EP2078318A1 - Procédé de fabrication d'une unité membrane-électrode - Google Patents

Procédé de fabrication d'une unité membrane-électrode

Info

Publication number
EP2078318A1
EP2078318A1 EP07820697A EP07820697A EP2078318A1 EP 2078318 A1 EP2078318 A1 EP 2078318A1 EP 07820697 A EP07820697 A EP 07820697A EP 07820697 A EP07820697 A EP 07820697A EP 2078318 A1 EP2078318 A1 EP 2078318A1
Authority
EP
European Patent Office
Prior art keywords
border
catalyst layer
polymer electrolyte
electrolyte membrane
membrane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07820697A
Other languages
German (de)
English (en)
Inventor
Sigmar BRÄUNINGER
Gunter Bechtloff
Werner Urban
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP07820697A priority Critical patent/EP2078318A1/fr
Publication of EP2078318A1 publication Critical patent/EP2078318A1/fr
Withdrawn legal-status Critical Current

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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/881—Electrolytic membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8814—Temporary supports, e.g. decal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H01M8/0263—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant having meandering or serpentine paths
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0276—Sealing means characterised by their form
    • 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
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • 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
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H01M8/1088—Chemical modification, e.g. sulfonation
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0276—Sealing means characterised by their form
    • H01M8/0278—O-rings
    • 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 method of manufacturing a membrane electrode assembly including an anode catalyst layer, a polymer electrolyte membrane, and a cathode catalyst layer, and to a fuel cell comprising such a membrane electrode assembly.
  • Fuel cells are energy converters that convert chemical energy into electrical energy.
  • a fuel for example hydrogen
  • an oxidant for example oxygen
  • the structure of the cells is basically the same for all types. They generally consist of two electrodes, an anode and a cathode, where the reactions take place, and an electrolyte between the two electrodes.
  • the electrolyte used is a polymer membrane which conducts ions (in particular H + ions).
  • the electrolyte has three functions. It establishes the ionic contact, prevents the electronic contact and also ensures the separation of the gases supplied to the electrodes.
  • the electrodes are usually supplied with gases, which are reacted in the context of a redox reaction.
  • the electrodes have the task of supplying the gases (for example hydrogen or methanol and oxygen or air), removing reaction products such as water or CO 2 , catalytically reacting the starting materials and removing or supplying electrons.
  • the conversion of chemical to electrical energy occurs at the three phase boundary of catalytically active sites (eg, platinum), ionic conductors (eg, ion exchange polymers), electron conductors (eg, graphite), and gases (eg, H 2 and O 2 ).
  • the largest possible active area is crucial.
  • the core of a PEM fuel cell is a double-sided catalyst coated polymer electrolyte membrane (CCM) or a membrane electrode assembly (MEA).
  • a bilayer catalyst-coated polymer electrolyte membrane (CCM) in this context means a three-layer, double-sided catalyst coated polymer electrolyte membrane comprising an outer anode catalyst layer on one side of a membrane layer, the central membrane layer and an outer cathode catalyst layer on the opposite side of the membrane layer from the anode catalyst layer.
  • the membrane layer consists of proton-conducting polymer materials, hereinafter referred to as ionomers.
  • the catalyst layers contain catalytically active components which catalytically support the respective reaction at the anode or cathode (for example oxidation of hydrogen, reduction of oxygen).
  • the catalytically active components used are preferably the metals of the platinum group of the Periodic Table of the Elements.
  • the membrane-electrode assembly comprises a double-sided catalyst coated polymer electrolyte membrane and at least one gas diffusion layer (GDL).
  • GDL gas diffusion layer
  • Membrane electrode units are known in the art, for example from WO 2005/006473 A2.
  • the membrane-electrode assembly described therein comprises an ion-conducting membrane having front and back faces, a first catalyst layer and a first gas diffusion substrate on the front side, and a second catalyst layer and a second gas diffusion substrate on the back side, the first gas diffusion substrate having a smaller area Expansion as the ion-conducting membrane and the second gas diffusion substrate having substantially the same areal extent as the ion-conducting membrane.
  • WO 00/10216 A1 relates to a membrane-electrode assembly with a polymer electrolyte membrane having a central and a peripheral region.
  • An electrode is disposed over the central region and a portion of the peripheral region of the polymer electrolyte membrane.
