the substrate.
  • all glass materials available as fibers such as. B. E, A, ECR, C, D, R, S and M glass can be used for the substrate.
  • E or S glass fibers are preferably used.
  • the preferred types of glass have a low content of BaO, Na 2 O or K 2 O.
  • the preferred types of glass preferably have a BaO content of less than 5% by weight, particularly preferably less than 1% by weight, a Na 2 O content of less than 5% by weight, particularly preferably less than 1% by weight and one K 2 O content of less than 5% by weight, particularly preferably less than 1% by weight. It may be advantageous if the fibers consist of types of glass which have none of the compounds BaO, Na 2 O or K 2 O, such as, for. B. E-glass, since such types of glass are more resistant to chemicals.
  • the fibers, particularly preferably glass fibers made of E or S glass, of the substrate are coated with a thin film made of SiO 2 .
  • a coating can e.g. B. be applied in that tetraethyl orthosilicate (TEOS) is applied to the fibers, individually or in the form of fabric, felt or fleece, the TEOS is dried and then at a temperature of 400 to 600 ° C, preferably at 420 to 500 ° C and most preferably at 440 to 460 ° C the TEOS is burned off. When it burns, silicon dioxide remains as a residue on the fiber surface.
  • TEOS tetraethyl orthosilicate
  • a glass fiber textile such as. B. a glass fiber fabric, felt or nonwoven
  • those are preferably used, which consist of fibers with a maximum thickness of 20 tex (mg / m), preferably from fibers with a maximum thickness of 10 tex and very particularly preferably with fibers a maximum thickness of 5.5 tex were produced.
  • the individual filaments of such fibers have z. B. a diameter of 5 to 7 microns.
  • the glass fiber fabric preferably used as a substrate has from 5 to 30 weft threads / cm and from 5 to 30 warp threads / cm, preferably from 10 to 30 weft threads / cm and from 10 to 30 warp threads / cm and very particularly preferably from 15 to 25 weft threads / cm and from 15 to 25 warps / cm.
  • the use of such glass fabrics can ensure that the membrane according to the invention has a sufficiently high strength and at the same time a sufficiently large porosity of the substrate.
  • glass fiber textiles in particular glass fiber nonwovens, glass fiber felts or glass fiber fabrics
  • the size is usually removed by heating the glass fiber textile, in particular glass fiber fabric, to up to 500 ° C. for 1 to 2 minutes and then subjecting the textile to thermal treatment at up to 300 ° C. for approx. 4 days.
  • a glass fiber textile treated in this way is considerably more brittle than glass fiber textile which still has the size.
  • the coating according to the invention is difficult to apply to and into a glass fiber textile as the substrate, which has the size, since the coating adheres poorly to the textile due to the size. It has surprisingly been found that burning off the size at temperatures below 500 ° C., preferably below 450 ° C. within 2 minutes, preferably within 1 minute, and a subsequent treatment with TEOS as described above, is sufficient to achieve a better durability To ensure coating of the glass fiber textile, in particular the glass fiber fabric.
  • a glass fiber textile provided with a porous ceramic coating is used as the material of the substrate.
  • Such glass fiber textiles coated with ceramic are known from WO 99/15262.
  • the ceramic coating is preferably applied to the glass fiber textile by applying a suspension which has at least one inorganic component and at least one, a compound of at least one metal, a semi-metal or a mixed metal with at least one element from the 3rd to 7th main group and a sol to which Glass fiber textile and by at least one heating, in which the suspension having at least one inorganic component is solidified on or in or else on and in the glass fiber textile.
  • the method for producing glass fiber textiles coated with ceramic is also known from WO 99/15262.
  • the suspension used to produce the coating has at least nanoscale zirconium phosphate particles with a particle size of less than 1 ⁇ m.
  • the suspension for producing the coating of the membrane according to the invention preferably has nanoscale zirconium phosphate particles with a primary particle size of 1 to 1000 nm, preferably nanoscale zirconium phosphate particles with a primary particle size 1 to 100 nm and very particularly preferably nanoscale zirconium phosphate particles with a primary particle size 10 to 100 nm on.
  • the coating according to the invention can also have agglomerates of zirconium phosphate particles with a size of 1 ⁇ m or more, preferably from 1 to 100 ⁇ m, particularly preferably from 1 to 25 ⁇ m.
  • the nanoscale zirconium phosphate particles are preferably produced in an upstream step.
  • all process paths that are suitable for the production of nanoscale powders such as B. gas phase process (analogous to Aerosil production, wire explosion process, microwave plasma process, etc.) but also liquid phase process.
  • the nanoscale zirconium phosphate particles are used to produce the suspension by shooting a solution of a soluble zirconium compound at each other and a solution which contains phosphorus-containing compounds in a microjet reactor.
