WO2017069033A1 - インターコネクタ-電気化学反応単セル複合体、および、電気化学反応セルスタック - Google Patents
インターコネクタ-電気化学反応単セル複合体、および、電気化学反応セルスタック Download PDFInfo
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- WO2017069033A1 WO2017069033A1 PCT/JP2016/080338 JP2016080338W WO2017069033A1 WO 2017069033 A1 WO2017069033 A1 WO 2017069033A1 JP 2016080338 W JP2016080338 W JP 2016080338W WO 2017069033 A1 WO2017069033 A1 WO 2017069033A1
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- interconnector
- electrochemical reaction
- single cell
- coat
- fuel
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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
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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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
- C25B9/77—Assemblies comprising two or more cells of the filter-press type having diaphragms
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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
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
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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
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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
- H01M8/2425—High-temperature cells with solid 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
- H01M8/24—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
- H01M8/2425—High-temperature cells with solid electrolytes
- H01M8/2432—Grouping of unit cells of planar configuration
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide 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
- H01M8/0208—Alloys
- H01M8/021—Alloys based on iron
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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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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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 technology disclosed in this specification relates to an interconnector-electrochemical reaction single cell complex.
- SOFC solid oxide fuel cell
- first direction a predetermined direction
- the composite includes a fuel cell single cell (hereinafter simply referred to as “single cell”) including an electrolyte layer and an air electrode and a fuel electrode facing each other in the first direction across the electrolyte layer, and a fuel electrode side of the single cell And an interconnector in which a through hole forming a fuel gas flow path is formed.
- single cell a fuel cell single cell
- the single cell including an electrolyte layer and an air electrode and a fuel electrode facing each other in the first direction across the electrolyte layer, and a fuel electrode side of the single cell
- an interconnector in which a through hole forming a fuel gas flow path is formed.
- first surface the surface of the interconnector included in one composite body opposite to the fuel electrode side
- first surface the surface of the interconnector included in one composite body opposite to the fuel electrode side
- first surface the surface of the interconnector included in one composite body opposite to the fuel electrode side
- first surface the surface of the interconnector included in one composite body opposite to the fuel electrode side
- first surface the first surface
- a technique is known in which an air chamber facing the air electrode of another composite is sealed by disposing a seal member that constitutes the fuel gas flow path between the other composite (see, for example, Patent Documents). 1).
- the above-mentioned coat constituting the first surface of the interconnector faces the air chamber and is exposed to an oxidizing atmosphere. Therefore, in general, the material for forming the coat is selected in consideration of oxidation resistance, but is not selected in consideration of reduction resistance.
- the coat is exposed to the fuel gas flow path between the interconnector and the seal member. For this reason, there is a problem that the coat becomes porous due to the reduction reaction between the fuel gas flowing in the fuel gas passage and the coat, and the sealing performance of the fuel gas passage is lowered.
- interconnector-electrolysis cell complex including a solid oxide electrolytic cell (hereinafter referred to as “SOEC”) that generates hydrogen using an electrolysis reaction of water and an interconnector.
- SOEC solid oxide electrolytic cell
- electrolytic cell stack configured by arranging a plurality of layers.
- the interconnector-fuel cell single cell composite and the interconnector-electrolytic cell composite are collectively referred to as an "interconnector-electrochemical reaction single cell composite”.
- the fuel cell stack and the electrolytic cell stack Are collectively referred to as an “electrochemical reaction cell stack”.
- An interconnector-electrochemical reaction single cell composite disclosed in this specification includes an electrolyte layer and an air electrode and a fuel electrode facing each other in a first direction with the electrolyte layer interposed therebetween.
- An interconnector-electrochemical reaction unit comprising: a single cell; and an interconnector formed on the fuel electrode side of the electrochemical reaction single cell, in which a first through-hole forming a fuel gas flow path is formed.
- the interconnector includes a coat constituting a first surface of the interconnector opposite to the fuel electrode side, and the coat is a part of the first surface of the interconnector.
- the first surface region constituting the first surface region of the interconnector facing the air electrode of another interconnector-electrochemical reaction single cell composite disposed adjacently is used.
- a second coat having higher reduction resistance than the first coat is disposed over the entire circumference of the fuel gas flow path. Thereby, it can suppress that the sealing performance of a fuel gas flow path falls due to the reductive reaction of a 1st coat and fuel gas.
- the interconnector has a second through hole forming an oxidant gas flow path, and the first surface region has the It is good also as a structure characterized by including the surface area
- the area where the second coat is formed can be reduced as compared with the case where the second coat also constitutes a surface area surrounding the second through hole. Can do.
- the second coat may include chromia.