  • a subgasket is disposed on the peripheral portion of the polymer electrolyte membrane so as to extend over the portion of the electrode which expands into the peripheral region of the polymer electrolyte membrane, and another seal is at least partially disposed on the subgasket.
  • WO 2006/041677 A1 relates to a membrane-electrode assembly comprising an assembly comprising a polymer electrolyte membrane, a gas diffusion layer and a catalyst layer between the polymer electrolyte membrane and the gas diffusion layer.
  • a sealing member is disposed over one or more components of the assembly with an outer edge of the gas diffusion layer overlapping with the sealing member.
  • the sealing element comprises a layer of a material that can be deposited and cured in situ.
  • US Pat. No. 6,500,217 B1 describes a method for applying electrode layers to a band-shaped polymer electrolyte membrane.
  • the front and back of the membrane is continuously printed in the desired pattern with the electrode layers using an ink containing an electrocatalyst and the printed electrode layers dried immediately after the printing process at elevated temperature, wherein the printing while maintaining a positionally accurate arrangement of the patterns of the electrode layers of Front and back to each other.
  • the membrane electrode assembly In a fuel cell, the membrane electrode assembly is typically inserted between two gas distribution plates.
  • the gas distribution plates serve as current collectors and as distributors for reaction fluid streams (for example hydrogen, oxygen or a liquid fuel, for example formic acid).
  • reaction fluid streams for example hydrogen, oxygen or a liquid fuel, for example formic acid.
  • the surfaces of the gas distribution plates facing the membrane-electrode assembly are usually provided with open-side channels or depressions.
  • a fuel cell stack a plurality of individual fuel cells are serially connected to each other to increase the overall output.
  • one side of a gas distribution plate acts as the anode of a fuel cell and the other side of the gas distribution plate acts as the cathode of an adjacent fuel cell.
  • the gas distribution plates (other than the end plates) are referred to as bipolar plates.
  • sealing frames are provided for this, which are arranged between the gas distributor plates and the membrane, optionally in conjunction with elastic seals. Clamping the gas distribution plates with the membrane-electrode assembly is intended to provide a fluid-tight seal through the sealing frames (and optionally the elastic seals).
  • the object of the present invention is therefore to avoid the disadvantages of the prior art and in particular to enable sealing and stabilization of the polymer electrolyte membrane of a membrane-electrode assembly, in particular in the region of the edge of the electrochemically active surface.
  • a method for producing a membrane-electrode assembly which contains an anode catalyst layer, a polymer electrolyte membrane and a cathode catalyst layer.
  • the inventive method comprises the steps of applying a first border of a UV-curable material on the polymer electrolyte membrane, wherein an inner region of the polymer electrolyte membrane remains free of the UV-curable material, applying a catalyst layer which covers the inner region of the polymer electrolyte membrane and with the first Border overlaps, applying a second border of the UV-curable material to the first border, the second border surrounding the catalyst layer, applying a third border of the UV-curable material to the second border, the third border overlapping the catalyst layer and Irradiating the first, second and third borders with UV radiation.
  • the second and third borders can be applied separately or together in one step onto the first border.
  • there is a border made of UV-cured material which is formed from the three largely superposed borders of UV-cured material.
  • the polymer electrolyte membrane preferably contains cation-conductive polymer materials.
  • a tetrafluoroethylene-fluorovinyl ether copolymer having acid functions, in particular sulfonic acid groups is used.
  • Such a material is marketed under the trade name Nafion ® from EI DuPont.
  • polymer electrolyte materials which can be used in the present invention are the following polymer materials and mixtures thereof:
  • Raymion ® (Chlorine Engineering Corp., Japan).
  • ionomer materials can also be used, for example sulfonated phenol-formaldehyde resins (linear or linked); sulphonated polystyrene (linear or linked); sulfonated poly-2,6-diphenyl-1,4-phenylene oxides, sulfonated polyaryl ether sulfones, sulfonated polyarylene ether sulfones, sulfonated polyaryl ether ketones, phosphonated poly-2,6-dimethyl-1, 4-phenylene oxides, sulfonated polyether ketones, sulfonated polyether ether ketones, aryl ketones or polybenzimidazoles ,
  • polystyrene resin styrene resin
  • the polymer electrolyte membrane used for the present invention preferably has a thickness between 20 and 100 ⁇ m, preferably between 40 and 70 ⁇ m.
