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WO2011020872A1 - Membrane à polyélectrolyte pour piles à combustible ht, et son procédé de production - Google Patents

Membrane à polyélectrolyte pour piles à combustible ht, et son procédé de production Download PDF

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Publication number
WO2011020872A1
WO2011020872A1 PCT/EP2010/062090 EP2010062090W WO2011020872A1 WO 2011020872 A1 WO2011020872 A1 WO 2011020872A1 EP 2010062090 W EP2010062090 W EP 2010062090W WO 2011020872 A1 WO2011020872 A1 WO 2011020872A1
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WIPO (PCT)
Prior art keywords
polymer
acid
heteroaromatic
electrolyte membrane
membrane
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Ceased
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PCT/EP2010/062090
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German (de)
English (en)
Inventor
Rouven Scheffler
Mirko Herrmann
Ulrich MÄHR
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Volkswagen AG
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Volkswagen AG
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Publication of WO2011020872A1 publication Critical patent/WO2011020872A1/fr
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. in situ polymerisation or in situ crosslinking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to a polymer electrolyte membrane with improved long-term stability for fuel cells, to a process for the production thereof and to a fuel cell having such a polymer electrolyte membrane.
  • MEA membrane-electrode unit
  • the fuel cell is formed by a multiplicity of stacked MEAs whose electrical powers add up.
  • a fuel in particular hydrogen H 2 or a hydrogen-containing gas mixture
  • an electrochemical oxidation of H 2 to H + takes place with emission of electrons.
  • the membrane which separates the reaction spaces gas-tight from each other and electrically isolated, takes place (water-bound or anhydrous) transport of protons H + from the anode compartment in the cathode compartment.
  • the electrons provided at the anode are supplied to the cathode via an electrical line.
  • the cathode is supplied with oxygen or an oxygen-containing gas mixture, so that a reduction of O 2 to O 2 " takes place with the electrons being taken in.
  • these oxygen ions in the cathode space are in charge with the protons transported through the membrane with the formation of water From chemical to electrical energy, fuel cells achieve improved efficiency over other electricity generators due to the Carnot factor bypass.
  • PEMs polymer electrolyte membranes
  • the membrane itself consists of a polymer electrolyte.
  • acid-modified polymers in particular perfluorinated polymers are often used.
  • the most common representative of this class of polymer electrolytes is a membrane of a sulfonated polytetrafluoroethylene copolymer (Handset name: Nafton, copolymer of tetrafluoroethylene and a sulfonyl acid fluoride derivative of a perfluoroalkyl vinyl ether).
  • Handset name Nafton, copolymer of tetrafluoroethylene and a sulfonyl acid fluoride derivative of a perfluoroalkyl vinyl ether.
  • the viscosity of the electrolytic substances decreases with increasing temperature and improves the mass transfer to the reactive centers of the electrodes.
  • the resulting product water is gaseous and can better be removed from the reaction zone, so that in the gas diffusion layer existing gas transport paths ⁇ pores and meshes) are kept free and also a washing out of the electrolytes and electrolyte additives is prevented.
  • high-temperature polymer electrolyte membrane fuel cells H-PEM bre ⁇ nstoffze! Len have been developed, which operate at operating temperatures of 120 to 180 0 C and require little or no humidification.
  • the electro-lytic conductivity of the membranes used here is based on liquid electrolytes bound by electrostatic complex bonding to the polymer backbone, in particular acids or bases, which ensure proton conductivity even when the membrane is completely dry above the boiling point of water.
  • the most promising approach involves the use of acid-doped basic N-heterocyclic polymers, in particular polyazoles, where the proton conduction is based on an acid bound as a complex in the polymer.
  • the solution of the polyazole (or its in situ polymerization) is carried out in solvents such as t, N-dimethylacetamide, which can subsequently be removed from the membrane only at high temperatures and complicated washing processes.
  • the impregnation of the membrane with acid for example phosphoric acid
  • the swelling process of the polybenzimidazole membrane with phosphoric acid alters the mechanical properties of the material such that continuous processing with constant web tension and control is not possible.
