WO2012163383A1 - Dispositif à membrane électrolytique pour pile à combustible, et son procédé de production - Google Patents

Dispositif à membrane électrolytique pour pile à combustible, et son procédé de production Download PDF

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Publication number
WO2012163383A1
WO2012163383A1 PCT/EP2011/006268 EP2011006268W WO2012163383A1 WO 2012163383 A1 WO2012163383 A1 WO 2012163383A1 EP 2011006268 W EP2011006268 W EP 2011006268W WO 2012163383 A1 WO2012163383 A1 WO 2012163383A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
electrolyte membrane
amplifier
perforated
coated
Prior art date
Application number
PCT/EP2011/006268
Other languages
German (de)
English (en)
Inventor
Dirk Lindenau
Matteo Scolari
Original Assignee
Daimler Ag
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 Daimler Ag filed Critical Daimler Ag
Publication of WO2012163383A1 publication Critical patent/WO2012163383A1/fr

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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018Polymeric electrolyte materials
    • H01M8/1065Polymeric electrolyte materials characterised by the form, e.g. perforated or wave-shaped
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • H01M4/8803Supports for the deposition of the catalytic active composition
    • H01M4/881Electrolytic membranes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0271Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0273Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0271Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028Sealing means characterised by their material
    • H01M8/0284Organic resins; Organic polymers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0271Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0286Processes for forming seals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0289Means for holding the electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04197Preventing means for fuel crossover
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1004Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018Polymeric electrolyte materials
    • H01M8/1058Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018Polymeric electrolyte materials
    • H01M8/1058Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/106Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018Polymeric electrolyte materials
    • H01M8/1069Polymeric electrolyte materials characterised by the manufacturing processes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0088Composites
    • H01M2300/0094Composites in the form of layered products, e.g. coatings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/22Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to a multilayer electrolyte membrane arrangement with an amplifier layer.
  • the invention further relates to a method for producing an electrolyte membrane arrangement for a fuel cell, in particular a
  • the polyelectrolyte membrane separates an anode side of the fuel cell from a cathode side.
  • hydrogen is catalytically oxidized to protons at the anode side by the emission of electrons.
  • the protons diffuse through the polymer electrolyte membrane to the cathode where they react with oxygen to form water.
  • chemical energy is converted into electrical energy which is used, one between anode and cathode
  • the prior art further includes fuel cells in which methanol, formic acid, methane, a coal gas, carbon or magnesium is used as fuel on the anode side.
  • methanol, formic acid, methane, a coal gas, carbon or magnesium is used as fuel on the anode side.
  • the polymer electrolyte membrane diffusing ion according to the type of fuel cell also hydroxide, oxonium, or radical dioxide ions can be used.
  • US 2005/0227132 A1 discloses a multilayer electrolyte membrane arrangement which has a porous amplifier layer with an aperture ratio between 50% and 90%.
  • the amplifier layer is completely in one
  • the polyelectrolyte membrane is coated on both sides with a catalyst layer, which is a Having carbon powder, which serves as a support material for a catalytic metal such as platinum.
  • the invention is based on the object, an improved over the prior art electrolyte membrane assembly and an improved method for
  • a multilayered electrolyte membrane assembly for a fuel cell has an amplifier layer with a perforated portion and a perforated portion
  • the perforated portion is coated with an ion-conductive material, so that a
  • the semipermeable membrane layer is formed.
  • the semipermeable membrane layer is particularly permeable only to molecules, ions or particles below a predeterminable size.
  • prior art polymer electrolyte membranes formed from the ion-conductive material are very thin (10-30 ⁇ ) and mechanically sensitive. Therefore, such polymer electrolyte membrane can be laboriously glued or welded, which also with the risk of damaging the
  • the amplifier layer is preferably formed from a mechanically, thermally and / or chemically resistant material.
  • the arrangement of the ionic conductive material on the support material of the amplifier layer increases the mechanical robustness and thus helps to avoid damage during production. In particular, so waste can be reduced during production.
  • the protruding edge region of the amplifier layer allows a simplified handling of the electrolyte membrane assembly during manufacture, whereby contact with the sensitive region of the semipermeable membrane layer is avoided.
  • the protruding edge region provides an enlarged joining surface, which in particular is quick and easy with other components the fuel cell can be glued and / or welded.
  • the amplifier layer is formed from a low cost material to reduce manufacturing costs.
  • the ionic conductive material is an ionomer, such as a sulfonated tetrafluoroethylene polymer, such that the semipermeable membrane layer of the electrolyte membrane assembly is permeable, at least for protons.
  • the ionically conductive material may have a permeability such that the semipermeable membrane layer formed by the ionically conductive material is permeable to at least one of a hydroxide ion, an oxonium ion, and a free radical dioxide ion.
  • the amplifier layer is of a low cost
  • Plastic material such as in particular a polymer formed, which has an increased mechanical, thermal and / or chemical robustness compared to the ion-conductive material. This advantageously reduces material costs and production costs.
  • At least one reinforcing frame element is materially connected to the edge region of the amplifier layer such that the frame element surrounds the edge of the semipermeable membrane layer.
  • the cohesive connection between the frame region and the edge region takes place in particular by means of a bond or a weld.