  • the anode and cathode catalyst layers of the membrane-electrode assembly contain at least one catalytic component which catalytically supports, for example, the reaction of oxidation of hydrogen or reduction of oxygen.
  • the catalyst layers may also contain a plurality of catalytic substances with different functions.
  • the particular catalyst layer may contain a functionalized polymer (ionomer) or a non-functionalized polymer.
  • an electron conductor is preferably used in the catalyst layers i.a. for conducting the electric current flowing in the fuel cell reaction and as carrier material for the catalytic substances.
  • the catalyst layers preferably contain as catalytic component at least one element from the 3rd to 14th group of the Periodic Table of the Elements (PSE), more preferably from the 8th to 14th group of the PSE.
  • the cathode catalyst layer preferably contains as a catalytic component at least one element selected from the group consisting of Pt, Co, Fe, Cr, Mn, Cu, V, Ru, Pd, Ni, Mo, Sn, Zn, Au, Ag, Rh, Ir and W.
  • the anode catalyst layer preferably contains as catalytic component at least one element selected from the group consisting of the elements Co, Fe, Cr, Mn, Cu, V, Ru, Pd, Ni, Mo, Sn, Zn, Au, Rh, Ir and W.
  • the method according to the invention for the production of a membrane-electrode unit comprises the application of a border made of a UV-curable material to the polymer layer. electrolyte membrane, wherein an inner region of the polymer electrolyte membrane remains free of the UV-curable material.
  • a UV-curable material is a material in the form of a liquid or paste which can be solidified by irradiation with UV rays, in particular a material which can be polymerized by UV irradiation. UV-curable material is used in the prior art for example for coating bipolar plates (US Pat. No.
  • UV-curable material for the present invention has the advantage that it can be solidified without thermal stress on the polymer electrolyte membrane. This advantage, for example, does not offer a heat-bonding method.
  • the application of the border from the UV-curable material, in particular to the polymer electrolyte membrane for example, by doctor blade, spray, casting, printing or extrusion process.
  • the UV-curable material is low in solvent or solvent. This has the advantage that contamination or swelling of the polymer electrolyte membrane by a solvent is avoided. Furthermore, there is no workplace exposure to solvents during processing of a solventless UV curable material.
  • solvent-containing UV-curable materials can also be used for the present invention.
  • the UV-curable material is preferably liquid at room temperature to allow for easy processing.
  • only one component is applied as the UV-curable material, so that no stirring, such as stirring, occurs. in a two-component adhesive is required.
  • the use of the UV-curable material also has the advantage that it ensures a high degree of flexibility with regard to the further processing time (ie with regard to the time of irradiation with UV radiation).
  • the border surrounds the inner region where no UV-curable material is applied to the polymer electrolyte membrane and which contains the electrochemically active surface in the finished membrane-electrode assembly.
  • the border of UV-curable material on the polymer electrolyte membrane is irradiated with UV radiation, so that the material hardens and a border of UV-cured material is formed on the polymer electrolyte membrane.
  • Thieves- Radiation of the first border with UV radiation can be carried out in the inventive method before applying the catalyst layer.
  • the irradiation may, however, also take place after the application of the second or third border, so that at the same time several borders of UV-curable material are cured by the irradiation with UV radiation.
  • UV curable materials known to those skilled in the art may be used.
  • UV-curable materials can be used, as described in DE 10103428 A1, EP 0463525 B1, WO 2001/55276 A1, WO 2003/010231 A1, WO 2004/081133 A1, WO 2004/083302 or WO 2004/058834 A1 ,
  • An example of a useful liquid UV-crosslinkable pressure sensitive adhesive is constructed as follows: 60-95% acrylate monomers or acrylated oligomers, 0-30% adhesion improvers (e.g., resins) and 1-10% photoinitiators. Upon irradiation with UV radiation, radicals form from the photoinitiators and the curing then takes place by the transfer of the radicals onto the monomers or oligomers. Suitable photoinitiators usually contain a benzoyl group and are available in various variants.
  • a lacquer / adhesive of the type KIWO AZOCOL Poly-Plus H-WR (Kissel + Wolf), which is customarily used for the coating of screen printing nets and remains flexible after UV crosslinking.
  • a catalyst layer (which is an anode or a cathode catalyst layer of the membrane Electrode assembly), which covers the inner region of the polymer electrolyte membrane and overlaps with the first border of UV-cured material.