  • 7,235,320 B2 describes a process for producing a polyazole-containing polymer electrolyte membrane in which by polymerization of a suitable monomer in the melt, a prepolymer is produced, this is dissolved in polyphosphoric acid and the polymerization is carried out by heating the solution to temperatures up to 300 0 C under inert gas. After conversion of the mixture into a flat membrane shape, the formation of a self-supporting membrane by exposure to atmospheric moisture or water vapor at optionally elevated temperatures, taking place over a period of up to 200 hours for the hydrolysis of phosphoric acid and thus to a sol-gel conversion and solidification of the membrane comes.
  • the high viscosity of the polymer solution which results from the use of polyphosphoric acid as solvent is a disadvantage of the processes described above. For this reason, in the membrane production at temperatures of about 150 ° C must be worked to make the polymer solution processable. However, these high process temperatures make the process expensive and expensive. Another disadvantage is seen in the long necessary treatment of the membrane with moisture to hydrolyze the polyphosphoric acid, whereby the self-supporting membrane is obtained. This process takes up to a few days, which is why only a very small space-time yield can be achieved. In addition, since phosphoric acid can not be selected as the solvent, additives can not be added to the polymer solution by which further improvements in conductivity and mechanical properties of the polymer electrolyte membrane could be achieved.
  • a common problem of acid-doped polymer electrolyte membranes is their low long-term stability, which is caused by washing out of the complexed electrolyte in fuel line operation, also due to the product water produced. The result is an irreversibly decreasing power of the fuel cell.
  • the membrane should furthermore be producible with the simplest and most cost-effective process whose process parameters, such as solvent, viscosity of the polymer solution and the associated process temperature, should be freely selectable within wide limits.
  • the polymer electrolyte membrane according to the invention for fuel cells comprises
  • the components of the electrolyte mixture i.e., the polyphosphoric acid or its hydrolysis products and the at least one further acid
  • the components of the electrolyte mixture are hydrogen bonded to the heteroaromatic nitrogen atoms of the at least one N-heteroaromatic polymer (complexed).
  • the chemical crosslinking of the polymer chains with an organic compound having at least two epoxide groups is significantly increased over the mere N-heteroaromatic polymer.
  • the storage time stability of a fuel cell with the polymer electrolyte membrane according to the invention is several hundred hours. This phenomenon can probably be explained by the fact that a chemical covalent crosslinking of the secondary aromatic amine function of the repeat units of the N-heteroaromatic polymer increases the stability against solution reactions or interactions with the electrolyte components.
  • This chemical crosslinking leads to improved mechanical properties of the polymer electrolyte membranes and to a higher chemical stability.
  • the polymer membrane must be stable against interactions or solution reactions of the electrolyte components with the polymer.
  • suitable crosslinkers are all organic compounds which have two or more epoxide functional groups in the molecule which react with the amine functions of the
  • Suitable derivatives include all compounds having the molecular skeleton according to formula 1 which carry substituents at one or more positions, in particular low molecular weight C 1 - to C 5 -alkyl, C 1 - to C 8 -alkenyl, C 1 - to C 5 -alkoxy, C1 to C5 alkenoxy groups, homo- or heteroaromatic C5 to C12 aryl groups, epoxide groups, amino, phosphonic, phosphonate, sulfonic acid, sulfonate and hydroxy groups.
  • polyphosphate phoric acid generally contains water, which is in a dynamic equilibrium between bound and free form (2 H 3 PO 4 ⁇ H> P 2 O 5 3H 2 O).
  • concentration of commercial polyphosphoric acid is usually specified with a content of at least 83 wt .-% of P 2 O 5 , ie it contains up to 17 wt .-% mathematically more or less bound H 2 O.
  • the at least one further acid Contain water for example, concentrated ortho-phosphoric acid usually contains about 15% by weight H 2 O.
  • the polymer electrolyte membrane can be calculated up to 25% by weight H 2 O 1, in particular up to 20% by weight H 2 O, in typical examples contain about 15 wt .-% H 2 O.
  • no water is added as such to the solution used for its preparation (see below), ie any water present originates exclusively from unavoidable water components of the components, in particular of the electrolyte mixture.
  • the polymer component contains 90 to 99.999% by weight of the at least one N-heteroaromatic polymer and 0.001 to 10% by weight of the crosslinker (organic diepoxide compound), in particular 95 to 99.99% by weight of the N-heteroaromatic Polymer and 0.01 to 5 wt .-% of the crosslinking agent, preferably about 99.965 wt .-% of the N-heteroaromatic polymer and about 0.035 wt .-% of the crosslinking agent.
