WO2010061711A1 - シール構造および該シール構造を備えた燃料電池 - Google Patents
シール構造および該シール構造を備えた燃料電池 Download PDFInfo
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- WO2010061711A1 WO2010061711A1 PCT/JP2009/068651 JP2009068651W WO2010061711A1 WO 2010061711 A1 WO2010061711 A1 WO 2010061711A1 JP 2009068651 W JP2009068651 W JP 2009068651W WO 2010061711 A1 WO2010061711 A1 WO 2010061711A1
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- hard carbon
- carbon film
- seal
- seal structure
- structure according
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
- C23C16/0236—Pretreatment of the material to be coated by cleaning or etching by etching with a reactive gas
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
- C23C16/0281—Deposition of sub-layers, e.g. to promote the adhesion of the main coating of metallic sub-layers
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/04—Coating on selected surface areas, e.g. using masks
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/343—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one DLC or an amorphous carbon based layer, the layer being doped or not
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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
- H01M8/02—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
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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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0276—Sealing means characterised by their form
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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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/028—Sealing means characterised by their material
- H01M8/0282—Inorganic material
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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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/028—Sealing means characterised by their material
- H01M8/0284—Organic resins; Organic polymers
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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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
- H01M8/242—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes comprising framed electrodes or intermediary frame-like gaskets
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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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
- H01M8/2483—Details of groupings of fuel cells characterised by internal manifolds
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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
- H01M2008/1095—Fuel cells with polymeric electrolytes
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
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- 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
Definitions
- the present invention relates to a seal structure and a fuel cell having the seal structure.
- a fuel cell is a type of power generation device that extracts electrical energy by electrochemically oxidizing a fuel such as hydrogen or methanol, and has recently attracted attention as a clean energy supply source.
- Fuel cells are classified into phosphoric acid type, molten carbonate type, solid oxide type, solid polymer electrolyte type, etc., depending on the type of electrolyte used.
- the polymer electrolyte fuel cell (PEFC) supplies hydrogen (fuel gas) to one side of a membrane electrode assembly (MEA) in which electrodes are arranged on both sides of the electrolyte membrane, and oxygen (oxidizing gas) to the other side.
- MEA membrane electrode assembly
- This is a type of fuel cell that generates electricity at the same time, and since power density equivalent to that of an internal combustion engine can be obtained, research on practical application is currently widely conducted as a power source for electric vehicles and the like.
- Various types of MEA packaging methods such as a stack type, a pleat type, and a hollow fiber type have been proposed. Of these, a sheet-like MEA is stacked while being separated by a sheet-like separator.
- Stack type fuel cells are widely used. Such a stack type fuel cell seals the fuel gas and the oxidizing gas inside the fuel cell by providing a sealing material between MEAs and separators that overlap each other or between separators.
- the stack type fuel cell described in Japanese Patent Application Laid-Open No. 2006-107862 has a sealing structure using an adhesive as a sealing material, and does not perform a surface treatment on the adhesive-coated surface of the metal separator, and the separator base. By applying the adhesive directly to the material, the adhesiveness of the adhesive is improved.
- the present invention has been made to solve the above problems, and provides a seal structure capable of improving adhesion and reducing costs without using a wide variety of seal materials, and a fuel cell including the seal structure
- the purpose is to do.
- a component having a sealing surface on a facing surface, and a sealing material interposed between the sealing surfaces so as to closely contact the sealing surface, and one of the sealing surfaces or Both have a seal structure characterized in that at least a hard carbon film is formed.
- a second aspect of the present invention is a fuel cell having the seal structure.
- FIG. 1 is a cross-sectional view showing a seal structure according to the first embodiment.
- FIG. 2 is a cross-sectional view showing a seal structure according to the second embodiment.
- FIG. 3 is a cross-sectional view showing a seal structure according to the third embodiment.
- FIG. 4 is a cross-sectional view showing a seal structure according to the fourth embodiment.
- FIG. 5 is a cross-sectional view showing a seal structure according to the fifth embodiment.
- FIG. 6 is a cross-sectional view showing a modification of the seal structure according to the fifth embodiment.
- FIG. 7 is a cross-sectional view showing another modification of the seal structure according to the fifth embodiment.
- FIG. 8 is a cross-sectional view showing still another modification of the seal structure according to the fifth embodiment.
- FIG. 1 is a cross-sectional view showing a seal structure according to the first embodiment.
- FIG. 2 is a cross-sectional view showing a seal structure according to the second embodiment.
- FIG. 3 is a
- FIG. 9 is a cross-sectional view showing a seal structure according to the sixth embodiment.
- FIG. 10 is a cross-sectional view showing a seal structure according to the seventh embodiment.
- FIG. 11 is a process diagram showing a process of generating cracks in the hard carbon film.
- FIG. 12 is a cross-sectional view showing a seal structure according to the eighth embodiment.
- FIG. 13 is an enlarged view of a portion XIII in FIG.
- FIG. 14 is an SEM photograph observing the surface of the component shown in FIG.
- FIG. 15 is a TEM photograph observing a cross section of the component shown in FIG.
- FIG. 16 is an SEM photograph observing a cross section of the component shown in FIG.
- FIG. 17 is a cross-sectional view showing the seal structure of the fuel cell according to the ninth embodiment.
- FIG. 18 is a cross-sectional view showing a sealing structure of a polymer electrolyte fuel cell according to the tenth embodiment.
- FIG. 19 is a perspective view of a fuel cell separator according to an eleventh embodiment.
- 20 is a cross-sectional view taken along line XX-XX in FIG.
- FIG. 21 is a graph showing the contact resistance of the hard carbon film.
- FIG. 22 is a cross-sectional view of the fuel cell separator of the twelfth embodiment.
- FIG. 23 is a cross-sectional view of a fuel cell separator according to a modification of the twelfth embodiment.
- FIG. 24 is a cross-sectional view of the fuel cell separator of the thirteenth embodiment.
- FIG. 25 is a schematic sectional view of a fuel cell stack according to the eleventh to thirteenth embodiments.
- FIG. 26 is a flowchart showing a method of manufacturing a fuel cell separator.
- FIG. 27 is a cross-sectional view illustrating the lamination of base materials.
- FIG. 28 is a cross-sectional view when an insulating hard carbon film is formed.
- FIG. 29 is a conceptual diagram of a vehicle equipped with a fuel cell stack to which the present invention is applied.
- FIG. 1 is a cross-sectional view showing a seal structure according to the first embodiment of the present invention.
- the seal structure according to the first embodiment seals between the first component 1 and the second component 2.
- the first component 1 and the second component 2 are each composed of base materials 4 and 5, hard carbon films (DLC, diamond-like carbon) 6 and 7 covering the opposing surfaces of the base materials 4 and 5, and It has.
- the surfaces of the hard carbon films 6 and 7 become seal surfaces 8 and 9 that are in close contact with the seal material 3.
- a sealing material 3 is interposed between the sealing surfaces 8 and 9 so that the sealing surfaces 8 and 9 are in close contact with each other.
- the base materials 4 and 5 of the first component 1 and the second component 2 are not limited as long as the hard carbon films 6 and 7 can be formed, and the first component 1 and the second component 2 Different materials may be used. Further, the hard carbon films 6 and 7 do not necessarily need to cover the entire surfaces of the base materials 4 and 5, and may cover a range including a portion that is in close contact with the sealing material 3.
- a non-conductive or conductive hard carbon film can be used depending on the application of the component.
- the hard carbon film having conductivity will be described in detail later.
- the seal structure according to the first embodiment since the hard carbon films 6 and 7 are formed on the seal surfaces of the first component 1 and the second component 2, the first component 1 and the second component 2 are formed. Even when substrates having different surface characteristics are used, the adhesion of the sealing material 3 can be exhibited uniformly, and a stable sealing performance can be obtained.
- the hard carbon films 6 and 7 have excellent adhesion with the sealing material 3 made of resin or the like, a seal structure with excellent adhesion can be realized.
- FIG. 2 is a cross-sectional view showing a seal structure according to the second embodiment of the present invention.
- two (a plurality of) second component parts 2 and a third component part 11 are in close contact with the first component part 1 similar to that of the first embodiment by the sealing material 3. It has a structure.
- the surfaces of the base members 5, 12 facing the first component 1 are covered with the hard carbon films 7, 13.
- the adhesion of the sealing material can be improved by applying the seal structure according to the present invention.
- FIG. 3 is a sectional view showing a seal structure according to the third embodiment of the present invention.
- the first component 1 and the second component 16 are in close contact with the seal material 3 as in the first embodiment, but the seal surface 17 of the second component 16 is attached to the seal surface 17. It is different from the first embodiment in that a hard carbon film is not formed.
- the material of the base material 4 of the first component 1 is not limited as long as a hard carbon film can be formed. Further, the base material of the second component 16 may be a material different from the base material 4 of the first component 1. For the sealing material 3, it is preferable to select a material having high adhesion to the base material of the second component 16.
- the hard carbon film 6 that can exhibit high adhesion even if the seal material 3 is changed is formed on the first component 1, the hard carbon film is not formed second.
- the sealing material 3 in accordance with the base material of the component parts, it is possible to realize good adhesion of the sealing material 3.
- FIG. 4 is a sectional view showing a seal structure according to the fourth embodiment of the present invention.
- the first component 1 and the second component 2 are in close contact with the seal material 18 as in the first embodiment, but the width W1 of the seal material 18, that is, the seal In a cross section perpendicular to the surfaces 8 and 9, the width W1 of the seal material 18 in the direction parallel to the seal surfaces 8 and 9 is the width W2 of the hard carbon films 6 and 7 of the first component 1 and the second component 2. That is, it differs from the first embodiment in that it is formed narrower than the width W2 in the direction parallel to the seal surfaces 8 and 9 of the hard carbon films 6 and 7 in the cross section perpendicular to the seal surfaces 8 and 9.
- the sealing material 18 reliably adheres only to the hard carbon film, the excellent adhesion of the sealing material can be exhibited uniformly, and a stable sealing performance can be obtained. Can do.
- FIG. 6 is a cross-sectional view showing a modification of the seal structure according to the fifth embodiment
- FIG. 7 is according to the fifth embodiment.