- the electrolyte may be a solid oxide.
- a plurality of interconnectors-electrochemical reaction single cell complexes arranged in the first direction, and the plurality of interconnectors-electrochemical reaction single cell complexes
- a seal member which is disposed between one interconnector-electrochemical reaction single cell complex adjacent to each other and the other interconnector-electrochemical reaction single cell complex, and constitutes the fuel gas flow path
- at least one of the plurality of interconnector-electrochemical reaction single cell complexes is any one of the interconnectors-electrochemical reaction described in (1) to (4) above.
- the contour line on the outer peripheral side of the second coat is a ring on the outer peripheral side of the seal member. It may be configured, characterized in that located inside the line. Since the contour line on the outer peripheral side of the second coat is located on the inner side of the contour line on the outer peripheral side of the seal member, exposure of the second coat to the air chamber is suppressed. Thereby, it is possible to suppress the occurrence of an influence such as a decrease in electrochemical reactivity due to the second coat being exposed to the air chamber.
- the outline on the inner peripheral side of the first coat is located outside the outline on the inner peripheral side of the seal member in the first direction view. It is good also as a structure characterized by this. Since the contour line on the inner peripheral side of the first coat is positioned outside the contour line on the inner peripheral side of the seal member, the first coat is positioned on the inner side of the contour line on the inner peripheral side of the seal member. Peeling off.
- a plurality of interconnectors-electrochemical reaction single cell composites arranged side by side in the first direction, and the plurality of interconnectors-electrochemical reaction single cell composites
- a seal member which is disposed between one interconnector-electrochemical reaction single cell complex adjacent to each other and the other interconnector-electrochemical reaction single cell complex, and constitutes the fuel gas flow path
- at least one of the plurality of interconnector-electrochemical reaction single cell complexes is any one of the interconnectors-electrochemical reaction described in (1) to (4) above.
- the contour line on the inner peripheral side of the first coat is a ring on the inner peripheral side of the seal member. May be configured, characterized in that it is located outside the line. Since the contour line on the inner peripheral side of the first coat is positioned outside the contour line on the inner peripheral side of the seal member, the first coat is positioned on the inner side of the contour line on the inner peripheral side of the seal member. Peeling off.
- the electrochemical reaction single cell included in each of the plurality of interconnector-electrochemical reaction single cell composites may be a fuel cell single cell. Good.
- an interconnector-electrical device including an electrochemical reaction single cell (a fuel cell single cell or an electrolysis cell) and an interconnector.
- Chemical reaction single cell composite interconnector-fuel cell single cell composite
- electrochemical reaction cell stack fuel cell stack or electrolytic cell stack
- FIG. 1 is a perspective view showing an external configuration of a fuel cell stack 100 in a first embodiment.
- FIG. 2 is an explanatory diagram showing an XZ cross-sectional configuration of a fuel cell stack 100 at a position II-II in FIG.
- FIG. 3 is an explanatory diagram showing a YZ cross-sectional configuration of a fuel cell stack 100 at a position of III-III in FIG. It is explanatory drawing which shows XZ cross-section structure of the two electric power generation units 102 adjacent to each other in the same position as the cross section shown in FIG. It is explanatory drawing which shows the YZ cross-section structure of the two electric power generation units 102 adjacent to each other in the same position as the cross section shown in FIG. FIG.
- FIG. 5 is an explanatory diagram showing an XY cross-sectional configuration (surface on the air electrode 114 side of a base material 156) of the interconnector 150 at the position VI-VI in FIG. 4;
- FIG. 5 is an explanatory diagram showing an XY cross-sectional configuration of an interconnector 150 at a position VII-VII in FIG. 4. It is explanatory drawing which shows the change state 1 between the interconnector 150 and the glass seal
- FIG. 1 is a perspective view showing an external configuration of the fuel cell stack 100 in the present embodiment
- FIG. 2 is an explanatory diagram showing an XZ cross-sectional configuration of the fuel cell stack 100 at a position II-II in FIG.
- FIG. 3 is an explanatory diagram showing a YZ cross-sectional configuration of the fuel cell stack 100 at the position III-III in FIG.
- XYZ axes orthogonal to each other for specifying the direction are shown.
- the positive Z-axis direction is referred to as “upward”
- the negative Z-axis direction is referred to as “downward”. It may be installed in different orientations. The same applies to FIG.
- the fuel cell stack 100 includes a plurality (seven in this embodiment) of power generation units 102 and a pair of end plates 104 and 106.
- the seven power generation units 102 are arranged side by side in a predetermined arrangement direction (vertical direction in the present embodiment).
- the pair of end plates 104 and 106 are arranged so as to sandwich an assembly composed of seven power generation units 102 from above and below.