  • the crosslinker organic diepoxide compound
  • the polymer electrolyte membrane contains 1 to 50 wt .-% of the polymer component (a) and 99 to 50 wt .-% of the electrolyte mixture (b), in particular 1 to 20 wt .-% of the polymer component and 99 to 80 wt .-% of the electrolyte mixture, preferably about 2 to 8 wt .-% of the polymer component and 98 to 92 wt .-% of Elektroiytgemischs, each based on the total mass of Poiymerelektrolytmembran, that is on the sum of polymer component and electrolyte mixture.
  • a proportion of about 4-5 wt .-% of the polymer component and about 96-95 wt .-% of the electrolyte mixture has been proven.
  • the at least one N-heteroaromatic polymer is selected according to an advantageous embodiment of the invention from the group of polyazoles and polyphosphazenes.
  • Particularly suitable representatives of this class of polymers are polybenzimidazoles, polypyridines, poly-pyrimidines, polyimidazoles, polybenzothiazoles, polybenzoxazoles, polyoxadiazoles, polyquinoxalines, polythiadiazoles, poly (tetrazapyrene), polyvinylpyridines and polyvinylimidazoles. All of these polymers are distinguished by their suitability, a large one To bind the amount of acid, in particular by hydrogen bonding to the nitrogen atoms present in the polymer chain stably.
  • the at least one N-heteroaromatic polymer comprises poly (2,5-benzimidazole) (ABPBi) according to formula (2) or a derivative thereof, optionally containing one or more further N-heteroaromatic polymers ,
  • Suitable derivatives of ABPBI include, for example, suifonic acid, sulfoate, phosphonic acid or phosphonate derivatives, which groups may be attached at any position on the benzene ring. These functional groups in particular improve the proton conductivity achieved. Preferably, these groups may be introduced by subsequent modification of the ABPBI, such as by sulfonation.
  • the ABPBI has an inherent viscosity of at least 2.2 dl / g, preferably at least 2.5 dl / g, measured in a 1 wt% ABPBI solution in 85 wt% H 3 PO 4 at 25 ° C.
  • the molecular weights of the polymer on which such a viscosity is based ensure optimum membrane-forming behavior and good mechanical properties of the membrane.
  • the ABPBI is used without a further N-heteroaromatic polymer.
  • a polymer mixture which, in addition to ABPBI, comprises at least one further N-heteroaromatic polymer, in particular from the abovementioned group of polyazoiene and polyphosphazenes.
  • Poly [2,2 '- (m-phenyl) -5,5'-benzimidazole] (PBI) according to Formal (3) is preferably used here, which increases the stability of the membrane to acids and even more stable operation of the high-temperature fuel cell guaranteed.
  • a mixture of two N-heteroaromatic polymers of 40 to 95 wt .-% ABPBI and 60 to 5 wt .-% of the other N-heteroaromatic polymer, in particular PBI can be used.
  • the polymer mixture contains 60 to 85 wt .-% ABPBI and 40 to 15 wt .-% of the other polymer, in particular PBI.
  • Preference is given to a mixture of about 75% by weight of ABPBI and 25% by weight of the other polymer, in particular PBI.
  • the additional acid present in the electrolyte mixture can in principle be an inorganic or organic acid, in particular phosphoric acid, phosphonic acid, phosphinic acid, sulfuric acid, sulfonic acid, perchloric acid, nitric acid, hydrochloric acid, formic acid, acetic acid, trifluoroacetic acid, a (per) halogenated alkyl- or arylsulfonic acid or (per ) halogenated alkyl or Arylphospho ⁇ kla, preferably phosphoric acid.
  • phosphoric acid, sulfuric acid, sulfonic acid, phosphonic acid and perchloric acid is preferred, in particular of phosphoric acid.
  • Another aspect of the present invention relates to an innovative process for the preparation of the polymer electrolyte membrane according to the invention with the steps:
  • an electrolyte mixture comprising polyphosphoric acid and at least one further acid
  • the electrolyte mixture which also acts as a solvent, of polyphosphoric acid and at least one other acid.