- FIG. 8 is sectional drawing which shows the further another modification of the seal structure which concerns on 5th Embodiment.
- the seal structure according to the fifth embodiment is the first to fourth embodiments in that a convex portion or a concave portion is formed on at least one of the facing surfaces of the component parts, and the sealing material is in close contact with the convex portion or the concave portion. And different.
- the surfaces of the base materials 26 and 27 of the first component 21 and the second component 22 that face each other protrude in a direction perpendicular to the surface.
- Protrusions 23 and 24 are formed.
- the opposing surfaces of the base materials 26 and 27 are covered with hard carbon films 28 and 29, respectively, and the tip surfaces of the convex portions 23 and 24 covered with the hard carbon films 28 and 29 are substantially parallel to each other.
- the sealing surfaces 30 and 31 that are in close contact with the sealing material 25 are opposed to each other.
- the sealing material 25 is interposed between the sealing surfaces 30 and 31 so that the sealing surfaces 30 and 31 are in close contact with each other.
- the base materials 26 and 27 of the first component 21 and the second component 22 are not limited in material as long as the hard carbon films 28 and 29 can be formed, and are different between the first component 21 and the second component 22. It may be a material.
- recesses 35 and 36 are formed on the surfaces of the base members 38 and 39 of the first component 33 and the second component 34 that face each other.
- the opposing surfaces of the base materials 38 and 39 are respectively covered with the hard carbon films 40 and 41, and the bottom surfaces of the recesses 35 and 36 covered with the hard carbon films 40 and 41 face each other substantially in parallel.
- the sealing surfaces 42 and 43 are in close contact with the sealing material 37.
- the sealing material 37 is interposed between the sealing surfaces 42 and 43 so that the sealing surfaces 42 and 43 are in close contact with each other.
- the seal structure according to another modified example of the fifth embodiment is to closely contact the second component 34 having the recess 36 and the first component 44 having the flat surface 45.
- the opposing surfaces of the base members 39 and 47 of the first component 44 and the second component 34 are respectively covered with the hard carbon films 41 and 48, and the recesses 36 covered with the hard carbon films 41 and 48.
- the bottom surface and the flat surface 45 are seal surfaces 43 and 49 that face each other substantially in parallel and are in close contact with the seal material 46.
- the sealing material 46 is interposed between the sealing surfaces 43 and 49 so that the sealing surfaces 43 and 49 are in close contact with each other.
- the seal structure according to still another modified example of the fifth embodiment is to closely contact the first component 21 having the convex portion 23 and the second component 34 having the concave portion 36.
- the opposing surfaces of the base members 26 and 39 of the first component 21 and the second component are respectively covered with the hard carbon films 28 and 41, and the convex portions 23 covered with the hard carbon films 28 and 41.
- the front end surface and the bottom surface of the recess 36 face each other substantially in parallel to form seal surfaces 30 and 43 that are in close contact with the seal material 50.
- the sealing material 50 is interposed between the sealing surfaces 30 and 43 so that the sealing surfaces 30 and 43 are in close contact with each other.
- this surface can be used as the seal surface, and stable sealing performance can be obtained.
- the hard carbon film has excellent adhesion to the sealing material, a seal structure with excellent adhesion can be realized.
- the hard carbon film since it is not necessary to cover the entire base material, the hard carbon film only needs to cover a range including a portion that is in close contact with the sealing material.
- the hard carbon coating may be formed only on a portion having an uneven shape.
- the wettability of the hard carbon film was evaluated by comparing the critical surface tension of the metal surface on which the hard carbon film was formed with the critical surface tension of the metal surface plated with gold.
- the metal surface on which the hard carbon film is formed has a critical surface tension of about 1.3 times that of the gold-plated metal surface. It can be seen that it has higher wettability.
- 9 to 16 relate to seal structures according to sixth to eighth embodiments of the present invention. These embodiments differ from the above-described embodiments in that grooves are formed on the seal surface on which the hard carbon film is formed.
- FIG. 9 is a sectional view showing a seal structure according to the sixth embodiment of the present invention.
- the first component 51 and the second component 52 are in close contact with each other with the sealing material 55.
- the first component 51 and the second component This is different from the first embodiment in that a crack 56 is formed in the hard carbon films 53 and 54 of 52.
- the crack 56 is formed in each of the hard carbon films 53 and 54, but may be formed only in one of the hard carbon films.
- the crack 56 may or may not reach the base materials 4 and 5 of the first component 51 and the second component 52.
- the seal structure according to the sixth embodiment since the cracks 56 are formed in the hard carbon films 53 and 54, the contact area between the seal material 55 and the hard carbon films 53 and 54 is increased and the adhesion is achieved by the anchor effect. The performance is further improved, and more stable sealing performance can be obtained.
- FIG. 10 is a cross-sectional view showing a seal structure according to a seventh embodiment of the present invention
- FIG. 11 is a process diagram showing a process of generating a crack in the hard carbon film.
- the seal structure according to the seventh embodiment is similar to the sixth embodiment in the hard carbon films 66 and 67 of the first component 61 and the second component 62 having the recesses 63 and 64.
- a crack 68 is formed.
- a seal material 65 is provided between the recesses 63 and 64 facing each other.
- the opposing surfaces of the base materials 69 and 70 are covered with the hard carbon films 66 and 67
- the recess 63 is covered with the hard carbon films 66 and 67.
- 64 serve as sealing surfaces 71, 72 that are in close contact with the sealing material 65.
- a base material having a predetermined shape is cut out from a flat plate material (base material processing step: S1).
- a hard carbon film forming process is performed on the surface to be the sealing surface of the base material (hard carbon film forming step: S2).
- a final molding process is performed so as to deform at least the hard carbon film on the surfaces to be the seal surfaces 71 and 72 (final molding step: S3).
- the final forming step S3 is performed by, for example, press working for forming a shape such as a channel on the base material. If press working is used, a tensile or compressive force is applied to the hard carbon film, and cracks can be formed in the hard carbon film formed on the seal surface.
- the seal structure according to the seventh embodiment it is possible to obtain the seal surfaces 71 and 72 by coating the concavo-convex shape of the component parts with the hard carbon films 66 and 67, and stable sealing performance can be obtained. Furthermore, by forming the cracks 68 in the hard carbon films 66 and 67, the contact area between the sealing material 65 and the hard carbon films 66 and 67 is increased, and an anchor effect is also produced. Sealing performance can be obtained.
- the sealing material 65 is not provided between the concave portions 63 and 64 as described above, a portion where a crack can be generated by deformation, such as a convex portion and a concave portion, or between the convex portions, is used as the sealing surface.
- Other configurations can be used as long as they exist.
- the sealing surface forming method is a sealing surface forming method for forming a sealing surface for adhering a component part to another component, and after forming a hard carbon film in advance on a surface to be a sealing surface of a material, By deforming at least the surface on which the hard carbon film is formed, cracks are generated in the hard carbon film to form a seal surface.
- This sealing surface forming method intentionally deforms the surface on which the hard carbon film is formed, thereby generating cracks in the hard carbon film to form a sealing surface. It can be made to improve the adhesiveness with the sealing material of the said site
- FIG. 12 is a cross-sectional view showing a seal structure according to the eighth embodiment.
- the first component 73 and the second component 74 are brought into close contact with a sealant 79.
- Each of the two component parts 74 includes, in addition to the substrates 4 and 5 and the hard carbon films 77 and 78, intermediate layers 75 and 76 interposed therebetween, and the intermediate layers 75 and 76 are columnar crystals. It has a structure, and is different from the above-described embodiment in that a gap 80 constituting the groove is formed between the crystals.
- the gap 80 is formed on both the sealing surfaces of the first component 73 and the second component 74, but is formed only on one seal surface. It is good also as a structure.
- the configuration of the second component 74 will be described with reference to FIGS. Since the configuration of the first component 73 is the same as that of the second component 74, the description thereof is omitted here.
- FIG. 13 is an enlarged view of a portion XIII in FIG.
- the second component 74 includes a base material 5, a hard carbon film 78 formed on the outermost surface of the second component 74, and a space therebetween. And an intermediate layer 76 having a columnar crystal structure interposed between and a gap 80 between the crystals.
- the intermediate layer 76 has a function of improving the adhesion between the base material 5 and the hard carbon film 78 and a function of preventing elution of ions from the base material 5. The function is more remarkably exhibited when the substrate 5 is made of aluminum or an alloy thereof.
- a material that imparts the above-mentioned adhesion is preferable.
- Group 4 metals Ti, Zr, Hf
- Group 5 metals V, Nb, Ta
- Group 6 metals Cr, Mo, W
- their carbides nitriding And carbonitrides.
- metals with low ion elution such as chromium (Cr), tungsten (W), titanium (Ti), molybdenum (Mo), niobium (Nb) or hafnium (Hf), or their nitrides, carbides or charcoal are preferable.
- Nitride is used.
- Cr or Ti or a carbide or nitride thereof is used.
- the role of the intermediate layer 76 is to ensure adhesion with the upper hard carbon film 78 and to prevent corrosion of the underlying base material 5.
- the base material 5 is made of aluminum or an alloy thereof, corrosion proceeds due to moisture reaching the vicinity of the interface, and an aluminum oxide film is formed.
- Chromium and titanium or their carbides or nitrides are particularly useful in that, due to the formation of a passive film, even if exposed portions are present, their own elution is hardly observed.
- the metal especially Cr or Ti
- the thickness of the intermediate layer 76 is not particularly limited. However, from the viewpoint of making the size of the final product as small as possible by making the second component 74 thinner, the thickness of the intermediate layer 76 is preferably 0.01 ⁇ m to 10 ⁇ m, more preferably 0.8 ⁇ m. The thickness is 02 ⁇ m to 5 ⁇ m, more preferably 0.05 ⁇ m to 5 ⁇ m, and particularly preferably 0.1 ⁇ m to 1 ⁇ m. If the thickness of the intermediate layer 76 is 0.01 ⁇ m or more, a uniform layer is formed, and the corrosion resistance of the substrate 5 can be effectively improved.
- the thickness of the intermediate layer 76 is 10 ⁇ m or less, an increase in the film stress of the intermediate layer 76 is suppressed, and a decrease in film followability to the base material 5 and the occurrence of peeling / cracking associated therewith are prevented.