  • the application of the catalyst layer can be carried out, for example, by applying a catalyst ink, which is a solution containing at least one catalytic component.
  • the catalyst ink which is optionally paste-like, can be applied in the process according to the invention by methods familiar to the person skilled in the art, for example by printing, spraying, knife coating or rolling.
  • the catalyst layer can be dried. Suitable drying methods are, for example, hot-air drying, infrared drying, microwave drying, plasma processes or combinations of these processes.
  • the overlapping of the catalyst layer with the first border made of UV-cured material affords the advantage that the polymer electrolyte membrane is inserted in the transition region between the catalyst layer and the outer region (in which the polymer electrolyte membrane protrudes above the catalyst layer), in which, for example, a sealing frame is inserted , reinforced and protected by the border of UV-cured material.
  • a first border made of a UV-curable material is applied to the polymer electrolyte membrane, an inner region of the polymer electrolyte membrane remaining free of the UV-curable material, then the first border is optionally irradiated with UV radiation. Then, a catalyst layer is applied which covers the inner area of the polymer electrolyte membrane and overlaps with the first border. Subsequently, further UV-curable material is applied to the first border and possibly irradiated with UV radiation.
  • the border can be made variable in terms of shape and thickness.
  • a second edge of the UV-curable material is applied to the first border, wherein the second border surrounds the catalyst layer and then a third border of the UV-curable material is applied to the second border, wherein the third border with the Catalyst layer overlaps.
  • the first, second and third borders are irradiated with UV radiation for curing.
  • UV radiation e.g. Mercury medium pressure lamps are used.
  • the irradiation of the first, second and third borders with UV radiation can take place together after each application of one of the borders or following the application of at least two borders.
  • a border of UV-cured material composed of the first, second and third borders has the advantage that the edge of the catalyst layer overlapping the first border is enclosed by the three borders and the resulting overall border UV-hardened material gives the polymer electrolyte membrane particular stability.
  • a gas diffusion layer applied to the catalyst layer preferably overlaps with its outer edge with the third border in this embodiment.
  • the border prevents rupture of the membrane at the edge of the electrochemically active surface. Without the border arranged according to the invention, this problem of membrane damage arises, in particular in the case of non-fluorinated membranes, when a sealing frame is used. In addition to this reinforcement function, the border assumes a sealing function. Furthermore, a border of UV-cured material with good adhesion to the polymer electrolyte membrane can prevent the membrane from swelling, becoming deformed or becoming mechanically unstable in the sealing area.
  • the first border is applied so thinly to the polymer electrolyte membrane that substantially no edges are formed, so that the mechanical pressure load in the edge region of the electrochemically active surface is reduced.
  • the thickness of the border formed from the three borders is preferably between 3 and 500 microns, more preferably between 5 and 20 microns.
  • the invention further relates to a fuel cell, comprising at least one membrane-electrode assembly containing an anode catalyst layer, a polymer electrolyte membrane and a cathode catalyst layer, wherein the polymer electrolyte membrane is connected on both sides with a respective border of a UV-cured material, wherein the respective border a first border, with which the anode catalyst layer or with which the cathode catalyst layer overlaps, comprises a second border arranged on the first border, which surrounds the anode catalyst layer or the cathode catalyst layer, and comprises a third border arranged on the second border; overlaps with the anode catalyst layer or with the cathode catalyst layer.
  • the fuel cell according to the invention is preferably operated with hydrogen or a liquid fuel.
  • the membrane-electrode unit of the fuel cell according to the invention is preferably produced by the process according to the invention.
  • the membrane-electrode assembly of the present invention preferably includes one or two gas diffusion layers disposed on the anode catalyst layer and / or on the cathode catalyst layer.
  • at least one of the anode or cathode catalyst layers is connected to a gas diffusion layer.
  • the gas diffusion layer can serve as a mechanical support for the electrode and ensures a good distribution of the respective gas over the catalyst layer and for the discharge of the electrons.
  • a gas Diffusion layer gas distribution layer is needed in particular for fuel cells, which are operated with hydrogen on the one hand and oxygen or air on the other hand.