  • the edge region projecting beyond the semipermeable membrane layer ensures a flat connection surface, so that in particular the connection between frame element and edge region can be made fluid-tight.
  • the semipermeable membrane layer is coated with a catalyst layer.
  • the catalyst layer may for example consist of a carbon support and a catalytically active material such as platinum.
  • the catalyst layer serves at least as part of an electrode of the
  • the semipermeable membrane layer is in particular with a
  • Catalyst layer coated to form an anode or a cathode can be arranged on the catalyst layers, which are correspondingly permeable to gases such as hydrogen or oxygen.
  • a first method step at least one subregion of an amplifier layer is perforated in such a way that an imperforate edge region surrounding the subregion is formed on the edge.
  • the perforated portion is coated with an ion-conductive material to form a semipermeable membrane layer of the electrolyte membrane assembly.
  • the electrolyte membrane arrangement thus formed has an increased mechanical, thermal and / or chemical robustness.
  • the manufacturing method allows an economical production of the electrolyte membrane arrangement, as a direct bonding or welding of the mechanically sensitive ion-conductive material of the semipermeable membrane layer is avoided. This reduces the risk of
  • a low-cost plastic material can be used for the amplifier layer, so that material costs are saved.
  • an ionomer can be used as the ion-conductive material.
  • the semipermeable membrane layer is printed or coated with a catalyst layer.
  • the catalyst layer comprises at least one catalytically active material such as platinum or a platinum alloy and forms an electrode of the fuel cell.
  • the semipermeable membrane layer is coated on both opposite sides to form the anode and the cathode of the fuel cell with the catalyst layer.
  • the catalytically active platinum alloy for example, platinum-ruthenium, platinum-nickel or platinum-cobalt alloys are suitable.
  • the frame element completely surrounds the semipermeable region of the amplifier layer at the edge, so that the semipermeable membrane layer and / or the catalyst layer arranged thereon are completely covered by an inner cutout surface of the frame element.
  • the amplifier layer is made
  • Electrolyte membrane assembly takes place either before the first process step or after the third process step, a separating step in which the roll goods are cut.
  • Process technology is particularly advantageous if the
  • Rolled goods enable a continuous production process, which can be integrated particularly advantageously into a correspondingly automated production line.
  • FIGS. 1A to 1 D schematically illustrate method steps for producing a
  • Fig. 2 shows a roll of a plastic film having portions which are perforated to produce the electrolyte membrane assembly and then coated with a catalyst layer.
  • Fig. 3 shows the electrolyte membrane assembly in a sectional view.
  • FIG. 4 shows a sectional view of the electrolyte membrane arrangement with enclosing frame elements.
  • FIGS. 1A to 1 D schematically illustrate individual method steps for producing an electrolyte membrane arrangement 1.
  • FIG. 1A shows an amplifier layer 2 for a multilayer
  • Electrolytic Membrane Arrangement 1 An inner portion 2.1 of the amplifier layer 2 is perforated in a first method step by means of suitable punching or perforating tools.
  • the amplifier layer 2 has a circumferential edge region 2.2, which is imperforate and the peripheral portion of the perforated portion 2.1 rotates.
  • the amplifier layer 2 is produced, for example, from individual sheets of a plastic film K or from rolls of the plastic film K, as shown in FIG.
  • individual sections A1 to An of the plastic film K are preferably first perforated in such a way that each inner partial area 2.1 of the section A1 to An is surrounded correspondingly by the imperforate edge area 2.2.
  • the plastic film K consists of a cost-effective material which has sufficient mechanical, thermal and chemical robustness.
  • Suitable plastic films may for example consist of a polymer, polyethylene or a polypropylene.
  • the subregion 2.1 is coated with an ion-conductive material, such as, for example, a sulfonated tetrafluoroethylene polymer.
  • an ion-conductive material such as, for example, a sulfonated tetrafluoroethylene polymer.
  • a semipermeable membrane layer 3 which is permeable to particles or ions below a predeterminable size, is formed.
  • the semipermeable membrane layer 3 is coated or printed with a catalyst layer 4.
  • a catalyst layer 4 For example, precious metal-containing inks are used.
  • the membrane layers 3 thus formed are provided with the catalyst layer 4.
  • the roll of plastic film K is cut and fed to the further manufacturing process.
  • the protruding edge region 2.2 of the amplifier layer 2 is arranged opposite one another
  • the frame element 5 materially connected.
  • the frame element 5 has an inner cutout surface 5.1, which overlaps with the catalyst layer 4.
  • the amplifier layer 2 is glued or welded to the frame element 5.
  • the edge region 2.2 ensures surface contact with the respective frame element 5.
  • FIG. 3 shows the electrolyte membrane arrangement 1 in a sectional view.
  • Amplifier layer 2 has an inner perforated portion 2.1.
  • Part 2.1 of the amplifier layer 2 is on both sides with the semipermeable
  • Membrane layer 3 coated so that an ion exchange between the
  • the semipermeable membrane layer 3 is permeable only to ions of a predeterminable size. According to various embodiments of the invention, the semipermeable membrane layer 3 according to the cell chemistry of
  • the edge region 2.2 of the amplifier layer 2 is uncoated and protrudes beyond the edge of the coated region of the membrane layer 3 and the catalyst layer 4. This allows a simplified handling and processing of
  • Electrolyte membrane assembly 1 during manufacture, so that damage to the sensitive membrane layer 3 can be avoided.
  • FIG. 4 shows the electrolyte membrane arrangement 1 with the frame elements 5, which are materially connected to the protruding edge regions 2.2 of the amplifier layer 2.
  • the two oppositely arranged frame elements 5 ensure the mechanical stability of the electrolyte membrane assembly 1.
  • Cut-out surface 5.1 of the frame member 5 overlaps with the region of the membrane layer 3 and the catalyst layer 4, so that this of the
  • a catalyst layer 4 is arranged on opposite sides of the amplifier layer 2.
  • the two opposing catalyst layers 4 serve as electrodes of the fuel cell.
  • gas diffusion layers may be arranged in a manner not shown, so that the cell chemistry of the fuel cell corresponding gases of the anode and the cathode can be fed.