  • the soluble zirconium compound used can be selected from zirconium nitrate, zirconium chloride, zirconium acetate, zirconium acetylacetonate or a zirconium alcoholate.
  • the solution used which contains phosphorus-containing compounds preferably has at least one compound selected Phosphoric acid and / or phosphate salts, in particular phosphate salts of the alkali metals, such as Na 3 PO, Na 2 HPO or NaH 2 PO.
  • water can serve as the solvent. If starting materials sensitive to hydrolysis, such as zirconium alcoholates, are used, then alcohols or other anhydrous solvents can also be used.
  • the solutions are implemented in the microjet reactor in a special high-pressure process for zirconium phosphate, in which the two are in a microjet reactor Solutions are shot at each other as a thin jet under very high pressure of up to a few hundred bar via nozzles of preferably 50 to 500 ⁇ m in diameter.
  • the reaction products can e.g. B. removed from the reactor by an air stream.
  • the primary particle and possibly also agglomerate size can be set in a targeted manner by the test conditions with which the microjet reactor is operated.
  • a colloidal suspension containing the zirconium phosphate is obtained directly by means of this method. Typical zirconium phosphate concentrations in this suspension are 0.01-50% by weight, and preferably 0.1-5% by weight. If necessary, the suspensions can also be further concentrated by evaporating the solvent used.
  • the zirconium phosphate particles mentioned can also be produced by converting the zirconium phosphate suspensions obtained from the microjet reactor into a powder which has nanoscale zirconium phosphate particles by spray drying. Spray drying can be carried out in a known manner and is preferably carried out at a temperature of 100 to 200 ° C, preferably at a temperature of 100 to 150 ° C.
  • other partially commercially available materials such as metal oxides, nitride carbides or zirconium phosphate particles, can also be added to the suspension in powder form. At least one oxide of the elements Al, Zr, Ti or Si is preferably added to the suspension.
  • the addition of metal oxides or other inorganic components has the advantage that the proton conductivity can be set to the desired value and an optimal infiltration of the substrate can be achieved, so that in the end a proton-conducting or gas-tight membrane for the reaction components in the fuel cell is formed.
  • At least one inorganic component which has a grain size of less than 5 ⁇ m, preferably from 10 to 1000 nm, and very particularly preferably from 100 to 1000 nm, is added to the suspension.
  • the suspension can other proton-conductive materials, such as iso- and heteropolyacids, or other nanoscale powders from the series Al 2 O 3 , ZrO 2 TiO 2 and SiO 2 are also added .
  • the suspension can also contain Bronsted acids or immobilizable silylic acids.
  • the suspension used which has nanoscale zirconium phosphate particles, can have at least one sol, at least one semimetal oxide sol or at least one mixed metal oxide sol or a mixture of these sols.
  • the brines 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 with at least one liquid, a solid or a gas.
  • B water, alcohol or an acid, as a solid ice or as a gas steam or at least a combination of these liquids, solids or gases. 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 is preferably at least one metal nitrate, a metal chloride, a metal carbonate, a metal alcoholate compound or at least one semimetal alcoholate compound, particularly preferably at least one metal alcoholate compound, a metal nitrate, a metal chloride, a metal carbonate or at least one semimetal alcoholate compound selected from the compounds of the elements Zr, AI , Si, or Ti, such as. B. zirconium alcoholates such. B. zirconium isopropylate, silicon alcoholates, or a metal nitrate, such as. B. zirconium nitrate hydrolyzed.
  • 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 are treated.
  • 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 are treated.
  • brine can be used, which were produced as described above, but also commercially available brine, such as. B. zirconium nitrate sol or silica sol.
  • the coating according to the invention is applied by solidifying the suspension in and on the substrate.
  • the suspension is applied to the carrier material by knife coating, rolling, spraying or similar processes. This is preferably done in a continuous process.
  • the suspension present on and in the substrate can be solidified by heating to 50 to 500 ° C.
  • the suspension present on and in the support is solidified by heating to 100 to 450 ° C., preferably by heating to 150 to 400 ° C. and very particularly preferably by heating to 150 to 300 ° C. It can be advantageous if the heating is carried out for 1 second to 15 minutes, preferably for 10 seconds to 5 minutes.
  • the application / infiltration can be carried out once or several times, a thermal treatment preferably taking place between the application steps, preferably at a temperature of 50 to 500 and preferably 150 to 300 ° C. for 1 minute to 1 hour. If pure fabrics or nonwovens are used, repeated coating is preferred.