  • the anode catalyst layer having a first gas diffusion layer and the cathode catalyst layer are connected to a second gas diffusion layer such that the first gas diffusion layer and the anode catalyst layer and the second gas diffusion layer and the cathode catalyst layer are flush with each other. If, for example, the anode catalyst layer and the cathode catalyst layer have different sized expansions, then the two gas diffusion layers according to this embodiment also have these different sized planar expansions and are flush with the respective catalyst layer on all sides.
  • the anode catalyst layer is connected to a first gas diffusion layer and the cathode catalyst layer is connected to a second gas diffusion layer so that at least one of the first or second gas diffusion layers with a gas diffusion layer edge projects beyond the anode or cathode catalyst layer.
  • the gas diffusion layers (for example made of carbon fleece or carbon paper) are preferably applied to the catalyst layers by application, rolling, hot pressing or other techniques familiar to the person skilled in the art.
  • a sealing frame for sealing the membrane-electrode assembly is placed on the border of UV-cured material.
  • the sealing frame is preferably a frame which fulfills at least one of the following functions:
  • a preformable sealing element made of, for example, silicone, polyisobutylene, rubber (synthetic or natural), fluoroelastomer or fluorosilicone can be used for the seal.
  • a deformable sealing element can serve for example an O-ring.
  • the sealing frame may be made of any gene, non-functionalized gas-tight polymer or consist of a polymer coated with such a polymer, wherein as the polymer in particular polyethersulfone, polyamide, polyimide, polyether ketone, polysulfone, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene (PE) or polypropylene (PP) can be used.
  • the respective sealing frame preferably covers a predominant portion of the surface of a border made of UV-cured material, as far as it extends beyond the catalyst layer.
  • a deformable sealing element can be arranged on one of the sealing frames so that it is located in a fuel cell between the sealing frame and a gas distributor plate and is clamped there.
  • the function of sealing adopted by the sealing frame according to an embodiment of the present invention can also be taken over by the border of UV-cured material, so that no sealing frame is required.
  • a preformable sealing element for example of silicone, polyisobutylene, rubber (synthetic or natural), fluoroelastomer or fluorosilicone can be used directly on the border of UV-cured material for sealing.
  • a deformable sealing element can serve for example an O-ring.
  • the UV-curable material is applied by screen printing, e.g. by rotary or flatbed screen printing.
  • the application of the UV-curable material by screen-printing technique has the advantage that the UV-curable material can be applied in one or more thin layers and cured immediately thereafter (for example, crosslinked), so that the polymer electrolyte membrane is stabilized.
  • the catalyst layer is applied by means of screen printing, so that the application of the UV-curable material with screen printing has production technical advantages.
  • application of the UV-curable material may also be by other methods, e.g. by flexo printing.
  • the border of UV-cured material surrounds on both sides of the polymer electrolyte membrane an inner region in which a catalyst layer which overlaps the first border is arranged.
  • the catalyst layer is covered with a gas diffusion layer and on the border is a seal arranged.
  • a gas distribution plate covers the gas diffusion layer and the gasket frame.
  • the gas distribution plate may be, for example, a bipolar plate or an end plate of a fuel cell or a fuel cell stack.
  • the gas distributor plate preferably contains channels for gases, the so-called "flow field", which distributes gaseous reactants (for example hydrogen and oxygen) over the gas diffusion layer at least on one surface
  • a bipolar plate is used for the electrical connection of the fuel cell, for the supply and distribution of reactants and coolants and for the separation of the gas spaces
  • the gas distributor plate can be, for example, a material selected from the group polyphenylene sulfide (PPS), liquid cristal polyester (LCP), Polyoxymethylene (POM), polyaryletherketone (PAEK), polyamide (PA), polybutylene terephthalate (PBT), polyphenylene oxide (PPO), polypropylene (PP) or polyethersulfone (PES) or any other technically used plastic containing plastic with electrically conductive particles be filled, insbeso Change with graphite or metal particles.
  • the gas distribution plate may be made of graphite, metal or graphite composites.
  • a deformable sealing element is arranged between the sealing frame and the gas distributor plate.
  • the gas distribution plate and / or the sealing frame grooves may be provided for receiving the deformable sealing element.
  • the gas distribution plate contains channels for conducting gases along the gas diffusion layer, wherein the channels have a gas inlet region and the border of UV-cured material (composed of three borders) covers the polymer electrolyte membrane adjacent to the gas inlet region. Frequently "burn through" of the polymer electrolyte membrane is observed in the entry region of the gases in the fuel cells known in the prior art
  • the membrane surface By expanding the region of the polymer electrolyte membrane covered with UV-hardened material into the active surface next to the gas inlet region, the membrane surface also becomes in this region A resulting asymmetric shape of the border can be easily applied, for example by screen printing of the UV-curable material on the polymer electrolyte membrane.