  • a further acid namely the viscosity of the solution can be adjusted within a wide range.
  • the viscosity of the solution compared to the exclusive use of polyphosphoric acid can be reduced so far that the transfer of the Polymeriösung in a flat membranegesta ⁇ t by simple and inexpensive standard methods, such as casting, spraying, doctoring can be done, in particular by doctoring (drawing method) even here relatively low temperatures are sufficient.
  • the preparation by the drawing process at temperatures of at most 100 ° C, in particular at a maximum of 80 ° C, preferably by about 60 0 C. Even by these comparatively low processing temperatures, the energy balance of the production is improved and reduces the technical complexity.
  • the at least one N-heteroaromatic polymer is preferably selected from the group of polyazoles and polyphosphazenes mentioned in connection with the polymer electrolyte membrane according to the invention and comprises in particular ABPB1 or a mixture of ABPBI and another N-heteroaromatic polymer, in particular PB1.
  • the weight ratios correspond to the above-mentioned areas.
  • the electrolyte mixture in the case of using a single N-heteroaromatic polymer, in particular ABPBI shares of 5 to 40 wt .-% Poiyphosphorklare H n + 2 P n O 3n + I (n> 1) according to formula 4 and 95 to 60 wt .-% of the further acid, in particular 10 to 30 wt .-% Poiyphosphorklare and 90 to 70 wt .-% of the further acid.
  • the Eiektrolytgemisch contains about 15 wt .-% Poiyphosphorklare and about 85 wt .-% of the further acid.
  • an electrolyte mixture from 30 to 70% by weight of polyphosphoric acid H n + 2 P n O 3n + I (n> 1) according to formula 4 and 70 to 30% by weight of the further acid, in particular from 40 to 60% by weight of polyphosphoric acid and 60 to 40 wt .-% of the further acid used, wherein according to a particularly preferred embodiment, a mixture of each 50 wt .-% polyphosphoric acid and 50 wt .-% of the further acid is preferred.
  • the acid used in the electrolyte mixture is preferably selected from the abovementioned acids, the use of phosphoric acid, sulfuric acid, sulfonic acid, phosphonic acid and perchloric acid, but in particular of phosphoric acid is preferred.
  • an acid as a solvent for the polymer allows the addition of additives which improve the material properties of the polymer electrolyte membrane to be generated, such as proton conductivity and mechanics.
  • additives include sulfonic, phosphinic, phosphonic, phosphoric and phosphoric acid esters having different non-long, partially fluorinated or perfluorinated alkyl or aryl radicals.
  • acids such as sulfuric acid, trifluoroacetic acid, methanesulfonic acid, acetic acid, formic acid, nitric acid and mixtures thereof.
  • heteropolyacids hexafluoroglutaric acid (HFGA), squarric acid (SA). It may also be helpful to add salts of the corresponding acids to phosphoric acid, as described, for example, in DE 102 46 459 A1.
  • perfluorosulfonimides and, for example, nitrogen-containing heterocycles such as imidazole or triazole and derivatives thereof and polysiloxanes, or else ionic liquids such as, for example, 1-butyl-3-methylimidazolium trifluoromethanesulfonate.
  • ionic liquids such as, for example, 1-butyl-3-methylimidazolium trifluoromethanesulfonate.
  • additives include surface-active substances, for example ZONYL from DuPont (see US Pat. No.
  • the precipitation of the polymer can be carried out, for example, by immersing the polymer solution brought into the planar membrane shape in a water bath or by pouring or spraying the polymer solution with water.
  • the contacting of the membrane with the Ver ⁇ etzer by spraying at least one side is at least one precipitated Polymeriektrolytrnembran with a particular aqueous solution of the organic diepoxide compound.
  • the sprayed polymer electrolyte membrane can be combined with another (sprayed or unsprayed) polymer electrolyte membrane, with the sprayed surface (s) abutting each other.
  • the networkability ung may be initiated thermally, in particular at temperatures in the range of 50 to 150 0 C. This can be done before their shoring or during the "retraction" of the membrane-Eiektroden unit in the fuel cell operation by heating the membrane.
  • the membrane produced by the process according to the invention is preferably made up and installed in a membrane-electrode assembly.