  • the membranes according to the invention represent a new class of proton-conducting membranes. These membranes can be used as a proton-exchanging membrane in fuel cells or in membrane electrode assemblies (MEA). In this way, fuel cells are available which have a membrane according to the invention as a proton-exchanging membrane.
  • MEA membrane electrode assemblies
  • the flexible membrane electrode unit for a fuel cell comprises an anode layer and a cathode layer, each on opposite sides of a proton-conducting membrane (electrolyte membrane) according to the invention, comprising a flat, provided with a plurality of openings, flexible substrate with a substrate located on and in this substrate Coating, the material of the substrate being selected from woven or non-woven, non-electrically conductive fibers of glass or ceramic or a combination of such materials and a coating which has proton-conducting nanoscale particles of zirconium phosphate with a primary particle size of less than 5 ⁇ m and is gas-tight or impermeable to the Reaction components in a fuel cell, such as.
  • B. is hydrogen, oxygen, air and / or methanol, are provided and wherein the anode layer and the cathode layer are porous and each comprise a catalyst for the anode and cathode reaction, a proton-conductive component and optionally a catalyst support.
  • the proton-conductive component of the anode and / or cathode layer 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
  • 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 or
  • 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 stand for 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.
  • 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 tetraethylorthosilicate
  • TMOS tetramethylorthosilicate
  • the proton-conductive 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. Pure hydrogen or a hydrogen produced by means of a reformer can be used as fuel. In a preferred embodiment, however, methanol is used. For this purpose, a liquid or gaseous mixture of water and methanol, preferably 0.5-5% methanol, is used on the anode side.
  • the membrane electrode assembly according to the invention is furthermore preferably flexible and preferably tolerates a bending radius of down to 5000 mm, preferably 100 mm, in particular down to 50 mm and particularly preferably down to 20 mm.
  • the membrane electrode unit according to the invention very particularly preferably tolerates a bending radius of down to 5 mm.
  • the catalyst can be the same on the anode and cathode side, but in the preferred embodiment it is different.
  • the catalyst carrier is electrically conductive in the anode layer and in the cathode layer.
  • an electrolyte membrane is coated with the 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 this case, the electrically conductive catalyst directly takes the electrons away from the membrane. electrode unit.
  • the method according to the invention for producing a membrane electrode unit according to the invention comprises the following steps: (A) Provision of an electrolyte membrane according to the invention, which is impermeable to the reaction components of the fuel cell reaction, for an electrolyte membrane
  • (B) Providing in each case an agent for producing an anode layer and a cathode layer, the agent in each case comprising: (B1) a condensable component which imparts proton conductivity after the condensation of the electrode layer, (B2) a catalyst which the anode reaction or the cathode reaction catalyzed, or a precursor compound of the catalyst, (B3) optionally a catalyst support and (B4) optionally a pore former,
  • Cathode layer can take place simultaneously or in succession.
  • the application of the agent in step (C) can, for. B. by printing, printing,
  • the agent according to step (B) for producing an anode layer or a cathode layer is preferably a suspension which is obtainable from
  • 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
  • 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 2 O 3 , ZrO 2 , TiO 2 or SiO 2 powder, H4) dispersing the catalyst and optionally the carrier and pore former.
  • a nanocrystalline proton-conducting metal oxide preferably Al 2 O 3 , ZrO 2 , TiO 2 or SiO 2 powder
  • 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 100 to 800 ° C, preferably 150 to 500 ° C, most preferably 180 to 250 ° C is heated.
  • the method according to the invention can also include the steps:
  • 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,
  • an open-pore gas diffusion electrode preferably an open-pore carbon paper, is pressed onto the catalyst or glued to the catalyst with an electrically conductive adhesive.
  • 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 20 to 500 ° C, preferably from 50 to 300 ° C and very particularly preferably at an elevated temperature of 100 to 200 ° C between the 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 heated to a temperature of 20 to 500 ° C., preferably 50 to 300 ° C., very particularly preferably 100 to 200 ° C.