- the columnar crystal structure of the intermediate layer 76 refers to a structure in which metal crystals constituting the intermediate layer 76 grow in a columnar shape in the film thickness direction.
- the average thickness of the columnar crystal in the cross section of the intermediate layer 76 (referring to the average value of the columnar crystal column thickness in the cross section of the intermediate layer 76) is preferably 35 nm (upper limit 80 nm, lower limit 20 nm).
- the gap 80 is a gap formed between the columnar crystals of the intermediate layer 76, and the width of each is not particularly limited, but in the plan view, the width is 0.1 nm to 20 nm, and the length is in the range of 0.01 ⁇ m to 10 ⁇ m. It is preferable that it exists in. In addition, it is preferable that a large number of gaps 80 are uniformly distributed on the surface of the intermediate layer 76.
- the depth of the gap 80 is not particularly limited, but is preferably as large as possible within the range of the thickness of the intermediate layer 76 from the viewpoint of increasing the anchor effect.
- the width of the gap 80 is shown to be constant from the outermost surface side end to the base material side end in the film thickness direction, but FIG. 13 shows the shape of the columnar crystals.
- the gap 80 is widened from the substrate side toward the outermost surface side, the gap is widened from the outermost surface side toward the substrate side, Includes those in which the width of the gap irregularly changes from the outermost surface side end portion to the base material side end portion.
- the columnar crystals adjacent to each other with the gap 80 interposed therebetween are shown not to contact each other, but the columnar crystals adjacent to each other with the gap 80 interposed therebetween are separated from the outermost surface side end portion. Also included are ones that are in contact with each other at one or a plurality of locations on the side surface up to the substrate side end. Locally, the gaps 80 are distributed in a layer of the intermediate layer 76 so as to form a three-dimensional gap network.
- the hard carbon film 78 formed on the outermost surface of the second component 74 is composed of particles 78a having a diameter of 50 nm to 100 nm. Further, the hard carbon film 78 is not formed on the gap 80 having a sufficiently large width on the outermost surface of the intermediate layer 76.
- the groove portion is constituted by the portion where the hard carbon film 78 is absent and the gap 80.
- an aluminum plate having a desired thickness, or an alloy plate, a titanium plate, a stainless steel plate, or the like is prepared.
- the surface of the constituent material of the prepared base material 5 is degreased and washed using an appropriate solvent.
- the solvent ethanol, ether, acetone, isopropyl alcohol, trichloroethylene, a caustic agent, or the like can be used.
- the degreasing and cleaning treatment include ultrasonic cleaning.
- the ultrasonic cleaning conditions are a processing time of about 1 to 10 minutes, a frequency of about 30 to 50 kHz, and a power of about 30 to 50 W.
- the oxide film formed on the surface of the constituent material of the substrate 5 is removed.
- the method for removing the oxide film include a cleaning treatment with an acid, a dissolution treatment by applying a potential, or an ion bombardment treatment.
- a method in which alkali immersion cleaning, removal of an oxide film with alkali (alkali etching), surface activation with a hydrofluoric acid mixed acid solution, and subsequent zincate treatment in a zinc substitution bath is preferably used.
- the conditions for the zincate treatment are not particularly limited.
- the bath temperature is 10 to 40 ° C. and the immersion time is 20 to 90 seconds. Note that the oxide film removing step may be omitted.
- the intermediate layer 76 and the hard carbon film 78 are sequentially formed on the surface of the constituent material of the base material 5 subjected to the above-described treatment.
- the chromium intermediate layer 76 is laminated on the surface of the base material 5 (for example, aluminum or an alloy thereof) at a bias voltage described later, using the constituent material (for example, chromium) of the intermediate layer 76 as a target.
- a layer containing carbon is laminated on the surface of the intermediate layer 76 on the surface of the intermediate layer 76 using the constituent material (for example, graphite) of the hard carbon film 78 in order.
- middle layer 76 and the hard carbon film 78 can be formed sequentially.
- the adhesion between the hard carbon film 78, the intermediate layer 76, and the substrate 5 directly adhered thereto and the vicinity thereof is maintained for a long period of time due to intermolecular force and slight carbon atom penetration.
- PVD physical vapor deposition
- FCVA filtered cathodic vacuum arc
- sputtering method examples include a magnetron sputtering method, an unbalanced magnetron sputtering (UBMS) method, a dual magnetron sputtering method, and an ECR sputtering method.
- ion plating method examples include an arc ion plating method.
- sputtering method and an ion plating method it is preferable to use sputtering method and an ion plating method, and it is especially preferable to use sputtering method.
- a carbon layer with a low hydrogen content can be formed.
- the film can be formed at a relatively low temperature, and there is an advantage that damage to the substrate 5 can be minimized.
- the intermediate layer 76 having the columnar crystal structure can be obtained by controlling the bias voltage or the like.
- the intermediate layer 76 and the hard carbon film 78 are formed by sputtering, a negative bias voltage may be applied to the substrate 5 during sputtering.
- the intermediate carbon 76 having the columnar crystal structure and the hard carbon film 78 in which the graphite clusters are densely assembled are formed by the ion irradiation effect.
- Such an intermediate layer 76 can enhance the anticorrosion effect of the base material 5, and even a metal that easily corrodes such as aluminum can be applied as the base material 5.
- the component 74 is applied as a conductive member, the hard carbon film 78 exhibits excellent conductivity, which is advantageous in that the contact resistance with other conductive members can be further reduced.
- the absolute value of the negative bias voltage to be applied is not particularly limited, and a voltage capable of forming the hard carbon film 78 is adopted.
- the magnitude of the applied voltage is preferably 50 to 500V, more preferably 100 to 300V.
- the intermediate layer 76 is formed with a low bias voltage (may be more than 0V, more than 0V to 50V) so as not to deteriorate the roughness of the interface with the substrate 5.
- the optimal columnar crystal structure can be controlled through preliminary experiments and the like.
- the hard carbon film 78 is formed by the UBMS method, it is preferable to form the intermediate layer 76 in advance by the same apparatus and manufacturing method, and form the hard carbon film 78 thereon. Thereby, the intermediate
- the intermediate layer 76 may be formed by another method or apparatus, and the hard carbon film 78 may be formed by a different apparatus or manufacturing method. Even in this case, the intermediate layer 76 and the hard carbon film 78 having excellent adhesion to the base material 5 are formed.
- the intermediate layer 76 and the hard carbon film 78 are formed on one surface of the substrate 5.
- the intermediate layer 76 and the hard carbon film 78 may be formed on the other surface of the base material 5 by the same method.
- the component 74 in which the intermediate layer 76 and the hard carbon film 78 are formed on both surfaces of the substrate 5 at the same time is manufactured.
- a commercially available film forming apparatus double-sided simultaneous sputtering film forming apparatus
- the intermediate layer 76 and the hard carbon film 78 are formed on one surface of the substrate 5, and then the intermediate layer 76 and the hard carbon film 78 are formed on the other surface of the substrate 5.
- 78 may be formed sequentially. Alternatively, first, the intermediate layer 76 is formed on one surface of the substrate 5 in the apparatus using chrome as a target, and then the intermediate layer 76 is formed on the other surface. Thereafter, the target is switched to carbon, and a hard carbon film 78 is formed on the intermediate layer 76 formed on one surface, and then the hard carbon film 78 is formed on the other surface. As described above, even when the intermediate layer 76 and the hard carbon film 78 are formed on both surfaces of the base material 5, the same technique as that for forming the film on one surface is employed.
- the intermediate layer 76 and the hard carbon film 78 were formed on the surface of the substrate 5 by the above method.
- 14 to 16 are TEM photographs and SEM photographs in which the surface of the substrate 5 after film formation is observed.
- an aluminum plate (aluminum A1050) was prepared as a material for the substrate 5.
- the thickness of the aluminum plate is 200 ⁇ m.
- ultrasonic cleaning was performed in ethanol solution for 3 minutes as a pretreatment, and then the base material 5 was placed in a vacuum chamber, and ion bombardment treatment with Ar gas was performed to remove the oxide film on the surface.
- this intermediate layer 76 a solid graphite is used as a target by the UBMS method, and a negative bias voltage having a magnitude of 140 V is applied to the aluminum plate, while Cr layers (intermediate layer) on both sides of the aluminum plate are applied. 76), a hard carbon film 78 having a thickness of 0.2 ⁇ m was formed.
- FIG. 14 confirms that fine particles 78a having a diameter of 50 to 100 nm are present on the outermost surface, and a gap 80 having a width of about 20 nm and a length of about 1 ⁇ m is formed between them.
- the average thickness of the columnar crystals in the cross section of the intermediate layer 76 (referring to the average thickness of the columnar crystals in the cross section of the intermediate layer 76) is 35 nm (upper limit 80 nm, lower limit 20 nm). And the width of the gap formed between them can be confirmed to be 50 nm. It can also be confirmed that the film thickness of the Cr intermediate layer 76 is in the range of 0.02 ⁇ m to 5 ⁇ m.
- the hard carbon films 77 and 78 are formed on the outermost surfaces of the component parts 73 and 74, so that the seal on the seal surface is achieved.
- the wettability of the material is improved.
- the seal material 79 and the components 73 and 74 (specifically, the hard carbon film 77 are formed by the gap 80 formed between the columnar crystals of the intermediate layers 75 and 76. 78, and the intermediate layer 75, 76), the contact area increases, and an anchor effect also occurs. Since the width of the gap 80 irregularly changes in the film thickness direction as described above, the anchor effect is further strengthened. For this reason, the adhesiveness of the sealing material on the sealing surface is further improved, and more stable sealing performance can be obtained.
- an adhesion strength test of the seal structure according to this embodiment was performed according to a method defined in Japanese Industrial Standard (JIS-K-6850).
- JIS-K-6850 Japanese Industrial Standard
- the adherend the Cr intermediate layer and the hard carbon film according to the present embodiment were formed on the surface of a stainless steel plate (Examples 1 and 2), and the surface of the same stainless steel plate was directly used. That is, a material plated with gold without using an intermediate layer (comparative example) was used.
- the adhesive an olefin-based adhesive and a silicone-based adhesive were used.
