WO2009139369A1 - Ensemble électrodes-membrane et son procédé de fabrication - Google Patents

Ensemble électrodes-membrane et son procédé de fabrication Download PDF

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Publication number
WO2009139369A1
WO2009139369A1 PCT/JP2009/058814 JP2009058814W WO2009139369A1 WO 2009139369 A1 WO2009139369 A1 WO 2009139369A1 JP 2009058814 W JP2009058814 W JP 2009058814W WO 2009139369 A1 WO2009139369 A1 WO 2009139369A1
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Prior art keywords
membrane
electrode assembly
membrane electrode
fuel
electrode
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PCT/JP2009/058814
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English (en)
Japanese (ja)
Inventor
智寿 吉江
敏之 藤田
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シャープ株式会社
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Publication of WO2009139369A1 publication Critical patent/WO2009139369A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • 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
    • 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
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • 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
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • 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
    • H01M8/1097—Fuel cells applied on a support, e.g. miniature fuel cells deposited on silica supports
    • 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
    • H01M8/023—Porous and characterised by the material
    • H01M8/0241—Composites
    • H01M8/0245—Composites in the form of layered or coated products
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a membrane electrode assembly capable of increasing the area of a fuel electrode and an air electrode, and capable of preventing mixing of fuel and air and leakage of fuel to the outside of a cell, and a method for manufacturing the same.
  • the fuel cell can be used for a long time so that the user can use the electronic device for a long time by refueling once, and even if the user runs out of the battery on the go, it does not wait for the battery to be charged. From the viewpoint of convenience that electronic devices can be used immediately by purchasing and replenishing fuel, there is an increasing expectation for practical use as a new power source for portable electronic devices that support the information society.
  • a fuel cell oxidizes fuel such as a hydrocarbon gas, hydrogen gas, or an alcohol aqueous solution at a fuel electrode, and uses an oxidation-reduction reaction in which oxygen in the air is reduced at an air electrode.
  • fuel such as a hydrocarbon gas, hydrogen gas, or an alcohol aqueous solution at a fuel electrode
  • Fuel cells are classified into phosphoric acid type, molten carbonate type, solid electrolyte type, solid polymer type, direct alcohol type, etc., according to the classification of the electrolyte material or fuel used.
  • the polymer electrolyte fuel cell and the direct alcohol fuel cell using an ion exchange membrane that is a solid polymer as an electrolyte material the electrolyte membrane is a thin film of sub-millimeter or less, and high power generation efficiency is obtained at room temperature.
  • Practical application as a small fuel cell for the purpose of application to portable electronic devices is being studied.
  • the direct alcohol fuel cell when an alcohol aqueous solution is supplied to the fuel electrode, the alcohol aqueous solution in contact with the fuel electrode is oxidized and separated into a gas such as carbon dioxide and protons.
  • a gas such as carbon dioxide and protons.
  • carbon dioxide is generated on the fuel electrode side by an oxidation reaction represented by the following formula.
  • Such a structure in which a fuel electrode, an electrolyte membrane, and an air electrode, which are central members for taking out electric power, are integrated, is called a membrane electrode composite.
  • the electrolyte membrane of the membrane electrode assembly is configured so that the outer circumference is about 1 to 2 cm larger than the fuel electrode and the air electrode. This is because the electrolyte membrane functions as a diaphragm to prevent mixing of fuel and air and leakage of fuel to the outside of the cell, and to prevent an electrical short circuit between the fuel electrode and the air electrode.
  • the outer peripheral portion of the electrolyte membrane that protrudes that is, the electrolyte membrane portion where the fuel electrode and the air electrode are not formed, cannot contribute to the oxidation-reduction reaction even if fuel and air are supplied.
  • the area of the fuel electrode and the air electrode Is about several cm 2 , and the area of the outer peripheral portion of the electrolyte membrane that protrudes becomes very large relative to the total area of the membrane electrode assembly.
  • Patent Document 1 discloses that a sealing portion is formed by applying a sealing material to the side surface of a laminated battery.
  • the present invention has been made to solve the above problems. That is, the present invention relates to a mixture of fuel and air in a membrane electrode assembly intended for application to a portable electronic device having a power consumption of several watts, particularly to a portable electronic device-mounted fuel cell.
  • An object of the present invention is to provide a membrane electrode assembly capable of preventing the leakage of fuel to the outside of the battery and designing the area of the fuel electrode and the air electrode larger than the limited installation area of the fuel cell, and a method for manufacturing the same.
  • the present invention is a membrane electrode assembly comprising an electrolyte membrane, a fuel electrode formed on one surface of the electrolyte membrane, and an air electrode formed on the other surface of the electrolyte membrane,
  • the membrane electrode assembly has, on at least one side thereof, a side surface composed of a continuous surface composed of at least an end surface of the fuel electrode, an end surface of the electrolyte membrane, and an end surface of the air electrode, and an insulating sealing layer covering the side surface. It is related with the membrane electrode composite provided.