- the arrangement direction (vertical direction) corresponds to the first direction in the claims.
- a plurality of (eight in the present embodiment) holes penetrating in the vertical direction are formed in the peripheral portion around the Z direction of each layer (power generation unit 102, end plates 104, 106) constituting the fuel cell stack 100.
- the holes formed in each layer and corresponding to each other communicate with each other in the vertical direction to form a communication hole 108 extending in the vertical direction from one end plate 104 to the other end plate 106.
- the holes formed in each layer of the fuel cell stack 100 to form the communication holes 108 are also referred to as “communication holes 108”.
- the bolts 22 extending in the vertical direction are inserted into the communication holes 108, and the fuel cell stack 100 is fastened by the bolts 22 and nuts 24 fitted on both sides of the bolts 22. 2 and 3, between the nut 24 fitted on one side (upper side) of the bolt 22 and the upper surface of the end plate 104 constituting the upper end of the fuel cell stack 100, and the bolt An insulating sheet 26 is interposed between the nut 24 fitted on the other side (lower side) of 22 and the lower surface of the end plate 106 constituting the lower end of the fuel cell stack 100.
- an insulating sheet disposed between the nut 24 and the surface of the end plate 106 on the upper and lower sides of the gas passage member 27 and the gas passage member 27, respectively. 26 is interposed.
- the insulating sheet 26 is made of, for example, a mica sheet, a ceramic fiber sheet, a ceramic powder sheet, a glass sheet, a glass ceramic composite agent, or the like.
- the outer diameter of the shaft portion of each bolt 22 is smaller than the inner diameter of each communication hole 108. Therefore, a space is secured between the outer peripheral surface of the shaft portion of each bolt 22 and the inner peripheral surface of each communication hole 108.
- the fuel cell stack 100 is located near the midpoint of one side (the X-axis positive direction side of two sides parallel to the Y-axis) on the outer periphery around the Z-direction.
- the space formed by the bolt 22 (bolt 22A) and the communication hole 108 into which the bolt 22A is inserted is introduced with the oxidant gas OG from the outside of the fuel cell stack 100, and the oxidant gas OG is generated by each power generation.
- oxidant gas introduction manifold 161 that is a gas flow path to be supplied to the unit 102, and is the midpoint of the side opposite to the side (X-axis negative direction side of two sides parallel to the Y-axis)
- the space formed by the bolts 22 (bolts 22B) located in the vicinity and the communication holes 108 into which the bolts 22B are inserted has an oxidant off-gas OOG that is a gas discharged from the air chamber 166 of each power generation unit 102.
- Burning Functions as the oxidizing gas discharging manifold 162 for discharging to the outside of the cell stack 100. In the present embodiment, for example, air is used as the oxidant gas OG.
- the oxidant gas introduction manifold 161 and the oxidant gas discharge manifold 162 correspond to the oxidant gas flow path in the claims.
- the oxidant gas introduction manifold 161 and the oxidant gas discharge manifold 162 are collectively referred to as an oxidant gas flow path.
- the communication hole 108 formed in each interconnector 150 and constituting the oxidant gas introduction manifold 161 or the oxidant gas discharge manifold 162 is a second through hole (hereinafter referred to as “air chamber communication hole 108A”) in the claims. ).
- the vicinity of the midpoint of one side (the side on the Y axis positive direction side of two sides parallel to the X axis) on the outer periphery of the fuel cell stack 100 around the Z direction The space formed by the bolt 22 (bolt 22D) located at the position and the communication hole 108 into which the bolt 22D is inserted is introduced with the fuel gas FG from the outside of the fuel cell stack 100, and the fuel gas FG is generated for each power generation.
- the space formed by the (bolt 22E) and the communication hole 108 into which the bolt 22E is inserted is a fuel cell stack in which the fuel off-gas FOG that is the gas discharged from the fuel chamber 176 of each power generation unit 102 is supplied to the fuel cell stack. 00 and to the outside to function as a fuel gas discharge manifold 172 for discharging.
- the fuel gas FG for example, hydrogen-rich gas obtained by reforming city gas is used.
- the fuel gas introduction manifold 171 and the fuel gas discharge manifold 172 correspond to fuel gas passages in the claims.
- the fuel gas introduction manifold 171 and the fuel gas discharge manifold 172 are collectively referred to as “fuel gas flow path”.
- the communication hole 108 formed in each interconnector 150 and constituting the fuel gas introduction manifold 171 or the fuel gas discharge manifold 172 is a first through hole in the claims (hereinafter referred to as “fuel chamber communication hole 108B”). Equivalent to.