Abstract

L'invention concerne un dispositif à membrane électrolytique multicouche (1) pour pile à combustible, présentant une couche d'amplification (2) présentant une région partielle perforée (2.1), et une région marginale non perforée (2.2) entourant, en bordure, la région partielle perforée (2.1). La région partielle perforée (2.1) est recouverte d'un matériau conducteur ionique, de façon qu'une couche de membrane semi-perméable (3) soit formée.
PCT/EP2011/006268 2011-06-01 2011-12-13 Dispositif à membrane électrolytique pour pile à combustible, et son procédé de production WO2012163383A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011106767A DE102011106767B3 (de) 2011-06-01 2011-06-01 Elektrolytmembrananordnung für eine Brennstoffzelle und Verfahren zu deren Herstellung
DE102011106767.5 2011-06-01

Publications (1)

Publication Number Publication Date
WO2012163383A1 true WO2012163383A1 (fr) 2012-12-06

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Application Number Title Priority Date Filing Date
PCT/EP2011/006268 WO2012163383A1 (fr) 2011-06-01 2011-12-13 Dispositif à membrane électrolytique pour pile à combustible, et son procédé de production

Country Status (2)

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DE (1) DE102011106767B3 (fr)
WO (1) WO2012163383A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5761417B1 (ja) * 2014-03-31 2015-08-12 大日本印刷株式会社 支持体付き電解質膜、及び、支持体付き触媒層−電解質膜積層体
US10333157B2 (en) 2014-11-25 2019-06-25 Johnson Matthey Fuel Cells Limited Membrane-seal assembly

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102158547B1 (ko) 2014-03-24 2020-09-22 존슨 맛쎄이 푸엘 셀스 리미티드 멤브레인-시일 어셈블리
GB201405209D0 (en) 2014-03-24 2014-05-07 Johnson Matthey Fuel Cells Ltd Process
CN112186216A (zh) * 2019-07-05 2021-01-05 深圳市南科燃料电池有限公司 封装方法和膜电极组件

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003007403A1 (fr) * 2001-07-13 2003-01-23 Ceramic Fuel Cells Limited Plaque de separation de gaz dans des piles a combustible
US20050227132A1 (en) 2004-03-04 2005-10-13 Yoshihiro Hori Composite electrolyte membrane, catalyst-coated membrane assembly, membrane-electrode assembly and polymer electrolyte fuel cell
US20060046121A1 (en) * 2004-08-30 2006-03-02 Asahi Glass Company, Limited Membrane-electrode assembly for polymer electrolyte fuel cells, and polymer electrolyte fuel cell
US20070054169A1 (en) * 2005-09-06 2007-03-08 Day Michael J Ceramic membranes with integral seals and support, and electrochemical cells and electrochemical cell stacks including the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003007403A1 (fr) * 2001-07-13 2003-01-23 Ceramic Fuel Cells Limited Plaque de separation de gaz dans des piles a combustible
US20050227132A1 (en) 2004-03-04 2005-10-13 Yoshihiro Hori Composite electrolyte membrane, catalyst-coated membrane assembly, membrane-electrode assembly and polymer electrolyte fuel cell
US20060046121A1 (en) * 2004-08-30 2006-03-02 Asahi Glass Company, Limited Membrane-electrode assembly for polymer electrolyte fuel cells, and polymer electrolyte fuel cell
US20070054169A1 (en) * 2005-09-06 2007-03-08 Day Michael J Ceramic membranes with integral seals and support, and electrochemical cells and electrochemical cell stacks including the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5761417B1 (ja) * 2014-03-31 2015-08-12 大日本印刷株式会社 支持体付き電解質膜、及び、支持体付き触媒層−電解質膜積層体
US10333157B2 (en) 2014-11-25 2019-06-25 Johnson Matthey Fuel Cells Limited Membrane-seal assembly

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