  • the side surface has an uneven shape.
  • the uneven shape is more preferably formed so that the side surface has a surface area of twice or more the projected area.
  • the present invention further includes a flow path plate provided adjacent to the fuel electrode, and the insulating sealing layer covers the end surface of the flow path plate and / or a part of the fuel electrode side surface. About the body.
  • the membrane electrode assembly of the present invention preferably further includes a permeable membrane disposed so as to cover the flow path of the flow path plate and adjacent to the fuel electrode.
  • the present invention has a side surface composed of a continuous surface composed of at least the end surface of the fuel electrode, the end surface of the electrolyte membrane, and the end surface of the air electrode on at least two opposite sides of the membrane electrode assembly.
  • the present invention relates to a membrane electrode assembly which includes an insulating sealing layer to be covered and whose ratio L / H between the length L and the width H of the membrane electrode assembly is 10 or more.
  • the membrane electrode assembly of the present invention having a long side and a short side having a length L and a width H, further comprising a metal conductive layer provided adjacent to the air electrode, wherein at least a part of the metal conductive layer is It is preferable that the membrane electrode assembly has an electrolyte membrane and a joint on the short side having the width H.
  • the present invention also relates to a membrane electrode composite stack in which a plurality of membrane electrode assemblies including the metal conductive layer are arranged in parallel or substantially in parallel with the opposing two sides.
  • the present invention provides a composite cutting step of cutting a first composite having a laminated structure composed of a fuel electrode, an electrolyte membrane, and an air electrode, and producing a second composite having a smaller area than the first composite. And an insulating sealing layer forming step of forming an insulating sealing layer on at least a cut surface of the second composite.
  • the insulating sealing layer forming step preferably includes a step of applying a precursor solution of the insulating sealing layer. More preferably, the precursor solution of the insulating sealing layer contains a solvent capable of dissolving the electrolyte membrane, and a part of the electrolyte membrane is dissolved with the solvent to form the insulating sealing layer.
  • the method for producing a membrane electrode assembly of the present invention may further include a step of joining the flow path plate to the fuel electrode of the second composite after the composite cutting step.
  • the precursor solution of the insulating sealing layer contains a solvent capable of dissolving the flow path plate, and a part of the flow path plate is dissolved with the solvent to form the insulating sealing layer.
  • the first complex may be cut while pressing around the cut portion of the first complex.
  • the adhesive strength at the interface between the side surface of the membrane electrode assembly comprising the fuel extreme surface, the electrolyte membrane end surface, and the air extreme surface and the insulating sealing layer can be increased, and the fuel and air are mixed.
  • leakage of fuel to the outside of the battery can be effectively prevented.
  • the area of the outer peripheral portion of the electrolyte membrane can be reduced as much as possible, or the outer peripheral portion that protrudes can be eliminated, and when mounted on a portable electronic device that allows only a limited mounting area Even so, the areas of the fuel electrode and the air electrode can be designed to be as large as possible, so that several watts of power necessary for power consumption can be supplied.
  • FIG. 2 is a cross-sectional view taken along line II-II shown in FIG. It is a figure which shows typically a preferable example of the manufacturing method of the membrane electrode assembly of this invention. It is a top view which shows typically another preferable example of the membrane electrode assembly of this invention. It is a perspective view which shows typically another preferable example of the membrane electrode assembly of this invention. It is a perspective view which shows typically another preferable example of the membrane electrode assembly of this invention. It is a perspective view which shows typically another preferable example of the membrane electrode assembly of this invention. It is a perspective view which shows typically the example of the stack structure (membrane electrode composite stack) which has arrange
  • the stack structure membrane electrode composite stack
  • FIG. 1 is a top view schematically showing a preferred example of the membrane electrode assembly of the present invention
  • FIG. 2 is a cross-sectional view taken along the line II-II shown in FIG.
  • a membrane electrode assembly 100 shown in FIGS. 1 and 2 includes an electrolyte membrane 101, a fuel electrode 102 formed on one surface of the electrolyte membrane 101, and an air electrode 103 formed on the other surface of the electrolyte membrane 101.
  • at least an insulating sealing layer 104 formed so as to be in contact with the side surfaces formed by the end face of the fuel electrode 102, the end face of the electrolyte membrane 101, and the end face of the air electrode 103 on two opposing sides of the membrane electrode assembly.
  • the side surface is a continuous surface composed of the end surface of the fuel electrode 102, the end surface of the electrolyte membrane 101, and the end surface of the air electrode 103.
  • the insulating sealing layer 104 is formed so as to cover the side surface.
  • the insulating sealing layer is formed on the side surface of the membrane electrode assembly including the fuel extreme surface, the electrolyte membrane end surface, and the air extreme surface, so that the outer peripheral portion of the electrolyte membrane is stable without being used as a diaphragm.
  • an electrical short circuit between the fuel electrode and the air electrode can be prevented.