  • FIG. 1 shows a prior art fuel cell prior to bracing
  • FIG. 2 shows a prior art fuel cell after bracing
  • FIG. 3 shows a schematic representation of a fuel cell which contains a border made of UV-cured material
  • FIGS. 4A to 4C three steps of the method according to the invention for the production of a membrane-electrode unit
  • Figure 5 is a schematic representation of a half of an embodiment of a fuel cell according to the invention.
  • FIGS. 6A and 6B show two views of a further embodiment of a device according to the invention
  • Figure 1 shows a schematic sectional view of a fuel cell of the prior art before the tension.
  • the fuel cell is constructed symmetrically with respect to your individual layers.
  • a catalyst layer 2 which is covered by a gas diffusion layer 3, is arranged in each case.
  • the polymer electrolyte membrane 1 protrudes beyond the catalyst layer 2 with the membrane edge 4.
  • a sealing frame 5 is arranged on both sides.
  • the membrane electrode unit with the polymer electrolyte membrane 1, the two catalyst layers 2, the two gas diffusion layers 3 and the two sealing frames 5 is enclosed by two gas distributor plates 6, which are connected to one another via clamping screws 7. For clamping the clamping screws are tightened, which act on the gas distributor plates 6 forces in the direction of tension 8.
  • Figure 2 shows a schematic sectional view of a fuel cell of the prior art after the tension.
  • the fuel cell is essentially constructed like the fuel cell according to FIG.
  • the same reference numerals designate like components of the fuel cell.
  • this fuel cell contains deformable sealing elements 10, which in each case were deformed between one of the sealing frames 5 and a gas distributor plate 6 during clamping and ensure the seal towards the polymer electrolyte membrane 1. Also in this embodiment, there is a risk of damage to the polymer electrolyte membrane 1 in the critical region 9.
  • Figure 3 shows a schematic sectional view of a fuel cell containing a border of UV-cured material.
  • this fuel cell contains a border 11 made of UV-cured material.
  • This fuel cell includes a membrane electrode assembly 12 including an anode catalyst layer 13, a polymer electrolyte membrane 1, and a cathode catalyst layer 14.
  • the polymer electrolyte membrane 1 is connected on both sides to a border 11 made of a UV-cured material, the respective border 11 overlapping the anode catalyst layer 13 or the cathode catalyst layer 14 (overlapping area 15).
  • the border 11 of UV-cured material surrounds an inner region 16, in which a catalyst layer 2, 13, 14 is arranged, which overlaps with the border 11 and which is covered with a gas diffusion layer 3.
  • a sealing frame 5 (made of Teflon, for example) is arranged on the border 11 and a gas distributor plate 6 covers the gas diffusion layer 3 and the sealing frame 5.
  • a deformable sealing element 10 is arranged between the sealing frame 5 and the gas distributor plate 6 (for example, an O-ring). Ring).
  • FIGS. 4A to 4C show diagrammatically the result of individual steps of the method according to the invention for producing a membrane-electrode assembly, in each case in a plan view (top) and in a sectional illustration (bottom).
  • FIG. 4A shows a polymer electrolyte membrane 1 which, according to one embodiment of the method according to the invention, serves as a starting layer for the production of a membrane-electrode assembly.
  • FIG. 4B shows a first border 17 made of a UV-curable material that has been applied to the polymer electrolyte membrane, wherein the inner region 16 of the polymer electrolyte membrane 1 is free of UV-curable material.
  • the border 17 is irradiated with UV radiation, so that the UV-curable material hardens.
  • Figure 4C shows a catalyst layer 2 applied to the inner region
  • FIG. 5 shows a schematic sectional representation of an embodiment of a fuel cell according to the invention, which is shown only half.
  • the layer sequence shown above the polymer electrolyte membrane 1 is repeated downward in the reverse order.
  • the fuel cell according to the invention according to FIG. 5 has a polymer electrolyte membrane 1, a catalyst layer 2, a gas diffusion layer 3, a sealing frame 5, a gas distributor plate 6 and a deformable sealing element 10 embedded in the grooves.