  • Another aspect of the present invention relates to a fuel cell, which has at least one, in particular a plurality of individual cells each having a membrane-electrode unit with a polymer electrolyte membrane according to the invention.
  • FIG. 1 shows a fuel cell comprising a multiplicity of individual cells
  • Figure 2 is a sectional view of a single cell of the fuel cell of Figure 1 with a membrane Etektrode ⁇ unit;
  • FIG. 3 shows the performance curve of a membrane-electrode unit with a crosslinked ABPBI polymer electrolyte membrane according to the invention in the long-term experiment with alternating voltage cycles and
  • FIG. 4 shows the performance curve of a membrane electrode assembly with a crosslinked ABPBI polymer electrolyte membrane according to the invention in the long-term experiment with alternating temperature cycles
  • FIG. 1 shows a fuel cell 10 which comprises a plurality of series-connected individual cells 12, of which a single one is shown in greater detail in FIG.
  • Each individual cell 12 comprises a membrane-electrode assembly 14 (MEA), each comprising a proton-conducting polymer electrolyte membrane 16 according to the present invention, and two electrodes 18, 20 adjoining the two outer membrane surfaces, namely an anode 18 and a cathode 20.
  • the individual cells 12 include between in each case two MEA 14 arranged bipolar plates 22 which electrically contact on both sides of the MEA composite and provide for the supply of the process gases and the discharge of the product water.
  • the bipolar plates 22 have a multiplicity of inner transport channels which serve to supply the reaction gases (hydrogen in the case of the anode and oxygen or air in the case of the cathode) and also to remove the product water on the cathode side. Materials for sealing and stabilizing the MEA 14 are not shown.
  • the fuel cell 10 further includes hydrogen supply lines 24 which supply the bipolar plates 22 with hydrogen gas.
  • An inner anode-side channel system of the bipolar plates 22 supplies the supplied hydrogen H 2 to the anodes 18 of the membrane-electrode assemblies 14, where it is oxidized to protons H + .
  • Via hydrogen derivatives 26 which are connected to a further anode-side internal channel system of the bipolar plates 22, the unused residual hydrogen (and product water which has diffused through the membrane 16) is removed and recycled.
  • air supply lines 28 are provided, with which air and thus oxygen to the bipolar plates 22 and from there via a cathode-side channel system of the same, the cathodes 20 is supplied.
  • the discharge of the remaining air and the product water takes place.
  • the stack of the individual cells 12 is bounded laterally by end plates 32. Not shown are other components of the fuel cell 10, such as a cooling system, control electronics, pumps, valves and the like.
  • the two electrodes 18, 20 each comprise a macroporous catalyst layer 34, which contacts the polymer electrolyte membrane 16 on both sides.
  • the catalyst layers 34 contain, as actually reactive centers of the electrodes, a catalytic material, which is usually a noble metal, such as platinum, iridium or ruthenium or transition metals, such as chromium, cobalt, nickel, iron, vanadium or tin, or Mixtures or alloys of these.
  • the catalytic substance is preferably fixed on a porous, electrically conductive carrier material.
  • the electrodes 18, 20 are designed as gas diffusion electrodes, which each comprise a gas diffusion layer (GDL for gas diffusion layer) 36, which adjoin the respective outer surfaces of the catalyst layers 34 facing away from the polymer membrane 16.
  • GDL gas diffusion layer
  • Function of the GDL 36 is to ensure a uniform flow of Katalysator für 34 with the reaction gases oxygen or air on the cathode side and hydrogen on the anode side.
  • the Polymerelektroiytmembran 16 has - as usual in high-temperature Bren ⁇ stoffzellen - a polymer component and bound to this complexed electrolyte component. The latter gives the polymer electrolyte membrane 16 its proton conductivity.
  • the polymer component contains at least one N-heteroaromatic polymer which in a preferred embodiment comprises ABPBI or a blend of ABbPBI and PBI which is covalently crosslinked with an organic diepoxide compound, in particular by chemical reaction with 1,4-butanediol diglycidyl ether (BDDGE) or a derivative of this.
  • the electrolyte component contains an electrolyte mixture of polyphosphoric acid and / or at least partially hydrolyzed polyphosphoric acid H n + 2 P n O 3n + I with n> 2 and at least one further acid, which in particular comprises phosphoric acid.