  • the side surface of the membrane electrode assembly as a continuous surface composed of the fuel extreme surface, the electrolyte membrane end surface, and the air extreme surface, the insulating sealing layer disposed so as to cover the side surface can be made uniform. Since it can be formed with a thickness, local stress concentration on the side surface due to swelling or shrinkage of the insulating sealing layer due to a change in the external environment does not occur, and the adhesive strength of the insulating sealing layer to the side surface can be improved.
  • the protruding outer peripheral portion of the electrolyte membrane is not necessarily required, and the exposed area of the side surface of the electrolyte membrane is reduced by the insulating sealing layer, so that contamination of impurity ions into the electrolyte membrane is suppressed, and the membrane electrode composite Long-term reliability of body output can be obtained.
  • each member constituting the membrane electrode assembly will be described in detail.
  • the insulating sealing layer in the membrane electrode assembly of the present invention has a function of preventing a short circuit while maintaining electrical insulation between the fuel electrode and the air electrode while preventing mixing of the fuel and air and leakage of the fuel.
  • the insulating sealing layer is preferably formed by applying the precursor solution of the insulating sealing layer to a side surface composed of a continuous surface composed of the fuel extreme surface, the electrolyte membrane end surface, and the air extreme surface. By forming the insulating sealing layer by applying the precursor solution, the film thickness of the insulating sealing layer can be controlled on a submillimeter order.
  • the precursor solution of the insulating sealing layer is, for example, a solution containing a resin or the like constituting the insulating sealing layer and a monomer resin that is cured by addition of photosensitivity or a polymerization initiator.
  • the material of the insulating sealing layer is not particularly limited as long as it is a material having good bonding properties with the electrolyte membrane, and an organic polymer or an inorganic polymer can be used.
  • the organic polymer include an epoxy resin, an acrylic resin, a polyisobutylene resin, and a fluorine resin
  • examples of the inorganic polymer include a silicone resin.
  • the precursor solution of the insulating sealing layer preferably contains an organic solvent that dissolves or softens the electrolyte membrane.
  • an organic solvent such as methanol or ethanol as the organic solvent. Since the bonding area with the insulating sealing layer increases due to the softening of the electrolyte membrane, the electrolyte membrane and the insulating sealing layer can be firmly bonded.
  • the electrolyte membrane when using the hydrocarbon polymer described later as the electrolyte membrane, the electrolyte membrane is temporarily dissolved by using an organic solvent such as dimethylacetamide or tetrahydrofuran, which has higher solubility than the alcohol solvent, and is insulated and sealed. By resolidifying with the formation of the layer, the electrolyte membrane and the insulating sealing layer can be firmly bonded.
  • an organic solvent such as dimethylacetamide or tetrahydrofuran, which has higher solubility than the alcohol solvent
  • the electrolyte membrane in the membrane electrode assembly of the present invention has a function of transmitting protons from the fuel electrode to the air electrode, and has a function of maintaining electrical insulation between the fuel electrode and the air electrode and preventing a short circuit.
  • the material of the electrolyte membrane is not particularly limited as long as it has proton conductivity and electrical insulation, and a polymer membrane, an inorganic membrane, or a composite membrane can be used.
  • polymer membrane examples include Nafion (registered trademark, manufactured by DuPont), Aciplex (registered trademark, manufactured by Asahi Kasei), Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.), which are perfluorosulfonic acid electrolyte membranes. It is done. Also, styrene-based graft polymer, trifluorostyrene derivative copolymer, sulfonated polyarylene ether, sulfonated polyetheretherketone, sulfonated polyimide, sulfonated polybenzimidazole, phosphonated polybenzimidazole, sulfonated polyphosphazene. Hydrocarbon electrolyte membranes such as can also be used.
  • Examples of the inorganic film include glass phosphate, cesium hydrogen sulfate, polytungstophosphoric acid, ammonium polyphosphate, and the like.
  • Examples of the composite film include a composite of an inorganic material such as tungstic acid, cesium hydrogen sulfate, or polytungstophosphoric acid and an organic material such as polyimide, polyetheretherketone, or perfluorosulfonic acid.
  • the fuel electrode and air electrode in the membrane electrode assembly of the present invention are provided with a catalyst layer comprising a porous layer having at least a catalyst and an electrolyte.
  • the catalyst for the fuel electrode decomposes a fuel such as hydrogen gas or aqueous methanol solution into protons and electrons, and the electrolyte has a function of conducting the generated protons to the electrolyte membrane.
  • the catalyst for an air electrode has a function of generating water from protons that have been conducted through an electrolyte and oxygen in the air.
  • the catalyst for the fuel electrode and the air electrode may be supported on the surface of a conductor such as carbon or titanium.
  • the size of the catalyst and the conductor is preferably in the submicron order.
  • the catalyst layer can be regarded as a substantially uniform layer, and even when the fuel electrode and the air electrode are cut, a membrane electrode assembly can be obtained without causing an electrical short circuit between the two electrodes.
  • the electrolyte for the fuel electrode and the air electrode is preferably an organic polymer material.