  • a first UV-cured border 17 is connected to the polymer electrolyte membrane.
  • the catalyst layer 2 overlaps with this first border
  • a second border 18 of the UV-cured material is applied to the first border and surrounds the catalyst layer 2.
  • a third border 19 of UV-cured material is applied, the third border overlaps with the catalyst layer 2 (second overlap area 20).
  • the gas diffusion layer 3 in turn overlaps with the third border 19 in the third overlap region 22.
  • FIG. 6A shows a schematic representation of a further embodiment of a fuel cell according to the invention.
  • This figure shows a fuel cell with a border 11 made of UV-cured material, which also surrounds the (not shown) polymer electrolyte membrane next to a gas inlet rich 23 a gas distribution plate 6 covered.
  • the channels 24 of the gas distribution plate 6 are shown, which serve to conduct gases (reactants) along the (not shown) gas diffusion layer. In these channels 24, a gas enters through the gas inlet region 23 and on the gas outlet region 25 again.
  • the border 11 also covers the polymer electrolyte membrane next to the gas inlet region 23, it is enlarged into the electrochemically active inner region 26 around the extension 27, which stabilizes this region.
  • Figure 6B shows such a structure of a fuel cell according to the invention in section (only one half).
  • the gas distribution plate 6 with the gas inlet region 23 and the channels 24 covers a membrane electrode assembly with gas diffusion layer 3, sealing frame 5, catalyst layer 2, border 1 1 of UV-cured material and polymer electrolyte membrane 1.
  • the border 11 is thereby extended so that they the polymer electrolyte membrane 1 adjacent to the gas inlet portion 23 covers and protects.
  • the border 11 comprises a first border 17, a second border 18 and a third border 19 made of UV-cured material, which surround the catalyst layer 2 at its outer edge.

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

Abstract

L'invention concerne un procédé de fabrication d'une unité membrane-électrode, qui contient une couche de catalyseur anodique (13), une membrane électrolytique polymère (1) et une couche de catalyseur cathodique (14), et une cellule électrochimique comportant une telle unité membrane-électrode. Le procédé selon la présente invention comprend les étapes consistant à appliquer une première bordure (17) constituée d'un matériau pouvant être durci par un rayonnement UV sur la membrane électrolytique polymère (1), un secteur intérieur (16) de la membrane électrolytique polymère (1) restant exempt de matériau pouvant être durci par un rayonnement UV, à déposer une couche de catalyseur (2) qui recouvre le secteur intérieur (16) de la membrane électrolytique polymère (1) et chevauche la première bordure (17), à appliquer une deuxième bordure (18), constituée du matériau pouvant être durci par rayonnement UV, sur la première bordure (17), la deuxième bordure (18) entourant la couche de catalyseur (2), à appliquer une troisième bordure (19), constituée du matériau pouvant être durci par un rayonnement UV, sur la deuxième bordure (18), la troisième bordure (19) chevauchant la couche de catalyseur (2) et à exposer les première, deuxième et troisième bordures (17, 18, 19) à un rayonnement UV.
EP07820697A 2006-10-02 2007-09-28 Procédé de fabrication d'une unité membrane-électrode Withdrawn EP2078318A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07820697A EP2078318A1 (fr) 2006-10-02 2007-09-28 Procédé de fabrication d'une unité membrane-électrode

Applications Claiming Priority (3)

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EP06121604 2006-10-02
EP07820697A EP2078318A1 (fr) 2006-10-02 2007-09-28 Procédé de fabrication d'une unité membrane-électrode
PCT/EP2007/060310 WO2008040682A1 (fr) 2006-10-02 2007-09-28 Procédé de fabrication d'une unité membrane-électrode

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EP (1) EP2078318A1 (fr)
JP (1) JP2010506352A (fr)
KR (1) KR20090082377A (fr)
CN (1) CN101553946A (fr)
CA (1) CA2665187A1 (fr)
TW (1) TW200832792A (fr)
WO (1) WO2008040682A1 (fr)

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Publication number Publication date
CN101553946A (zh) 2009-10-07
TW200832792A (en) 2008-08-01
KR20090082377A (ko) 2009-07-30
JP2010506352A (ja) 2010-02-25
WO2008040682A1 (fr) 2008-04-10
CA2665187A1 (fr) 2008-04-10
US20100216048A1 (en) 2010-08-26

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