  • the glass plate was placed in a room temperature water bath for about 15 seconds, causing the membrane to be abruptly solidified.
  • the polymer electrolyte membrane could be withdrawn from the glass plate.
  • a 0.5% strength by weight solution of 1,4-butanediol diglycidyl ether (BDDGE) in water was prepared. With the aid of an atomizer, 0.05 g of this solution was sprayed onto one side of two polymer electrolyte membranes and then both membranes were placed on top of each other with their sprayed sides.
  • the crosslinking of the ABPB1 by the BDDGE was thermally initiated. This can be done either before the assembly and the installation of the membrane or - as in this case - during the initial Bre ⁇ nstoffzellen ceremoniess (Zellkonditio- ntechnik).
  • the polymer electrolyte membrane according to the invention had a thickness in the range of 130-160 .mu.m based on the structure of the two interconnected membranes and could be used for the construction of a membrane-electrode assembly.
  • Example 2 comparative example: Preparation of a non-cross-linked ABPBI polymer electrolyte membrane
  • the preparation was carried out analogously to Example 1, except that no spraying with the BDDGE Vernetzeriösung before joining the precipitated polymer electrolyte membranes.
  • the thickness of the comparative membranes was also in the range of 130-160 microns.
  • Example 3 Determination of the Conductivity of the Polymer Electrolyte Membranes
  • the proton conductivity of the samples prepared according to Examples 1 and 2 was determined by means of impedance spectroscopy. For this a piece of 2 cm x 4 cm was cut out of each sample. This sample was clamped in a 4-electrode-in-plane conductivity cell (company: Fumatech MK3). As an impedance meter, a Zahner IM6 was used. The impedance measurement was carried out with an amplitude of 10 mV in the frequency range from 200 kHz to 1 Hz. For the proton conductivity was for the sample according to Beispie!
  • Example 4 Determination of the Power Density of a Membrane-Electrode Unit
  • the polymer electrolyte membranes prepared according to Examples 1 and 2 were installed with two gas diffusion electrodes to a membrane electrode assembly.
  • the Pt loading of the electrodes used was 1, 3 mg / crn z.
  • the electrodes were placed on the membrane and clamped in a test cell with a torque of 5 Nm.
  • the power density of the membrane-electrode units thus produced was determined on a test stand (company Fuelcon). For both samples at a temperature of 160 0 C, a pressure of 2.5 bar, a stoichiometry for hydrogen: air of 1, 5 to 2, volume flows of 0.1 l / min for hydrogen and 0.33 l / min for air, a power density of 0.48 W / cm 2 at a voltage of 0.6 V obtained.

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Abstract

L'invention concerne une membrane à polyélectrolyte pour piles à combustible, comprenant : (a) un composant polymère renfermant au moins un polymère N-hétéroaromatique basique, en particulier ABPBI qui, par réaction avec un composé diépoxyde organique, en particulier 1,4-batandioldiglycidyléther, est réticulé covalent, et (b) un mélange d'électrolyte comprenant - un acide polyphosphorique et/ou un acide polyphosphorique au moins partiellement hydrolysé Hn+2PnO3n+1 où n≥2 et - au moins un autre acide, l'acide polyphosphorique et/ou l'acide phosphorique au moins partiellement hydrolysé, et au moins l'autre acide se présentant lié, via des ponts hydrogène, aux atomes d'azote hétéroaromatiques d'au moins un polymère N-hétéroaromatique. La membrane à polyélectrolyte selon l'invention peut être produite au moyen d'un procédé qui comprend les étapes suivantes : (a) production d'une solution polymère renfermant - au moins un polymère N-hétéroaromatique et - un mélange d'électrolyte comprenant un acide polyphosphorique et au moins un autre acide, (b) transformation de la solution polymère en une forme plate, (c) précipitation de la solution polymère amenée sous une forme plate, au moyen d'eau liquide, et (d) mise en contact de la membrane précipitée avec un composé diépoxyde organique, et déclenchement de la réticulation.
PCT/EP2010/062090 2009-08-20 2010-08-19 Membrane à polyélectrolyte pour piles à combustible ht, et son procédé de production Ceased WO2011020872A1 (fr)

Applications Claiming Priority (2)

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DE102009028758.2 2009-08-20
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