  • FIG. 3 is a diagram schematically showing a preferred example of the method for producing a membrane electrode assembly of the present invention.
  • the membrane electrode assembly of the present invention as shown in FIG. 1 includes the fuel electrode of the first composite 301 having a laminated structure including a fuel electrode 102, an electrolyte membrane 101, and an air electrode.
  • an insulating sealing layer is formed on the cut surface 303 of the second composite 302. It is produced by this. That is, the side surface composed of a continuous surface composed of the fuel extreme surface, the electrolyte membrane end surface, and the air extreme surface is a cut surface 303 formed by cutting the first composite 301.
  • a sufficiently large membrane electrode complex (first complex) is produced, and then the membrane electrode complex (second complex) having a desired size is separated.
  • first complex the membrane electrode complex
  • second complex the membrane electrode complex having a desired size
  • the method for manufacturing a membrane electrode assembly of the present invention it is possible to consolidate the production of complex fuel electrodes and air electrodes and the production line of the complex into one, so that the manufacturing cost can be greatly reduced. .
  • FIG. 4 is a top view schematically showing another preferred example of the membrane electrode assembly of the present invention.
  • a membrane electrode assembly 400 shown in FIG. 4 includes an electrolyte membrane 401, a fuel electrode 402 (not shown) formed on one surface of the electrolyte membrane 401, and an air electrode formed on the other surface of the electrolyte membrane 401.
  • the side surface is a continuous surface composed of the end surface of the fuel electrode 402, the end surface of the electrolyte membrane 401, and the end surface of the air electrode 403.
  • the chevron-shaped uneven shape is formed.
  • the side surface composed of the fuel extreme surface, the electrolyte membrane end surface, and the air extreme surface has an uneven shape, the adhesion area between the side surface and the insulating sealing layer increases, so that the fuel and air Mixing and leakage of fuel to the outside of the battery can be prevented more effectively.
  • the concavo-convex shape does not necessarily have to be a mountain shape, but it is preferable that the concavo-convex shape is formed so that the side surface has a surface area that is twice or more the projected area.
  • the projected area of the side surface is an area obtained from the length and thickness of one side of the side surface, and the surface area of the side surface means an area obtained from the side length and thickness of one side of the side surface. That is, taking as an example the membrane electrode assembly shown in FIG. 4 having a mountain-shaped uneven shape, referring to FIG. 4, the length of one side of the side is A and the thickness is B (not shown).
  • FIG. 5 is a perspective view schematically showing still another preferred example of the membrane electrode assembly of the present invention.
  • the membrane electrode assembly 500 shown in FIG. 5 includes an electrolyte membrane 501, a fuel electrode 502 (not shown) formed on one surface of the electrolyte membrane 501, and the other of the electrolyte membrane 501, as in the above embodiment.
  • Insulation seal formed so as to be in contact with the side surface formed by the end face of the fuel electrode 502, the end face of the electrolyte membrane 501, and the end face of the air electrode 503 on the two opposite sides of the air electrode 503 formed on the surface.
  • At least a stop layer 504 is provided.
  • the side surface is a continuous surface composed of an end surface of the fuel electrode 502, an end surface of the electrolyte membrane 501, and an end surface of the air electrode 503.
  • the ratio L / H of the length L to the width H of the membrane electrode assembly 500 is 10 or more.
  • FIG. 6 is a perspective view schematically showing still another preferred example of the membrane electrode assembly of the present invention.
  • a membrane electrode assembly 600 shown in FIG. 6 is similar to that of the above-described third embodiment, but the end face of the fuel electrode 602 (not shown) and the electrolyte membrane on two opposite sides and another side of the membrane electrode assembly.
  • the side surface is a continuous surface composed of the end surface 601 and the end surface of the air electrode 603, and the insulating sealing layer 604 is formed on these side surfaces.
  • An insulating sealing layer may be formed on the side surface composed of the fuel extreme surface, the electrolyte membrane end surface, and the air extreme surface on all four sides of the membrane electrode assembly.
  • the width H of the membrane electrode assembly is preferably 10 mm or less.
  • the width H is 10 mm or less, oxygen in the air is easily taken in, a predetermined space is provided, and another membrane electrode composite is laminated on the air electrode of the membrane electrode composite.
  • the width H is short, it is possible to suppress a decrease in output due to lack of oxygen.
  • FIG. 7 is a perspective view schematically showing an example of a stack structure (membrane electrode composite stack) in which a plurality of membrane electrode composites of the present invention are arranged.
  • the membrane electrode composite stack shown in FIG. 7 has a membrane electrode composite 700 having a structure similar to that of the membrane electrode composite 600 shown in FIG. 6 parallel or substantially parallel to the side surface on which the insulating sealing layer is provided.
  • a plurality are arranged at predetermined intervals. In this way, when other membrane electrode complexes are arranged in a direction where there is no protruding outer peripheral portion of the electrolyte membrane, it is possible to widen the interval between the membrane electrode complexes. Even when stacked, air is easily supplied to the air electrode.