  • 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 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, 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 may contain an acid or its salt, which is the result of a chemical reaction in the course of a solidification process after
  • this acid can e.g. B. simple Bronsted acid, such as sulfuric or phosphoric acid, or a silylsulfonic or silylphosphonic acid.
  • 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 coating 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 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 which comprises the following components: (T1) a condensable component which, after the condensation of an anode layer or a cathode layer of a membrane electrode assembly, gives proton conductivity to a fuel cell, (T2) a catalyst which controls the anode reaction or the Catalyzed cathode reaction in a fuel cell, or a precursor compound of the catalyst,
  • T3 optionally a catalyst support (T4) optionally a pore former
  • T5 optionally additives to improve foam behavior, viscosity and adhesion.
  • the condensable component which after the condensation gives the anode layer or the cathode layer proton conductivity, is preferably selected from (I) hydrolyzable compounds of phosphorus and / or hydrolyzable nitrates, oxynitrates, chlorides, oxychlorides, carbonates, alcoholates, acetates, acetylacetonates of a metal or semimetal , preferably
  • 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 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 comprises carbon black, metal powder, metal oxide powder, carbon or carbon.
  • a prefabricated gas distributor which contains the gas diffusion electrode, consisting of 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. For this it is necessary that the membrane or gas distributor have thermoplastic properties at the pressing temperature.
  • the gas distributor can also be fixed on the membrane with an adhesive. This adhesive must have ion-conducting properties and can in principle consist of the material classes already mentioned.
  • 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 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 be used.
  • 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.
  • the mobile or stationary systems are preferably vehicles or house energy systems.
  • Aqueous solutions of phosphoric acid (0.2M) and zirconium nitrate (0.05M) were shot through 100 ⁇ m nozzles at a pressure of 60 bar in a microjet reactor according to WO 00/61275.
  • the product obtained is opaque / milky-cloudy.
  • the particle size distribution shows a distribution comparable to that of Example 1.
  • the suspension can be further concentrated by spinning off water and becomes sol-like / viscous, but remains milky / opaque. This sol or suspension is long-term stable.
  • Aerosil 200 (Degussa AG) are added to the suspension from Example 1. This suspension is then homogenized again for 24 h using a magnetic stirrer.
  • Example 1 50 g of the suspension from Example 1 are mixed with 5 g of Al 2 O 3 and 0.23 g of TODS (2- [2- (2-methoxyethoxy) ethoxy] acetic acid).
  • An S2 glass fabric is coated with this slip in a continuous process and dried at 150 to 200 ° C. within 5 minutes.
  • the membrane has an unexpectedly high conductivity of 0.2 mS / cm and is flexible.
  • a glass fabric was coated directly with the suspension from Example 1 in a continuous process.
  • the suspension was knife-coated onto an S2 glass fabric (CS interglass) and solidified at a temperature of 160 ° C. within 10 minutes.
  • the membrane obtained shows a good conductivity of approximately 1 mS / cm.
  • the membrane shows a similarly good flexibility as the original fabric.
  • a glass fabric is coated directly with a doctor knife using the suspension from Example 2.
  • the membrane is then solidified in a chamber furnace at 300 ° C. for 15 minutes.
  • the then water-insoluble membrane has a conductivity of approx. 2 mS / cm at 92% relative humidity (RH) and 23 ° C. Due to the resistance in water and methanol, this membrane is very suitable for the DMFC.
  • Example 7 An S-glass fabric with a thickness of 70 ⁇ m is infiltrated with the suspension from Example 1 by a doctoring process five times. Between the infiltration steps, the tissue is pre-consolidated with a hot air blower at approx. 150 ° C. After the last one Coating, in which the last small pores are filled, the membrane is finally solidified by hot air at 300 ° C for 15 minutes.
  • This membrane stable in water and methanol, has a conductivity of approx. 4 mS / cm at 80% relative air humidity and can be used in a DMFC.
  • An S-glass fabric with a thickness of 70 ⁇ m is infiltrated with the suspension from Example 3 by a doctoring process three times. Between the infiltration steps, the tissue is pre-consolidated with a hot air blower at approx. 150 ° C. After the last coating, in which the last small pores are filled, the membrane is finally solidified by hot air at 300 ° C for 15 minutes.
  • This membrane stable in water and methanol, has a conductivity of approx. 1 mS / cm at 80% relative air humidity and can be used in a DMFC.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