- the maximum load at break of each test piece is proportional to the adhesive strength of each test piece. By dividing the maximum load at break of each example by the maximum load at break of the comparative example, the ratio of the bond strength of each example to the bond strength of the comparative example was determined. The obtained results are shown in Table 2.
- columnar crystal thickness refers to the average value of the columnar crystal column thickness in the cross section of the intermediate layer. From Table 2, Examples 1 and 2 have an adhesive strength 1.3 to 1.5 times that of the comparative example, and the seal structure according to this embodiment exhibits better adhesion. I understand.
- FIG. 17 is a cross-sectional view showing a seal structure of a fuel cell according to the ninth embodiment of the present invention.
- the seal structure according to the ninth embodiment is applied to a polymer electrolyte fuel cell (PEFC).
- PEFC polymer electrolyte fuel cell
- the fuel cell 90 is a unit of a fuel cell in which a set of sheet-like separators 95 (95 is not described in the drawing) and a sheet-like membrane electrode assembly 96 are laminated.
- the unit cell 94 is a stack type fuel cell made of a stacked body in which a plurality of single cells 94 are stacked.
- the number of stacked layers is not particularly limited, and may be a single unit cell 94 or a fuel cell stack in which a plurality of unit cells 94 are stacked.
- the separators 95a and 95c are obtained, for example, by forming a concavo-convex shape as shown in FIG. 17 by subjecting a thin plate having a thickness of 0.5 mm or less to a press treatment.
- the protrusions viewed from the MEA side of the separators 95 a and 95 c are in contact with the membrane electrode assembly 96. Thereby, the electrical connection with the membrane electrode assembly 96 is ensured.
- the recesses (spaces between the separator and the MEA generated due to the uneven shape of the separators) viewed from the MEA side of the separators 95a and 95c are gases for allowing the gas to flow during the operation of the fuel cell 90. Functions as a flow path.
- a fuel gas for example, hydrogen
- an oxidant gas for example, air
- the fuel cell 90 first has a solid polymer electrolyte membrane 97 and a pair of catalyst layers (an anode catalyst layer 98a and a cathode catalyst layer 98c) that sandwich the membrane.
- the laminate of the solid polymer electrolyte membrane 97 and the catalyst layers 98a and 98c is further sandwiched between a pair of gas diffusion layers (GDL) (anode gas diffusion layer 99a and cathode gas diffusion layer 99c).
- GDL gas diffusion layers
- the polymer electrolyte membrane 97, the pair of catalyst layers 98a and 98c, and the pair of gas diffusion layers 99a and 99c are laminated, and the electrolyte membrane support portion 100 is joined to the edge portion to form a membrane electrode joint.
- a body (MEA) 96 is constructed.
- the electrolyte membrane support unit 100 is formed of, for example, a thermosetting resin.
- the membrane electrode assembly 96 is further sandwiched between a pair of separators (anode separator 95a and cathode separator 95c). In the fuel cell stack, the membrane electrode assembly 96 is sequentially stacked via the separator 95 to constitute a stack.
- the recesses seen from the side opposite to the MEA side of the separators 95a and 95c serve as a refrigerant flow path 101 for circulating a refrigerant (for example, water) for cooling the fuel cell during operation of the fuel cell 90.
- a refrigerant for example, water
- the separator 95 is usually provided with a manifold (not shown). This manifold functions as a connection means for connecting cells when a stack is formed. With such a configuration, the mechanical strength of the fuel cell stack can be ensured.
- the conductive members constituting the separators 95a and 95c have a metal base layer 102 (base material) and a conductive carbon layer 103 (hard carbon film) formed on both surfaces of the metal base layer 102. Note that an intermediate layer made of another material may be interposed between the metal base layer 102 and the conductive carbon layer 103 as described above.
- the separator 95 and the electrolyte membrane support 100 are in close contact with each other by the first seal material 104, and the separators 95a and 95c that overlap each other are in close contact with each other by the second seal material 105 at the edge. .
- the electrolyte membrane support portions 100 that overlap each other are in close contact with each other by the third sealing material 106 at the edge.
- the metal base layer 102 is a main layer of a conductive member that constitutes the separator 95, and contributes to ensuring conductivity and mechanical strength.
- the metal constituting the metal base layer 102 is not particularly limited, and those conventionally used as constituent materials for metal separators can be used as appropriate.
- a constituent material of a metal base material layer iron, titanium, aluminum, and these alloys are mentioned, for example. These materials can be preferably used from the viewpoint of mechanical strength, versatility, cost performance, or processability.
- the iron alloy includes stainless steel.
- a metal base material layer is comprised from stainless steel, aluminum, or an aluminum alloy.
- the conductivity of the contact surface with the gas diffusion base material which is a constituent material of the gas diffusion layer can be sufficiently ensured. As a result, even if moisture enters the gaps between the rib shoulder film and the like, durability can be maintained due to the corrosion resistance of the oxide film formed on the metal base layer itself made of stainless steel.
- the thickness of the metal base layer 102 is not particularly limited. From the viewpoint of ease of processing and mechanical strength, and improvement of the energy density of the battery by reducing the thickness of the separator itself, it is preferably 50 to 500 ⁇ m, more preferably 80 to 300 ⁇ m, still more preferably 80 to 200 ⁇ m. In particular, the thickness of the metal base layer 102 when stainless steel is used as the constituent material is preferably 80 to 150 ⁇ m. On the other hand, when aluminum is used as a constituent material, the thickness of the metal base layer 102 is preferably 100 to 300 ⁇ m. When it is within the above range, it has excellent strength as a separator and is excellent in processability and can achieve a suitable thickness.
- the conductive carbon layer 103 is a layer containing conductive carbon. The presence of this layer ensures the conductivity of the conductive member constituting the separator 95) and improves the corrosion resistance as compared with the case of the metal base material layer 102 alone, and also improves the adhesion to the sealing material. be able to.
- the conductive carbon layer is applied to the hard carbon film that is in close contact with the sealing material. However, if the hard carbon film is provided only at the portion in contact with the sealing material, the conductivity in the hard carbon film is Since it is unnecessary, it is not always necessary to have conductivity.
- the conductive carbon layer 103 is defined by the intensity ratio R (I D / I G ) between the D band peak intensity (I D ) and the G band peak intensity (I G ) measured by Raman scattering spectroscopy. Is preferred. Specifically, the intensity ratio R (I D / I G ) is preferably 1.3 or more.
- the configuration requirement will be described in more detail.
- the intensity ratio R (I D / I G ) between the D band peak intensity (I D ) and the G band peak intensity (I G ) is the graphite cluster size of the carbon material and the disorder of the graphite structure (crystal structure defect), Used as an index such as sp 2 bond ratio. That is, in the present invention, it can be used as an index of contact resistance of the conductive carbon layer 103 and can be used as a film quality parameter for controlling the conductivity of the conductive carbon layer 103.
- the R (I D / I G ) value is calculated by measuring the Raman spectrum of the carbon material using a microscopic Raman spectrometer. Specifically, the peak intensity of 1300 ⁇ 1400 cm -1 called the D band (I D), the relative intensity ratio of the peak intensity of 1500 ⁇ 1600 cm -1 called the G band (I G) (peak area ratio ( I D / I G )).
- the R value is preferably 1.3 or more.
- the R value is more preferably 1.4 to 2.0, still more preferably 1.4 to 1.9, and further preferably 1.5 to 1.8. If this R value is 1.3 or more, a conductive carbon layer having sufficient conductivity in the stacking direction can be obtained. Moreover, if R value is 2.0 or less, the reduction
- the conductive carbon layer 103 may be substantially composed only of polycrystalline graphite or may be composed only of polycrystalline graphite, but the conductive carbon layer 103 is other than polycrystalline graphite. Other materials may also be included. Examples of the carbon material other than polycrystalline graphite that can be included in the conductive carbon layer 103 include graphite block (high crystalline graphite), carbon black, fullerene, carbon nanotube, carbon nanofiber, carbon nanohorn, and carbon fibril. Specific examples of carbon black include, but are not limited to, ketjen black, acetylene black, channel black, lamp black, oil furnace black, or thermal black. Carbon black may be subjected to a graphitization treatment.
- These carbon materials may be used in combination with a resin such as a polyester resin, an aramid resin, or a polypropylene resin.
- a resin such as a polyester resin, an aramid resin, or a polypropylene resin.
- materials other than the carbon material that can be included in the conductive carbon layer 103 include gold (Au), silver (Ag), platinum (Pt), ruthenium (Ru), palladium (Pd), rhodium (Rh), and indium.
- noble metals such as (In); water-repellent substances such as polytetrafluoroethylene (PTFE); and conductive oxides.
- materials other than polycrystalline graphite only 1 type may be used and 2 or more types may be used together.
- the thickness of the conductive carbon layer 103 is not particularly limited. However, it is preferably 1 to 1000 nm, more preferably 2 to 500 nm, and still more preferably 5 to 200 nm. If the thickness of the conductive carbon layer is within such a range, sufficient conductivity can be ensured between the gas diffusion base material and the separator. Moreover, the advantageous effect that a high corrosion-resistant function can be given with respect to a metal base material layer can be show
- the Vickers hardness of the conductive carbon layer 103 is defined.
- “Vickers hardness (Hv)” is a value that defines the hardness of a substance, and is a value inherent to the substance.
- the Vickers hardness means a value measured by a nanoindentation method.
- the nanoindentation method is a method in which the diamond indenter is continuously loaded and unloaded with a very small load on the sample surface, and the hardness is measured from the obtained load-displacement curve. Larger means that the substance is harder.
- the Vickers hardness of the conductive carbon layer 103 is preferably 1500 Hv or less, more preferably 1200 Hv or less, further preferably 1000 Hv or less, and particularly preferably 800 Hv or less. If the Vickers hardness is a value within such a range, excessive mixing of sp 3 carbon having no conductivity is suppressed, and the conductivity of the conductive carbon layer 103 can be prevented from being lowered. On the other hand, the lower limit value of the Vickers hardness is not particularly limited, but if the Vickers hardness is 50 Hv or higher, the hardness of the conductive carbon layer 103 is sufficiently ensured.
- the conductive carbon layer 103 and the intermediate layer can be more firmly adhered to each other, and an excellent conductive member can be provided.