  • the membrane electrode assembly 700 may have a structure as shown in FIG.
  • the membrane electrode assembly 700 has a long side with a length L and a short side with a width H, and is formed adjacent to the air electrode, like the membrane electrode assembly 1400 shown in FIG. 14 to be described later.
  • a membrane electrode assembly including a metal conductive layer is preferable.
  • the material constituting the insulating sealing layer in the present embodiment generates water by taking out the output and reacting protons, electrons, and oxygen in the air at the air electrode, and the water forms the insulating sealing layer. Since it contacts, it is preferable that it is a water resistant resin. Further, when the output is increased due to the stack structure, the amount of heat generated with respect to the heat radiation area increases, and the membrane electrode assembly operates at a high temperature. For this reason, it is preferable that the material which comprises an insulating sealing layer is resin which has high heat resistance also with respect to the temperature around 100 degreeC. Thereby, even in a long-term operation, the function of the insulating sealing layer can be stably maintained for a long time.
  • FIG. 8 is a cross-sectional view schematically showing still another preferred example of the membrane electrode assembly of the present invention.
  • a membrane electrode assembly 800 shown in FIG. 8 includes a membrane electrode assembly similar to that in Embodiment 1, and a flow path plate 805 having the same width as the membrane electrode assembly, which is disposed adjacent to the fuel electrode 802. And an insulating sealing layer 804 is provided on a side surface including the end face of the flow path plate 805, the end face of the fuel electrode 802, the end face of the electrolyte membrane 801, and the end face of the air electrode 803.
  • the side surface includes a continuous surface composed of an end surface of the flow path plate 805, an end surface of the fuel electrode 802, an end surface of the electrolyte membrane 801, and an end surface of the air electrode 803.
  • the laminated structure including the fuel electrode 802, the electrolyte membrane 801, and the air electrode 803 is joined to the flow path plate 805 by the insulating sealing layer 804, so that the fuel is supplied to the flow path 806 of the flow path plate 805.
  • the fuel When supplied to the fuel, it is possible to prevent fuel leakage.
  • the channel plate in the membrane electrode assembly 800 of this embodiment has a function of supplying fuel to the fuel electrode 802.
  • the material of the flow path plate is a polymer material (plastic material) such as acrylic, ABS, polyvinyl chloride, polyethylene, polyethylene terephthalate, polyetheretherketone, Teflon (registered trademark), and copper, stainless steel, titanium, etc.
  • Metal materials can be used.
  • the material of the flow path plate is preferably a metal material, and more preferably a corrosion-resistant metal material such as stainless steel or titanium. This is because when the material of the flow path plate is metal, the effect of collecting electrons from the fuel electrode is imparted, the internal resistance of the membrane electrode assembly is reduced, and the reduction in output can be suppressed.
  • the flow path plate When a plastic material such as acrylic, ABS, polyvinyl chloride, polyethylene, or polyethylene terephthalate is used as the material constituting the flow path plate, the flow path plate is dissolved or softened in the precursor solution of the insulating sealing layer.
  • An organic solvent such as an ether or ester compound such as diethyl ether or ethyl acetate; a ketone compound such as acetone or methyl ethyl ketone; and an aromatic compound such as toluene or benzene is preferably contained.
  • an organic solvent such as an ether or ester compound such as diethyl ether or ethyl acetate; a ketone compound such as acetone or methyl ethyl ketone; and an aromatic compound such as toluene or benzene is preferably contained.
  • FIG. 9 is a cross-sectional view schematically showing still another preferred example of the membrane electrode assembly of the present invention.
  • a membrane electrode assembly 900 shown in FIG. 9 includes a flow path plate 905 having a larger width than the laminated structure including the fuel electrode 902, the electrolyte membrane 901, and the air electrode 903 adjacent to the fuel electrode 902.
  • An insulating sealing layer 904 formed so as to cover a side surface composed of the end surface, the end surface of the electrolyte membrane 901, and the end surface of the air electrode 903 and a part of the surface of the flow path plate 905 (the surface on the fuel electrode 902 side) is provided.
  • the side surface is a continuous surface composed of the end surface of the fuel electrode 902, the end surface of the electrolyte membrane 901, and the end surface of the air electrode 903. That is, the insulating sealing layer 904 is formed so as to cover the side surface, and is in contact with the surface of the flow path plate 905 on which the laminated structure including the fuel electrode 902, the electrolyte membrane 901, and the air electrode 903 is not laminated. It is formed and covers the flow path plate surface.
  • the accuracy of the width of the membrane electrode assembly can be affected by the accuracy of the thickness of the insulating sealing layer because the insulating sealing layer is formed by applying the precursor solution.
  • the width of the electrolyte membrane, the fuel electrode and the air electrode is smaller than the width of the flow path plate, the insulating sealing layer is not formed beyond the width of the flow path plate, The width of the membrane electrode assembly can be adjusted with high accuracy. Controlling the width of such a membrane electrode assembly improves the accuracy of the interval between the membrane electrode assemblies when a stack structure as shown in FIG. 7 in which a plurality of membrane electrode assemblies of the present invention are arranged is constructed. This prevents the supply of oxygen in the air from being obstructed unintentionally.