L'invention concerne des membranes céramiques conductrices de protons, à base de phosphates de zirconium, des procédés de fabrication associés et l'utilisation de ces membranes dans des piles à combustible et dans des assemblages membrane-électrode. Les membranes céramiques selon l'invention constituent une nouvelle catégorie de membranes conductrices de protons. Pour les réaliser, on produit tout d'abord du phosphate de zirconium à l'échelle nanométrique selon un procédé spécial dans un réacteur à microjet. Ce matériau est alors placé sous forme de suspension sur un support souple, puis il est compacté. On obtient ainsi une membrane conductrice de cations/protons, imperméable et souple, pouvant être aisément utilisée dans une pile à combustible.
PCT/EP2003/000163 2002-02-13 2003-01-10 Membranes ceramiques conductrices de protons a base de phosphates de zirconium, procedes de realisation associes et utilisation de ces membranes dans des assemblages membrane-electrode et dans des piles a combustible WO2003069712A2 (fr)

Priority Applications (1)

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AU2003244864A AU2003244864A1 (en) 2002-02-13 2003-01-10 Proton-conducting ceramic membranes on the basis of zirconium phosphates, method for the production thereof, and use thereof in meas and fuel cells

Applications Claiming Priority (2)

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DE10205849A DE10205849A1 (de) 2002-02-13 2002-02-13 Protonenleitende Keramikmembranen auf der Basis von Zirkoniumphosphaten, Verfahren zu deren Herstellung und die Verwendung derselben in MEAs und Brennstoffzellen
DE10205849.0 2002-02-13

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103825031A (zh) * 2014-03-18 2014-05-28 哈尔滨工业大学 一种醇类燃料电池的自呼吸式阴极结构
US9023553B2 (en) 2007-09-04 2015-05-05 Chemsultants International, Inc. Multilayered composite proton exchange membrane and a process for manufacturing the same

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2871792B1 (fr) * 2004-06-22 2007-02-09 Rhodia Chimie Sa Phosphate de zirconium cristallise a haut facteur de forme, son procede de preparation et son utilisation dans un materiau macromoleculaire
DE102007011424A1 (de) 2007-03-08 2008-09-11 Lanxess Deutschland Gmbh Polymerelektrolytmembran mit funktionalisierten Nanopartikeln
DE102008002457A1 (de) 2008-06-16 2009-12-17 Elcomax Membranes Gmbh Verwendung eines protonenleitfähigkeitverleihenden Materials bei der Herstellung von Brennstoffzellen
DE102010029502A1 (de) * 2010-05-31 2011-12-01 Deutsches Zentrum für Luft- und Raumfahrt e.V. Elektrochemische Funktionsstruktur und Verfahren zur Herstellung
CN104681833B (zh) * 2015-02-05 2017-02-22 成都新柯力化工科技有限公司 一种纳米陶瓷纤维管燃料电池质子交换膜及制备方法
DE102017109815B3 (de) * 2017-05-08 2018-10-25 Michael Steidle Textiles Gebilde

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EP0838258A1 (fr) * 1996-10-21 1998-04-29 "VLAAMSE INSTELLING VOOR TECHNOLOGISCH ONDERZOEK", afgekort "V.I.T.O." membrane conductrice de protons
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
WO2000023510A1 (fr) * 1998-10-16 2000-04-27 Johnson Matthey Public Limited Company Substrat
US6059943A (en) * 1997-07-30 2000-05-09 Lynntech, Inc. Composite membrane suitable for use in electrochemical devices

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EP0838258A1 (fr) * 1996-10-21 1998-04-29 "VLAAMSE INSTELLING VOOR TECHNOLOGISCH ONDERZOEK", afgekort "V.I.T.O." membrane conductrice de protons
US6059943A (en) * 1997-07-30 2000-05-09 Lynntech, Inc. Composite membrane suitable for use in electrochemical devices
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
WO2000023510A1 (fr) * 1998-10-16 2000-04-27 Johnson Matthey Public Limited Company Substrat

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9023553B2 (en) 2007-09-04 2015-05-05 Chemsultants International, Inc. Multilayered composite proton exchange membrane and a process for manufacturing the same
CN103825031A (zh) * 2014-03-18 2014-05-28 哈尔滨工业大学 一种醇类燃料电池的自呼吸式阴极结构

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TW200416067A (en) 2004-09-01
WO2003069712A3 (fr) 2004-07-01
AU2003244864A8 (en) 2003-09-04
DE10205849A1 (de) 2003-08-21
AU2003244864A1 (en) 2003-09-04

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