- the Vickers hardness of the conductive carbon layer 103 is more preferably 80 Hv or more, further preferably 100 Hv or more, and particularly preferably 200 Hv or more.
- the Vickers hardness of the hard carbon film in this specification is contained in the said range.
- the method for manufacturing the conductive member described above is not particularly limited, and can be manufactured by appropriately referring to a conventionally known method. Hereinafter, an example for manufacturing a conductive member will be described. Further, since various conditions such as the material of each component of the conductive member constituting the separator 95 are as described above, the description thereof is omitted here.
- a stainless steel plate having a desired thickness is prepared, and then using a suitable solvent, the surface of the constituent material of the prepared metal base layer is degreased and washed. Subsequently, the oxide film formed on the surface (both sides) of the constituent material of the metal base layer is removed, and then the conductive carbon layer is formed on the surface of the constituent material of the metal base layer subjected to the above treatment. Is deposited.
- the details of these steps and the method suitably used for laminating (film-forming) conductive carbon have already been described in detail in the eighth embodiment, and thus description thereof is omitted here.
- a negative bias voltage may be applied to the metal base layer during sputtering.
- a conductive carbon layer having a structure in which graphite clusters are densely assembled can be formed by the ion irradiation effect. Since such a conductive carbon layer can exhibit excellent conductivity, a conductive member (separator) having a low contact resistance with other members (for example, MEA) can be provided.
- the magnitude (absolute value) of the negative bias voltage to be applied is not particularly limited, and a voltage capable of forming a conductive carbon layer can be adopted.
- the magnitude of the applied voltage is preferably 50 to 500V, more preferably 100 to 300V.
- the conductive carbon layer 103 is formed by the UBMS method, it is preferable to form an intermediate layer in advance and form the conductive carbon layer thereon. Thereby, the conductive carbon layer excellent in adhesiveness with the underlayer can be formed. However, when the conductive carbon layer is formed by another method, a conductive carbon layer having excellent adhesion to the metal substrate layer can be formed even when the intermediate layer is not present.
- the electrolyte layer is composed of, for example, a solid polymer electrolyte membrane 97.
- the solid polymer electrolyte membrane 97 has a function of selectively permeating protons generated in the anode catalyst layer 98a during operation of the fuel cell to the cathode catalyst layer 98c along the film thickness direction.
- the solid polymer electrolyte membrane 97 also has a function as a partition wall for preventing the fuel gas supplied to the anode side and the oxidant gas supplied to the cathode side from being mixed.
- the solid polymer electrolyte membrane 97 is roughly classified into a fluorine-based polymer electrolyte membrane and a hydrocarbon-based polymer electrolyte membrane depending on the type of ion exchange resin that is a constituent material.
- ion exchange resins constituting the fluorine-based polymer electrolyte membrane include Nafion (registered trademark, manufactured by DuPont), Aciplex (registered trademark, manufactured by Asahi Kasei Co., Ltd.), Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.), and the like.
- Perfluorocarbon sulfonic acid polymer perfluorocarbon phosphonic acid polymer, trifluorostyrene sulfonic acid polymer, ethylene tetrafluoroethylene-g-styrene sulfonic acid polymer, ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride- Examples include perfluorocarbon sulfonic acid polymers. From the viewpoint of improving power generation performance such as heat resistance and chemical stability, these fluorine-based polymer electrolyte membranes are preferably used, and particularly preferably fluorine-based polymer electrolytes composed of perfluorocarbon sulfonic acid polymers. A membrane is used.
- hydrocarbon electrolyte examples include sulfonated polyethersulfone (S-PES), sulfonated polyaryletherketone, alkylsulfonated polybenzimidazole, alkylphosphonated polybenzimidazole, sulfonated polybenzimidazole alkyl, Examples include phosphonated polybenzimidazole alkyl, sulfonated polystyrene, sulfonated polyetheretherketone (S-PEEK), and sulfonated polyphenylene (S-PPP).
- S-PES sulfonated polyethersulfone
- S-PEEK sulfonated polyetheretherketone
- S-PPP sulfonated polyphenylene
- the thickness of the electrolyte layer may be appropriately determined in consideration of the characteristics of the obtained fuel cell, and is not particularly limited.
- the thickness of the electrolyte layer is usually about 5 to 300 ⁇ m. When the thickness of the electrolyte layer is within such a range, the balance of strength during film formation, durability during use, and output characteristics during use can be appropriately controlled.
- the catalyst layers are layers in which the cell reaction actually proceeds. Specifically, the oxidation reaction of hydrogen proceeds in the anode catalyst layer 98a, and the reduction reaction of oxygen proceeds in the cathode catalyst layer 98c.
- the catalyst layer includes a catalyst component, a conductive catalyst carrier that supports the catalyst component, and an electrolyte.
- a composite in which a catalyst component is supported on a catalyst carrier is also referred to as an “electrode catalyst”.
- the catalyst component used in the anode catalyst layer is not particularly limited as long as it has a catalytic action in the oxidation reaction of hydrogen, and a known catalyst can be used in the same manner.
- the catalyst component used in the cathode catalyst layer is not particularly limited as long as it has a catalytic action for the oxygen reduction reaction, and a known catalyst can be used in the same manner. Specifically, it can be selected from metals such as platinum, ruthenium, iridium, rhodium, palladium, osmium, tungsten, lead, iron, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium, aluminum, and alloys thereof. .
- those containing at least platinum are preferably used in order to improve catalytic activity, poisoning resistance to carbon monoxide, heat resistance, and the like.
- the composition of the alloy depends on the type of metal to be alloyed, the content of platinum is preferably 30 to 90 atomic%, and the content of the metal to be alloyed with platinum is preferably 10 to 70 atomic%.
- an alloy is a generic term for a metal element having one or more metal elements or non-metal elements added and having metallic properties.
- the alloy structure consists of a eutectic alloy, which is a mixture of the component elements as separate crystals, a component element completely melted into a solid solution, and a component element composed of an intermetallic compound or a compound of a metal and a nonmetal.
- the catalyst component used in the anode catalyst layer and the catalyst component used in the cathode catalyst layer can be appropriately selected from the above.
- descriptions of the catalyst components for the anode catalyst layer and the cathode catalyst layer have the same definition for both. Therefore, they are collectively referred to as “catalyst components”.
- the catalyst components of the anode catalyst layer and the cathode catalyst layer do not have to be the same, and can be appropriately selected so as to exhibit the desired action as described above.
- the shape and size of the catalyst component are not particularly limited, and the same shape and size as known catalyst components can be adopted.
- the shape of the catalyst component is preferably granular.
- the average particle diameter of the catalyst particles is preferably 1 to 30 nm.
- the “average particle diameter of catalyst particles” in the present invention is the average of the crystallite diameter determined from the half-value width of the diffraction peak of the catalyst component in X-ray diffraction or the average particle diameter of the catalyst component determined from a transmission electron microscope image. It can be measured as a value.
- the catalyst carrier functions as a carrier for supporting the above-described catalyst component and an electron conduction path involved in the transfer of electrons between the catalyst component and another member.
- any catalyst carrier may be used as long as it has a specific surface area for supporting the catalyst component in a desired dispersion state and sufficient electron conductivity, and the main component is preferably carbon.
- Specific examples include carbon particles made of carbon black, activated carbon, coke, natural graphite, artificial graphite and the like.
- the main component is carbon means that the main component contains carbon atoms, and is a concept that includes both carbon atoms and substantially carbon atoms. In some cases, elements other than carbon atoms may be included in order to improve the characteristics of the fuel cell.
- substantially consisting of carbon atoms means that contamination of about 2 to 3% by mass or less of impurities can be allowed.
- the BET specific surface area of the catalyst carrier may be a specific surface area sufficient to carry the catalyst component in a highly dispersed state, but is preferably 20 to 1600 m 2 / g, more preferably 80 to 1200 m 2 / g.
- the specific surface area of the catalyst carrier is in such a range, the balance between the dispersibility of the catalyst component on the catalyst carrier and the effective utilization rate of the catalyst component can be appropriately controlled.
- the size of the catalyst carrier is not particularly limited, but from the viewpoint of easy loading, catalyst utilization, and catalyst layer thickness control within an appropriate range, the average particle size is about 5 to 200 nm, preferably 10 to 10 nm. About 100 nm is preferable.
- the amount of the catalyst component supported is preferably 10 to 80% by mass, more preferably 30 to 70% by mass, based on the total amount of the electrode catalyst.
- the supported amount of the catalyst component is within such a range, the balance between the degree of dispersion of the catalyst component on the catalyst support and the catalyst performance can be appropriately controlled.
- the amount of the catalyst component supported on the electrode catalyst can be measured by inductively coupled plasma emission spectroscopy (ICP).
- the catalyst layer contains an ion conductive polymer electrolyte in addition to the electrode catalyst.
- the polymer electrolyte is not particularly limited, and conventionally known knowledge can be referred to as appropriate.
- the ion exchange resin which comprises the electrolyte layer mentioned above can be added to a catalyst layer as a polymer electrolyte.
- the gas diffusion layers diffuse gas (fuel gas or oxidant gas) supplied through the gas flow paths 96a and 96c of the separator to the catalyst layers 98a and 98c. And a function as an electron conduction path.
- the material which comprises the base material of gas diffusion layer 99a, 99c is not specifically limited, A conventionally well-known knowledge can be referred suitably.
- a sheet-like material having conductivity and porosity such as a carbon woven fabric, a paper-like paper body, a felt, and a non-woven fabric can be used.
- the thickness of the substrate may be appropriately determined in consideration of the characteristics of the obtained gas diffusion layer, but may be about 30 to 500 ⁇ m. If the thickness of the substrate is within such a range, the balance between mechanical strength and diffusibility such as gas and water can be appropriately controlled.
- the gas diffusion layer preferably contains a water repellent for the purpose of further improving water repellency and preventing flooding.
- the water repellent is not particularly limited, but fluorine-based high repellents such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), polyhexafluoropropylene, and tetrafluoroethylene-hexafluoropropylene copolymer (FEP). Examples thereof include molecular materials, polypropylene, and polyethylene.
- the gas diffusion layer has a carbon particle layer (microporous layer; MPL, not shown) made of an aggregate of carbon particles containing a water repellent agent on the catalyst layer side of the substrate. You may have.