  • FIG. 10 is a cross-sectional view schematically showing still another preferred example of the membrane electrode assembly of the present invention.
  • the membrane electrode assembly 1000 shown in FIG. 10 uses, as a flow path plate, a flow path plate 1005 in which a groove for allowing the insulating sealing layer 1004 to permeate the surface of the fuel electrode 1002 is used.
  • the insulating sealing layer 1004 covers a side surface composed of a continuous surface composed of the end surface of the fuel electrode 1002, the end surface of the electrolyte membrane 1001, and the end surface of the air electrode 1003, and the end surface of the flow path plate 1005 and the surface on the fuel electrode 1002 side. A part of is covered.
  • the side surface of the fuel electrode 1002 and a part of the surface on the flow path plate 1005 side are bonded to the insulating sealing layer 1004, so that fuel leakage can be more effectively prevented.
  • FIG. 11 is a cross-sectional view schematically showing still another preferred example of the membrane electrode assembly of the present invention.
  • a membrane electrode assembly 1100 shown in FIG. 11 is the same as Embodiment 6 except that a flow path plate 1105 having a side surface (end surface) having a mountain-shaped uneven shape is used as the flow path plate. Thereby, since the side surface of the flow path plate 1105 and the insulating sealing layer 1104 are firmly bonded, the leakage of fuel can be more effectively prevented.
  • FIG. 12 is a cross-sectional view schematically showing still another preferred example of the membrane electrode assembly of the present invention.
  • a membrane electrode assembly 1200 shown in FIG. 12 includes a permeable membrane 1207 disposed between the fuel electrode 1202 and the flow path plate 1205.
  • the osmosis membrane 1207 is formed so as to cover the flow path 1206 of the flow path plate 1205 and to be adjacent to the fuel electrode 1202.
  • Other configurations are the same as those in the seventh embodiment.
  • the insulating sealing layer 1204 is formed so as to cover the side surface including the end surface of the osmotic membrane 1207, the end surface of the fuel electrode 1202, the end surface of the electrolyte membrane 1201, and the end surface of the air electrode 1203, and the osmotic membrane 1207, the fuel electrode 1202, and the electrolyte membrane 1201.
  • the air electrode 1203 are formed so as to be in contact with the surface of the non-laminated channel plate 1205 and cover the surface of the channel plate.
  • the osmotic membrane a membrane that allows the liquid fuel to pass through in the thickness direction by permeating and diffusing the liquid fuel can be used.
  • a membrane used in a membrane separation process such as dialysis, reverse osmosis, and pervaporation can be used.
  • the leakage of fuel can be suppressed by covering the flow path of the flow path plate with the permeable membrane.
  • the osmosis membrane can also give the function of limiting the supply rate of liquid fuel to the fuel electrode, the liquid fuel supply rate to the fuel electrode can be easily controlled by selecting the type of osmosis membrane to be used. it can.
  • an electrolyte with extremely high proton conductivity exhibits high solubility in liquid fuel.
  • supply of the liquid fuel to the anode by the osmosis membrane is also possible. By adjusting the speed, it is possible to prevent the electrolyte from dissolving and the fuel electrode from flowing out of the catalyst layer.
  • the material constituting the osmotic membrane is preferably a polymer membrane, particularly an organic polymer membrane, in that it is flexible and does not easily crack or break.
  • the organic polymer membrane is a solid polymer electrolyte membrane in that the utilization efficiency of the catalyst in the fuel electrode catalyst layer in which the continuity of the proton conduction path with the electrolyte membrane is not maintained can be improved. It is more preferable.
  • the solid polymer electrolyte membrane include a hydrocarbon solid polymer electrolyte membrane. Since the hydrocarbon-based solid polymer electrolyte membrane has a small swelling rate when in contact with the liquid fuel, the use of the hydrocarbon-based solid polymer electrolyte membrane affects the interface with the fuel electrode and the channel plate.
  • solid polymer electrolyte membrane examples include perfluorosulfonic acid, styrene-based graft polymer, trifluorostyrene derivative copolymer, sulfonated polyarylene ether, sulfonated polyether ether ketone, sulfonated polyimide, sulfonated poly
  • solid polymer electrolyte membranes having high proton conductivity such as benzimidazole, phosphonated polybenzimidazole, and sulfonated polyphosphazene.
  • a hydrocarbon solid polymer electrolyte membrane made of one or more polymer materials selected from the group consisting of a styrene-based graft polymer, a sulfonated polyarylene ether, a sulfonated polyetheretherketone, and a sulfonated polyimide is preferable.
  • a polymer membrane having a functional group such as hydroxyl group, amino group, carboxyl group, sulfone group, phosphoric acid group, ether group, ketone group may be used.