- MPL microporous layer
- the carbon particles contained in the carbon particle layer are not particularly limited, and conventionally known materials such as carbon black, graphite, and expanded graphite can be appropriately employed. Among them, carbon black such as oil furnace black, channel black, lamp black, thermal black, acetylene black and the like can be preferably used because of excellent electron conductivity and a large specific surface area.
- the average particle diameter of the carbon particles is preferably about 10 to 100 nm. Thereby, while being able to obtain the high drainage property by capillary force, it becomes possible to improve contact property with a catalyst layer.
- Examples of the water repellent used for the carbon particle layer include the same water repellents as described above.
- fluorine-based polymer materials can be preferably used because of excellent water repellency, corrosion resistance during electrode reaction, and the like.
- the mixing ratio of the carbon particles to the water repellent in the carbon particle layer is about 90:10 to 40:60 (carbon particles: water repellent) in terms of mass ratio in consideration of the balance between water repellency and electron conductivity. It is good.
- thermosetting resin for example, olefin resin, urethane resin, silicone resin, phenol resin, epoxy resin or unsaturated polyester can be used.
- the manufacturing method of the fuel cell is not particularly limited, and conventionally known knowledge can be appropriately referred to in the field of the fuel cell.
- the fuel used when operating the fuel cell is not particularly limited.
- hydrogen, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, secondary butanol, tertiary butanol, dimethyl ether, diethyl ether, ethylene glycol, diethylene glycol and the like can be used.
- hydrogen and methanol are preferably used in that high output is possible.
- a fuel cell stack having a structure in which a plurality of membrane electrode assemblies are stacked and connected in series via a separator may be formed so that the fuel cell can exhibit a desired voltage.
- the shape of the fuel cell is not particularly limited, and may be determined as appropriate so that desired battery characteristics such as voltage can be obtained.
- the first seal material 104 is between the hard carbon film and the resin material (electrolyte film support).
- the second sealing material 105 is in close contact with the hard carbon film
- the third sealing material 106 is in close contact with the resin material.
- the first to third sealing materials Even if the same sealing material is applied to 104, 105, 106, high adhesion can be realized in the sealing materials 104, 105, 106. That is, even if the same sealing material is applied to the first to third sealing materials 104, 105, and 106 by selecting the sealing material in accordance with the material of the electrolyte membrane support portion 90 on which the hard carbon film is not formed, all High adhesion can be realized in the sealing materials 104, 105, and 106.
- the conductive carbon layer 103 is used for the hard carbon film of the separator 95, the corrosion resistance and conductivity of the separator 95 can be secured, so that the hard carbon film is formed only for improving the adhesion with the sealing materials 104 and 105. There is no need to do.
- the separator 95 is shape
- FIG. 18 is a sectional view showing a sealing structure of a polymer electrolyte fuel cell (PEFC) according to the tenth embodiment of the present invention.
- PEFC polymer electrolyte fuel cell
- the fuel cell 109 according to the tenth embodiment has substantially the same configuration as the fuel cell 90 according to the ninth embodiment, and is different only in the configuration in which the hard carbon film 108 is formed on the electrolyte membrane support portion 107. .
- the electroconductivity is unnecessary for the electrolyte membrane support part 107, it is desirable to form the non-conductive hard carbon film 108.
- all of the first to third seal materials 104, 105, and 106 have the hard carbon films adhered to each other. Therefore, by applying the same sealing material to the first to third sealing materials 104, 105, and 106, high adhesion can be realized in all the sealing materials regardless of the material of the base material covered with the hard carbon film.
- FIG. 19 is a perspective view of a fuel cell separator according to an eleventh embodiment
- FIG. 20 is a cross-sectional view taken along line XX-XX in FIG. 19
- FIG. 21 is a graph showing contact resistance.
- the fuel cell separator 110 has a flat substrate 111.
- the base material 111 has a surface 113 (one surface) that extends in the surface direction of the base material 111, and an outer peripheral end surface 114 that extends from the outer peripheral edge of the surface 113 in the thickness direction of the base material 111.
- the surface 113 is formed with a manifold opening 115 for flowing fuel gas, oxidant gas, or cooling water, and a flow channel groove 112 for forming a flow channel communicating with the manifold opening 115.
- the fuel gas is, for example, hydrogen or methanol.
- the oxidant gas is, for example, air.
- the surface of the channel groove 112 is covered with a conductive conductive hard carbon film 120.
- the active area 116 of the surface 113 is covered with the conductive hard carbon film 120.
- the active area 116 is a region including the channel groove 112 on the surface 113, and an electrochemical reaction proceeds in the membrane electrode assembly when the separator 110 and the membrane electrode assembly (not shown) are stacked. This refers to the area that faces and opposes the area to be operated.
- the separator 110 further has an insulating hard carbon film 130 that is insulating.
- the insulating hard carbon film 130 covers the outer peripheral end surface 114 of the substrate 111 and the area around the area covered with the conductive hard carbon film 120 on the surface 113.
- a sealing material 140 is disposed on the surface 113 so as to surround a region covered with the conductive hard carbon film 120, and the insulating hard carbon film 130 includes an outer peripheral end surface 114 and an outer peripheral edge of the surface 113.
- the conductive hard carbon film 120 is in contact with the sealing material 140 at the outer peripheral edge in the surface direction. Note that the sealing material 140 is disposed on the surface 113 so as to surround the flow path groove 112, the periphery of the manifold opening 115 communicating with the flow path groove 112, and the periphery of the other manifold opening 115. .
- the base material 111 is made of metal and contributes to securing conductivity and mechanical strength. There is no restriction
- the constituent material of the base material 111 include iron, titanium, aluminum, and alloys thereof.
- the conductive hard carbon film 120 is a film containing conductive carbon.
- the conductive hard carbon film 120 is defined by an intensity ratio R (ID / IG) between a D band peak intensity (ID) and a G band peak intensity (IG) measured by Raman scattering spectroscopy.
- the intensity ratio R (ID / IG) is 1.3 or more.
- R is preferably 1.4 to 2.0, more preferably 1.4 to 1.9, and further preferably 1.5 to 1.8. If this R value is 1.3 or more, the conductive hard carbon film 120 with sufficient conductivity in the stacking direction can be obtained.
- R value is 2.0 or less, the reduction
- the conductive hard carbon film 120 has a polycrystalline graphite structure.
- “Polycrystalline graphite” has an anisotropic graphite crystal structure (graphite cluster) in which the graphene surface (hexagonal network surface) is laminated microscopically, but a large number of such graphite structures are aggregated macroscopically. Isotropic crystal. Therefore, it can be said that the polycrystalline graphite is a kind of diamond-like carbon (DLC).
- DLC diamond-like carbon
- the conductive hard carbon film 120 may be composed only of polycrystalline graphite, but the conductive hard carbon film 120 may include materials other than polycrystalline graphite. Examples of the carbon material other than polycrystalline graphite that can be included in the conductive hard carbon film 120 include carbon black, fullerene, carbon nanotube, carbon nanofiber, carbon nanohorn, and carbon fibril.
- the insulating hard carbon film 130 is a carbon film containing insulating carbon and has excellent insulating properties.
- the insulating hard carbon film 130 is, for example, a carbon film having a diamond-like crystal structure or a carbon film containing hydrogen.
- the thickness of the insulating carbon layer 130 is not particularly limited. However, it is preferably 1 to 1000 nm, more preferably 2 to 500 nm, and still more preferably 5 to 200 nm. If the thickness of the insulating carbon layer is a value within this range, sufficient insulation can be ensured. In addition, an advantageous effect of imparting higher corrosion resistance to the metal substrate layer can be obtained.
- FIG. 21 is a graph showing the contact resistance of the hard carbon film under the condition where the contact surface pressure is 1 MPa. As shown in FIG.
- the contact resistance of the oxide film produced by the pickling treatment is 100 to 1000 m ⁇ ⁇ cm 2
- the contact resistance of the insulating hard carbon film 130 is 5000 to 11000 m ⁇ ⁇ cm 2
- the insulating hard carbon film 130 has superior insulating properties as compared with the oxide film.
- the contact resistance of the conductive hard carbon film 120 is 20 m ⁇ ⁇ cm 2 or less.
- the separator for a fuel cell serves to electrically connect single cells to each other and to flow fuel gas or oxidant gas through the fuel cell stack. For this reason, it is preferable that the separator for fuel cells is excellent in both conductivity and corrosion resistance.
- the separator for fuel cells is excellent in both conductivity and corrosion resistance.
- the separator when the separator is cooled by cooling water, external air may come into contact with the outer peripheral portion to cause dew condensation, and the separator and other equipment or other articles may cause water due to dew condensation. There is a risk of electrical connection via the cable. The same was true when water flowing through the separator or water generated in the fuel cell stack adhered to the outer periphery of the separator.
- the outer peripheral portion of the separator is easy to come into contact with other devices or the like due to the configuration, and there is a possibility that electrical connection through attached water or electrical connection by direct contact may occur.
- a passive film is formed on the surface of the outer peripheral portion, a temporary insulation can be obtained, but the insulation is not sufficient as described with reference to FIG.
- an insulating hard carbon film 130 showing superior insulating properties as compared with an oxide film covers the outer peripheral end surface 114 of the substrate 111. For this reason, even when water adheres to the outer peripheral portion of the separator 110, the separator 110 can inhibit electrical connection with other articles or devices by the insulating hard carbon film 130 and has excellent insulating properties. Further, since the insulation at the outer peripheral portion is good, for example, it is not necessary to separately provide an insulating cover or the like, and the apparatus can be downsized or the cost can be reduced.
- the separator 110 Since the separator 110 has the conductive hard carbon film 120, the separator 110 has high corrosion resistance as compared with the case of the base material 111 alone while ensuring conductivity.
- the insulating hard carbon film 130 covers not only the outer peripheral end surface 114 of the substrate 111 but also the area around the area covered with the conductive hard carbon film 120 on the surface 113.
- the insulating hard carbon film 130 covers not only the outer peripheral end surface 114 but also the region from the outer peripheral edge of the surface 113 to the sealing material 140. For this reason, for example, since the electrical connection through the surface 113 between the water produced by condensation on the outer peripheral portion of the separator 110 and the base material 111 can be prevented, the insulating hard carbon film 130 covers only the outer peripheral end surface 114. Compared to the above, the insulation is further improved.
- FIG. 22 is a cross-sectional view of a fuel cell separator according to a twelfth embodiment.
- the fuel cell separator 200 of the twelfth embodiment is substantially the same as the eleventh embodiment, but the range in which the insulating hard carbon film 230 covers the substrate 210 is different from the eleventh embodiment. .
- the insulating hard carbon film 230 includes an outer peripheral end surface 213, a region from the outer peripheral edge of the surface 212 (one surface) to the seal material 240, and a seal material 240 to a conductive hard carbon film 220 on the surface 212. And an area up to the outer peripheral edge. That is, the boundary between the conductive hard carbon film 220 and the insulating hard carbon film 230 is located inside the sealing material 240.
- the twelfth embodiment ensures insulation not only on the outside of the sealing material 240 but also on the inside of the sealing material 240, and in addition to the effects of the eleventh embodiment, it can be said that the insulation can be further improved. There is an effect.
- FIG. 23 is a cross-sectional view of a fuel cell separator according to a modification of the twelfth embodiment. As shown in FIG. 23, even if the position of the boundary between the region covered with the insulating hard carbon film 230A and the region covered with the conductive hard carbon film 220A is shifted in the surface direction on both surfaces of the separator 200A. Good.
- FIG. 24 is a cross-sectional view of the fuel cell separator of the thirteenth embodiment.
- the separator 300 of the thirteenth embodiment is substantially the same as the eleventh embodiment, except that the insulating hard carbon film 330 covers the substrate 310 and the conductive hard carbon film 320 is based on the range.
- the range covering the material 310 is different from the eleventh embodiment.
- the insulating hard carbon film 330 covers only the outer peripheral end surface 313, and the conductive hard carbon film 320 covers the entire surface 312 (one surface).
- the thirteenth embodiment has substantially the same effect as the eleventh embodiment.
- the film formation time of the insulating hard carbon film 330 can be shortened compared to the eleventh embodiment.
- the insulating hard carbon film and the conductive hard carbon film are formed so as not to overlap each other.
- the insulating hard carbon film is formed on the conductive hard carbon film. It may be formed to overlap.
- the insulating hard carbon film 130 may be formed so as to overlap in a range where insulation is required.
- FIG. 25 is a schematic cross-sectional view of the fuel cell stack.
- the fuel cell stack 500 has a structure in which a plurality of single cells 502 that exhibit a power generation function are stacked.
- the single cell 502 includes a membrane electrode assembly 501 that promotes an electrochemical reaction, and a pair of separators 400 that sandwich the membrane electrode assembly 501.
- the separator 400 has the same configuration as that in the eleventh embodiment.
- the separator 400 may have a configuration similar to that of the twelfth embodiment.
- the fuel cell stack 500 has a configuration in which the separators 400 overlap each other at a portion where the single cells 502 are in contact with each other. Between the separators 400 that overlap each other, the insulating hard carbon coatings 430 are in contact with each other.
- the fuel cell stack 500 includes the separator 400 having the same configuration as the separator according to the eleventh embodiment or the twelfth embodiment, the same effects as those described above can be obtained.
- the insulating hard carbon films 430 are in contact with each other in the separators 400 that overlap each other, it is possible to suppress the ingress of water and ensure the insulation between the inside and the outside of the fuel cell stack 500.
- FIG. 26 is a flowchart showing a method of manufacturing a fuel cell separator
- FIG. 27 is a cross-sectional view for explaining lamination of base materials
- FIG. 28 is a cross-sectional view when an insulating hard carbon film is formed.
- the base material 111 is first formed (S11). Then, the base material 111 is put into a conductive hard carbon film forming apparatus, and a conductive hard carbon film 120 is formed (S12). Next, the base material 111 is taken out (S13), and the base material 111 is laminated via the buffer member disposed on the surface 113 (lamination process: S14). The laminated base material 111 (laminated body) is put into an insulating hard carbon film forming apparatus to form an insulating hard carbon film (insulating hard carbon film forming step: S15). Thereafter, the laminated body is taken out (S16).
- a metal plate such as stainless steel or titanium is pressed to form the base material 111 having a predetermined shape.
- the substrate 111 is ultrasonically cleaned in ethanol as a pretreatment. Then, the base material 111 is installed in the vacuum chamber, and ion bombardment treatment with Ar gas is performed to remove the surface oxide film and impurities.
- UBMS unbalanced magnetron sputtering
- Cr is used as a target, and a Cr film is formed on both surfaces of the substrate 111.
- the conductive hard carbon film 120 is formed on necessary portions of both surfaces of the base material 111 by applying a negative bias voltage of 110 V to the base material 111 using solid graphite as a target by the UBMS method.
- the base material 111 when the base material 111 is laminated, the base material 111 is laminated with a buffer member interposed between the laminated members.
- a buffer member is disposed on the surface 113 so as to surround the flow channel groove 112, and among the plurality of stacked base materials 111, the channel A cover 520 for covering the groove 112 is disposed.
- the cover 20 may be a resin film or a metal plate as long as it can mask the flow channel 112.
- the sealing material 140 is used as a buffer member.
- the film formation of the insulating hard carbon film 130 is the same as the film formation of the conductive hard carbon film 120 from the pretreatment to the film formation of the Cr film.
- a hydrocarbon gas such as benzene or methane gas is used as a raw material, and plasma is generated by high frequency discharge in a vacuum chamber, and carbon or hydrogen is formed on the substrate 111 by a plasma CVD method. Evaporate.
- the insulating hard carbon film 130 is formed on the outer peripheral end surface 114 and the region from the outer peripheral edge to the seal material 140 on the surface 113.
- the insulating hard carbon film 130 may be formed on the conductive hard carbon film 120 in an overlapping manner. That is, in S12, a conductive hard carbon film is formed on the entire surface 113 of the base material 111, and in S15, the insulating hard carbon film is formed so as to overlap in a range where insulation is required. Good.
- the insulating hard carbon film 130 is formed on the outer peripheral end surface 114 of the substrate 111 and the region of the surface 113 from the outer peripheral edge to the sealing material 140. For this reason, the manufactured separator 110 has the effects described in the eleventh embodiment, and the method for manufacturing a fuel cell separator of the present invention can provide a fuel cell separator having excellent insulating properties.
- the separator manufacturing method since the insulating coating 130 is formed in a state where the base materials 111 are laminated, a plurality of base materials 111 can be formed at a time, and the productivity is good.
- the flow path grooves 112 formed on the outer surfaces 113 of the base material 111 located at both ends in the stacking direction are covered with the cover 520, and the other flow path grooves 112 are sealing materials positioned between the layers. Since it is sealed by 140 (buffer member), the insulating hard carbon film 130 is not formed in the channel groove 112 and can be reliably formed at a necessary location.
- the sealing material 140 is used as a buffering member disposed between the base material 111 and the base material 111, a buffering member is prepared separately from the sealing material 140. It is not necessary to reduce the cost.
- the fuel cell or the fuel cell stack according to the above-described embodiment can be mounted as a driving power source in a vehicle, for example.
- FIG. 29 is a conceptual diagram of a vehicle equipped with the fuel cell stack of the above-described embodiment.
- the fuel cell stack 801 may be mounted under the seat at the center of the vehicle body of the fuel cell vehicle 800. If it is installed under the seat, the interior space and the trunk room can be widened.
- the place where the fuel cell stack 801 is mounted is not limited to the position under the seat, but may be a lower part of the rear trunk room or an engine room in front of the vehicle.
- a vehicle equipped with the fuel cell of the above-described form is also included in the technical scope of the present invention.
- the seal structure of the present embodiment is not limited to the fuel cell and can be used for various applications.
- PEFC phosphoric acid fuel cell
- MCFC molten carbonate fuel cell
- SOFC solid oxide fuel cell
- AFC alkaline fuel cell
- a combination of each element of the above embodiment and the above embodiment is also included in the technical scope of the present invention.
- the groove portions according to the sixth to eighth embodiments are applied to the seal structures, fuel cell separators, fuel cells, or vehicles according to the first to fifth and ninth to thirteenth embodiments. Included in the range.
- the seal structure according to the present invention since the hard carbon film is formed on the seal surface that is in close contact with the seal structure, a seal structure in which the adhesion with the seal material is further improved is provided. According to the seal structure, it is not necessary to consider the adhesion of the base material to the seal material, and the cost can be reduced by reducing the types of seal materials. In addition, since the fuel cell having the seal structure has a simple structure and excellent productivity, it can be suitably used in many applications regardless of whether it is for mobile use, stationary use, or automobile use.