  • a film obtained by copolymerizing a combination of monomers such as hydroxyethyl methacrylate, polyvinyl pyrrolidone, dimethylacrylamide, and glycerol methacrylate.
  • FIG. 13 is a cross-sectional view schematically showing still another preferred example of the membrane electrode assembly of the present invention.
  • the membrane electrode assembly 1300 shown in FIG. 13 uses a flow path plate 1305 having a concavo-convex shape on the surface of the osmotic membrane 1307 as a flow path plate, and the osmotic membrane 1307 penetrates to the concave portion of the concavo-convex shape.
  • Other configurations are the same as those in the tenth embodiment. With such a configuration, the adhesive force between the flow path plate and the permeable membrane becomes stronger, so that leakage of fuel flowing through the flow path 1306 can be sufficiently prevented.
  • FIG. 14 is a cross-sectional view schematically showing still another preferred example of the membrane electrode assembly of the present invention. Similarly to the membrane electrode assembly shown in FIG. It is a figure which shows the cross section when cut
  • a membrane electrode assembly 1400 shown in FIG. 14 includes an electrolyte membrane 1401, a fuel electrode 1402 formed on one surface of the electrolyte membrane 1401, an air electrode 1403 formed on the other surface of the electrolyte membrane 1401, and a fuel electrode.
  • the metal conductive layer 1408 has a junction with the electrolyte membrane 1401 on the short side having the width H of the membrane electrode assembly 1400 having the long side having the length L and the short side having the width H. It is preferable. As a result, the metal conductive layer 1408 swells at the joint, and unnecessary stress is generated at the interface between the air electrode 1403 and the metal conductive layer 1408, and the occurrence of peeling can be suppressed, and the metal conductive layer 1408 Contact with the fuel electrode 1402 is prevented, and electrical insulation can be maintained well.
  • the metal conductive layer in the membrane electrode assembly of the present embodiment has a function of supplying electrons to the air electrode and a function of performing electrical wiring.
  • the material of the metal conductive layer is preferably a material that has a small specific resistance and can suppress a decrease in voltage even when current is taken in the plane direction, has electronic conductivity, and has corrosion resistance in an acidic atmosphere.
  • a metal material is more preferable.
  • noble metals such as Au, Pt, and Pd
  • metals other than noble metals such as Ti, Ta, W, Nb, Ni, Al, Cr, Ag, Cu, Zn, and Su
  • Si and nitriding of these metals And alloys such as stainless steel, Cu—Cr, Ni—Cr, and Ti—Pt are preferably used.
  • the material constituting the metal conductive layer contains at least one element selected from the group consisting of Pt, Ti, Au, Ag, Cu, Ni and W, among others.
  • the metal conductive layer is made of soft Au, Cu, Ag, It is preferable to use Zn, Su or the like.
  • the metal conductive layer can be easily cut, and a membrane electrode assembly can be obtained without causing an electrical short circuit between the fuel electrode and the air electrode.
  • the thickness is preferably 100 ⁇ m or less
  • the average fiber diameter of the fibers is preferably 100 ⁇ m or less.
  • the porosity is preferably 70% or more.
  • Example 1 As the electrolyte membrane, Nafion (registered trademark) 117 (manufactured by DuPont) having a size of 40 ⁇ 40 mm and a thickness of about 175 ⁇ m was used.
  • Nafion (registered trademark) 117 manufactured by DuPont having a size of 40 ⁇ 40 mm and a thickness of about 175 ⁇ m was used.
  • the catalyst paste was prepared according to the following procedure.
  • Catalyst-supported carbon particles (TEC66E50, manufactured by Tanaka Kikinzoku Co., Ltd.) comprising Pt particles, Ru particles, and carbon particles and having a Pt loading amount of 32.5 wt% and a Ru loading amount of 16.9 wt%, and 20 wt% Nafion alcohol
  • a solution manufactured by Aldrich
  • n-propanol, isopropanol, and zirconia balls are put in a fluorine polymer container at a predetermined ratio and mixed at 500 rpm for 50 minutes using a stirrer, thereby An electrode catalyst paste was prepared.
  • catalyst-carrying carbon particles (TEC10E50E, manufactured by Tanaka Kikinzoku Co., Ltd.) having a Pt-carrying amount of 46.8 wt% composed of Pt particles and carbon particles, the same conditions as the production conditions of the catalyst paste for the fuel electrode are used.
  • a catalyst paste for the air electrode was prepared.
  • each water repellent layer of a set of carbon paper 25BC, manufactured by SGL having a size of 23 ⁇ 23 mm and having a water repellent layer formed on one side
  • a fuel electrode having a thickness of about 300 ⁇ m and an air electrode were produced.
  • the fuel electrode and the electrolyte membrane are arranged so that the surfaces of the fuel electrode and the air electrode coated with the catalyst paste are in contact with the electrolyte membrane, and the positions of the fuel electrode and the air electrode are respectively overlapped with the center of the front and back of the electrolyte membrane.