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Abstract
Description
特開2006-107862号公報に記載のスタック型燃料電池は、シール材として接着剤を使用したシール構造を備えており、金属セパレータの接着剤塗布面に対して表面処理を行わず、セパレータの基材に直接接着剤を塗布することで、接着剤の接着性を向上させている。
図1は、本発明の第1実施形態に係るシール構造を示す断面図である。
図2は、本発明の第2実施形態に係るシール構造を示す断面図である。
図3は、本発明の第3実施形態に係るシール構造を示す断面図である。
図4は、本発明の第4実施形態に係るシール構造を示す断面図である。
図5は、本発明の第5実施形態に係るシール構造を示す断面図、図6は、第5実施形態に係るシール構造の変形例を示す断面図、図7は、第5実施形態に係るシール構造の他の変形例を示す断面図、図8は、第5実施形態に係るシール構造の更に他の変形例を示す断面図である。
図9は、本発明の第6実施形態に係るシール構造を示す断面図である。
図10は、本発明の第7実施形態に係るシール構造を示す断面図、図11は、硬質炭素皮膜にクラックを生じさせる工程を示す工程図である。
図12は、第8実施形態に係るシール構造を示す断面図である。
第8実施形態に係るシール構造は、第1実施形態と同様に、第1構成部品73と第2構成部品74の間をシール材79で密着させるものであるが、第1構成部品73および第2構成部品74が、各々、基材4,5および硬質炭素皮膜77,78に加えて、それらの間に介在する中間層75、76を備えており、該中間層75、76が、柱状結晶構造を有しており、その結晶の間に、前記溝部を構成する隙間80が形成されている点で、上述の実施形態と異なる。
図17は、本発明の第9実施形態に係る燃料電池のシール構造を示す断面図である。
金属基材層102は、セパレータ95を構成する導電部材の主層であり、導電性および機械的強度の確保に寄与する。
導電性炭素層103は、導電性炭素を含む層である。この層の存在によって、セパレータ95)を構成する導電部材の導電性を確保しつつ、金属基材層102のみの場合と比較して耐食性が改善されるとともに、シール材との密着性を向上させることができる。なお、本実施形態では、導電性炭素層をシール材と密着させる硬質炭素皮膜に適用しているが、硬質炭素皮膜をシール材と接する部位にのみ設けるのであれば、硬質炭素皮膜において導電性は不要であるため、かならずしも導電性を備える必要はない。
上述した導電部材を製造する方法は、特に制限はなく、従来公知の手法を適宜参照することにより製造することが可能である。以下、導電部材を製造するための一例を示す。また、セパレータ95を構成する導電部材の各構成要素の材質などの諸条件については、上述した通りであるため、ここでは説明を省略する。
電解質層は、例えば、固体高分子電解質膜97から構成される。この固体高分子電解質膜97は、燃料電池の運転時にアノード触媒層98aで生成したプロトンを膜厚方向に沿ってカソード触媒層98cへと選択的に透過させる機能を有する。また、固体高分子電解質膜97は、アノード側に供給される燃料ガスとカソード側に供給される酸化剤ガスとを混合させないための隔壁としての機能をも有する。
触媒層(アノード触媒層98a,カソード触媒層98c)は、実際に電池反応が進行する層である。具体的には、アノード触媒層98aでは水素の酸化反応が進行し、カソード触媒層98cでは酸素の還元反応が進行する。
ガス拡散層(アノードガス拡散層99a,カソードガス拡散層99c)は、セパレータのガス流路96a,96cを介して供給されたガス(燃料ガスまたは酸化剤ガス)の触媒層98a,98cへの拡散を促進する機能、および電子伝導パスとしての機能を有する。
シール材は、特に限定されないが、例えば、熱硬化性樹脂を適用できる。熱硬化性樹脂には、例えばオレフィン樹脂、ウレタン樹脂、シリコーン樹脂、フェノール樹脂、エポキシ樹脂または不飽和ポリエステル等が使用できる。
図18は、本発明の第10実施形態に係る固体高分子形燃料電池(PEFC)のシール構造を示す断面図である。
図19は、第11実施形態に係る燃料電池用セパレータの斜視図、図20は、図19のXX-XX線に沿う断面図、図21は、接触抵抗を示すグラフである。
また、好ましい実施形態において、当該Rは、好ましくは1.4~2.0であり、より好ましくは1.4~1.9であり、さらに好ましくは1.5~1.8である。このR値が1.3以上であれば、積層方向の導電性が十分に確保された導電性硬質炭素皮膜120が得られる。また、R値が2.0以下であれば、グラファイト成分の減少を抑制することができる。さらに、導電性硬質炭素皮膜120自体の内部応力の増大をも抑制でき、下地である基材111との密着性を一層向上できる。
図21は、接触面圧を1MPaとした条件下での硬質炭素皮膜の接触抵抗を示すグラフである。図21に示すように、酸洗処理によって生成した酸化皮膜の接触抵抗が100~1000mΩ・cm2であるのに対し、絶縁性硬質炭素皮膜130の接触抵抗は、5000~11000mΩ・cm2であり、絶縁性硬質炭素皮膜130は酸化皮膜に比べて、優れた絶縁性を有する。なお、導電性硬質炭素皮膜120の接触抵抗は、20mΩ・cm2以下である。
しかし、従来の燃料電池用セパレータでは、セパレータが冷却水によって冷却されているとき、外周部分に外気が触れて結露が生じる場合があり、セパレータと他の機器または他の物品とが、結露による水を介して電気的に接続する虞があった。また、セパレータを流れる水、または燃料電池スタック内で生成された水等がセパレータの外周部に付着したときも同様であった。特に、構成上、セパレータの外周部分は他の機器等に接触し易く、付着した水を介しての電気的接続、または直接接触することによる電気的接続が生じる虞があった。
外周部分の表面に不動態皮膜を形成した場合、一応の絶縁性を得ることができるが、図21を用いて説明した通り、その絶縁性は十分でなかった。
図22は、第12実施形態の燃料電池用セパレータの断面図である。
図23は、第12実施形態の変形例に係る燃料電池用セパレータの断面図である。
図23に示すように、絶縁性硬質炭素皮膜230Aで覆われた領域と導電性硬質炭素皮膜220Aで覆われた領域との境界の位置は、セパレータ200Aの両面において、面方向にずれていてもよい。
図24は、第13実施形態の燃料電池用セパレータの断面図である。
図25は、燃料電池スタックの概略断面図である。
図26は、燃料電池用セパレータの製造方法を示すフロー図、図27は、基材の積層を説明する断面図、図28は、絶縁性硬質炭素皮膜を成膜したときの断面図である。以下の説明で参照する図面においては、上述した部材を一部簡略化して示す。
また、上記実施形態の各要素ならびに上記実施形態を適宜組み合わせたものも、本発明の技術的範囲に包含される。例えば、第6~8実施形態に係る溝部を、第1~5および第9~13実施形態に係るシール構造、燃料電池用セパレータ、燃料電池、または車両に適用したものは、本発明の技術的範囲に包含される。
また、当該シール構造を有する燃料電池は、簡素な構造で生産性に優れることから、モバイル用、定置用、自動車用を問わず、多くの用途において好適に利用できる。
Claims (15)
- 対峙する面にシール面を有する構成部品と、
前記シール面の間に介在して、前記シール面を密着させるシール材と、
を備え、
前記シール面の一方または両方に、少なくとも硬質炭素皮膜が形成されていることを特徴とするシール構造。 - 前記シール面に形成された硬質炭素皮膜の幅が、前記シール材の幅よりも広いことを特徴とする請求項1に記載のシール構造。
- 前記構成部品は、対峙する面の少なくとも一方に、凸部または凹部を有しており、
該凸部の先端面または凹部の底面に、前記硬質炭素皮膜が形成されたシール面が設けられていることを特徴とする請求項1または2に記載のシール構造。 - 前記硬質炭素皮膜が形成されたシール面に、溝部が形成されていることを特徴とする請求項1~3のいずれか1項に記載のシール構造。
- 前記構成部品は、基材と、前記硬質炭素皮膜と、前記基材と前記硬質炭素皮膜との間に介在する中間層と、を備えており、
前記溝部は、前記中間層の結晶間に形成された隙間を含むことを特徴とする請求項4に記載のシール構造。 - 前記中間層は、柱状結晶構造を有しており、
前記隙間は、前記中間層の柱状結晶間の隙間からなることを特徴とする請求項5に記載のシール構造。 - 前記溝部は、前記硬質炭素皮膜に形成されたクラックであることを特徴とする請求項4に記載のシール構造。
- 前記構成部品は、隣接する二つの燃料電池用セパレータ、または、膜電極接合体および該膜電極接合体に隣接する燃料電池用セパレータであり、
前記セパレータは、前記硬質炭素皮膜が形成されたシール面を有することを特徴とする請求項1~7のいずれか1項に記載のシール構造。 - 前記シール面に形成された硬質炭素皮膜が、導電性を有することを特徴とする請求項1~8のいずれか1項に記載のシール構造。
- 前記構成部品は、面方向に広がる一の面、および該一の面の外周縁から厚さ方向に延設された外周端面を有する扁平形状の基材と、少なくとも前記外周端面を覆う絶縁性硬質炭素皮膜と、を有する燃料電池用セパレータであることを特徴とする請求項1~9のいずれか1項に記載のシール構造。
- 前記一の面には、流路溝が形成されており、
前記一の面の前記流路溝を含む領域が、導電性硬質炭素皮膜によって覆われていることを特徴とする請求項10に記載のシール構造。 - 前記絶縁性硬質炭素皮膜が、前記外周端面と、前記一の面における、前記導電性硬質炭素皮膜によって覆われた領域の周囲の領域と、を覆うことを特徴とする請求項11に記載のシール構造。
- 前記導電性硬質炭素皮膜が、前記一の面の全体を覆うことを特徴とする請求項11に記載のシール構造。
- 前記シール材は、前記一の面上に、前記導電性硬質炭素皮膜によって覆われた領域の周囲を囲むように配置されており、
前記絶縁性硬質炭素皮膜は、前記外周端面と、前記一の面の外周縁から前記シール材までの範囲の前記一の面と、を覆うことを特徴とする請求項12に記載のシール構造。 - 請求項1~14のいずれか1項に記載のシール構造を有する燃料電池。
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CA2744995A CA2744995C (en) | 2008-11-28 | 2009-10-30 | Sealing structure and fuel cell having the sealing structure |
US13/131,706 US9350027B2 (en) | 2008-11-28 | 2009-10-30 | Sealing structure and fuel cell having the sealing structure |
CN200980147689.8A CN102227842B (zh) | 2008-11-28 | 2009-10-30 | 密封构造及具有该密封构造的燃料电池 |
EP09828960.6A EP2360761B1 (en) | 2008-11-28 | 2009-10-30 | Sealing structure and fuel cell comprising the sealing structure |
JP2010540433A JP5003823B2 (ja) | 2008-11-28 | 2009-10-30 | シール構造および該シール構造を備えた燃料電池 |
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Also Published As
Publication number | Publication date |
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US9350027B2 (en) | 2016-05-24 |
EP2360761A1 (en) | 2011-08-24 |
CA2744995A1 (en) | 2010-06-03 |
CN102227842B (zh) | 2014-03-12 |
JP2012023042A (ja) | 2012-02-02 |
JPWO2010061711A1 (ja) | 2012-04-26 |
EP2360761B1 (en) | 2014-08-27 |
CN102227842A (zh) | 2011-10-26 |
US20110229791A1 (en) | 2011-09-22 |
CA2744995C (en) | 2013-08-06 |
EP2360761A4 (en) | 2013-12-11 |
JP5003823B2 (ja) | 2012-08-15 |
JP5365669B2 (ja) | 2013-12-11 |
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