  • the fuel electrode and the air electrode were bonded to the electrolyte membrane by hot pressing at 130 ° C. for 2 minutes to produce a membrane electrode assembly.
  • the membrane electrode assembly surface other than the cutting portion is pressed with an acrylic plate at intervals of 2 mm, and cut perpendicularly to the membrane electrode assembly with a stainless steel blade edge.
  • a plurality of membrane electrode composites having a width of 2 mm and a length of 40 mm were obtained.
  • the obtained membrane electrode composite having a width of 2 mm is sandwiched between two acrylic plates, aligned so that the side surface of the acrylic plate and the cut surface of the membrane electrode composite are aligned, and the cut surface and the side surface of the acrylic plate
  • an acrylic squeegee was slid to form an insulating sealing layer made of an epoxy resin on the entire cut surface.
  • the film thickness of the obtained epoxy resin was about 100 ⁇ m, and the width of the finally obtained membrane electrode assembly was about 2.2 mm and the length was 40 mm.
  • Example 2 A membrane electrode assembly was produced in the same manner as in Example 1 except that a regular triangular crest-shaped cutting edge with an amplitude of 0.5 mm was used as the cutting tooth. As a result of cross-sectional observation of the obtained membrane electrode assembly, the epoxy resin was sufficiently bonded to the respective end faces of the electrolyte membrane, the air electrode, and the fuel electrode.
  • Example 3 The membrane electrode before applying the epoxy resin in Example 1 to the cut surface on the flow path plate having a depth of 0.2 mm, a width of 1.0 mm, and a width of 2.0 mm. After the composite is laminated so that the fuel electrode is in contact with the flow path plate, it is sandwiched between two acrylic plates, and then consists of the flow path plate end face, the fuel extreme face, the electrolyte membrane end face, and the air extreme face. An epoxy resin was applied to the side surface to form an insulating sealing layer.
  • a Teflon (registered trademark) tube was connected to one end of the channel of the channel plate of the obtained membrane electrode composite, and a 3 mol / L aqueous methanol solution was supplied at a rate of 0.1 ml / min with a liquid feed pump. At this time, no leakage of fuel from the portion where the flow path plate and the membrane electrode assembly were bonded by the epoxy resin was observed.
  • the membrane electrode assembly of the present invention which can be designed to have a larger area for the fuel electrode and the air electrode than the restricted fuel cell installation area, and can prevent mixing of fuel and air and leakage of fuel to the outside of the cell, is portable.
  • the present invention can be suitably applied to electronic devices.

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

Abstract

L’invention concerne un ensemble électrodes-membrane (100), comprenant une membrane électrolyte (101), une électrode à combustible (102) formée sur une surface de la membrane électrolyte (101), et une électrode oxydoréductrice (103) formée sur l’autre surface de la membrane électrolyte (101). L’ensemble électrodes-membrane (100) présente, au moins sur un bord, une surface latérale constituant une surface continue comprenant au moins une face d’extrémité de l’électrode à combustible (102), une face d’extrémité de la membrane électrolyte (101) et une face d’extrémité de l’électrode oxydoréductrice (103), et la surface latérale est recouverte d’une couche d’étanchéité isolante (104). L’invention concerne également un procédé de fabrication de l’ensemble électrodes-membrane.
PCT/JP2009/058814 2008-05-13 2009-05-12 Ensemble électrodes-membrane et son procédé de fabrication WO2009139369A1 (fr)

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Cited By (1)

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JP2012074286A (ja) * 2010-09-29 2012-04-12 Dainippon Printing Co Ltd 膜−電極接合体中間体、膜−電極接合体、及び固体高分子形燃料電池、並びに膜−電極接合体中間体及び膜−電極接合体の製造方法

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US9283523B2 (en) * 2012-05-25 2016-03-15 Pbi Performance Products, Inc. Acid resistant PBI membrane for pervaporation dehydration of acidic solvents
JP7402193B2 (ja) * 2021-03-31 2023-12-20 森村Ｓｏｆｃテクノロジー株式会社 燃料電池単セルおよび燃料電池スタック

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JP2006236957A (ja) * 2005-01-31 2006-09-07 Uchiyama Mfg Corp 燃料電池用構成部材
WO2007058839A1 (fr) * 2005-11-14 2007-05-24 3M Innovative Properties Company Systeme de moulage de joint pour ensemble membrane-electrode
JP2007188849A (ja) * 2006-01-11 2007-07-26 Kokichi Uematsu 燃料電池セル及びスタックの構造
WO2007084472A2 (fr) * 2006-01-17 2007-07-26 Henkel Corporation Composants de pile à combustible à agent d'étanchéité intégré et procédés et systèmes pour les produire
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JP2012074286A (ja) * 2010-09-29 2012-04-12 Dainippon Printing Co Ltd 膜−電極接合体中間体、膜−電極接合体、及び固体高分子形燃料電池、並びに膜−電極接合体中間体及び膜−電極接合体の製造方法

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