- the fuel cell stack 100 is provided with four gas passage members 27.
- Each gas passage member 27 has a hollow cylindrical main body portion 28 and a hollow cylindrical branch portion 29 branched from the side surface of the main body portion 28.
- the hole of the branch part 29 communicates with the hole of the main body part 28.
- a gas pipe (not shown) is connected to the branch portion 29 of each gas passage member 27.
- a forming the oxidant gas introduction manifold 161 communicates with the oxidant gas introduction manifold 161.
- the hole of the main body portion 28 of the gas passage member 27 disposed at the position of the bolt 22 ⁇ / b> B that forms the oxidant gas discharge manifold 162 communicates with the oxidant gas discharge manifold 162. Further, as shown in FIG. 3, the hole of the main body portion 28 of the gas passage member 27 arranged at the position of the bolt 22D forming the fuel gas introduction manifold 171 communicates with the fuel gas introduction manifold 171 and the fuel gas The hole of the main body portion 28 of the gas passage member 27 disposed at the position of the bolt 22 ⁇ / b> E forming the discharge manifold 172 communicates with the fuel gas discharge manifold 172.
- the pair of end plates 104 and 106 are substantially rectangular flat plate-shaped conductive members, and are formed of, for example, stainless steel.
- One end plate 104 is disposed on the upper side of the power generation unit 102 located on the uppermost side, and the other end plate 106 is disposed on the lower side of the power generation unit 102 located on the lowermost side.
- a plurality of power generation units 102 are held in a pressed state by a pair of end plates 104 and 106.
- the upper end plate 104 functions as a positive output terminal of the fuel cell stack 100
- the lower end plate 106 functions as a negative output terminal of the fuel cell stack 100.
- FIG. 102 is an explanatory diagram showing an XZ cross-sectional configuration of two power generation units 102 adjacent to each other at the same position as the cross section shown in FIG. 2, and FIG. 5 is adjacent to each other at the same position as the cross section shown in FIG.
- FIG. 6 is an explanatory diagram showing a YZ cross-sectional configuration of two power generation units 102, and FIG. 6 shows an XY cross-sectional configuration of the interconnector 150 at the position VI-VI in FIG.
- FIG. 7 is an explanatory view
- FIG. 7 is an explanatory view showing an XY cross-sectional configuration of the interconnector 150 at the position VII-VII in FIG.
- the power generation unit 102 that is the minimum unit of power generation includes a single cell 110, a separator 120, an air electrode side frame 130, an air electrode side current collector 134, and a fuel electrode side frame. 140, a fuel electrode side current collector 144, and a pair of interconnectors 150 constituting the uppermost layer and the lowermost layer of the power generation unit 102.
- a hole corresponding to the above-described communication hole 108 into which the bolt 22 is inserted is formed in the peripheral portion around the Z direction in the separator 120, the air electrode side frame 130, the fuel electrode side frame 140, and the interconnector 150.
- the single cell 110 corresponds to a fuel cell single cell or an electrochemical reaction single cell in the claims.
- the interconnector 150 is a substantially rectangular flat plate-shaped conductive member.
- the interconnector 150 is formed of a base material 156 made of a metal containing Cr (chromium) such as ferritic stainless steel, and the air electrode 114 side of the base material 156. And coats (136, 137) constituting the first surface 151 of the interconnector 150 on the air electrode 114 side.
- the interconnector 150 ensures electrical continuity between the power generation units 102 and prevents reaction gas from being mixed between the power generation units 102. In the present embodiment, when two power generation units 102 are arranged adjacent to each other, one interconnector 150 is shared by two adjacent power generation units 102.
- the upper interconnector 150 in a power generation unit 102 is the same member as the lower interconnector 150 in another power generation unit 102 adjacent to the upper side of the power generation unit 102. Further, since the fuel cell stack 100 includes the pair of end plates 104 and 106, the power generation unit 102 located at the top in the fuel cell stack 100 does not include the upper interconnector 150 and is located at the bottom. The power generation unit 102 does not include the lower interconnector 150 (see FIGS. 2 and 3).
- the single cell 110 includes an electrolyte layer 112 and an air electrode (cathode) 114 and a fuel electrode (anode) 116 that face each other in the vertical direction (the arrangement direction in which the power generation units 102 are arranged) with the electrolyte layer 112 interposed therebetween.
- the single cell 110 of the present embodiment is a fuel electrode-supported single cell that supports the electrolyte layer 112 and the air electrode 114 with the fuel electrode 116.
- the electrolyte layer 112 is a substantially rectangular flat plate-shaped member.
- YSZ yttria stabilized zirconia
- ScSZ scandia stabilized zirconia
- SDC samarium doped ceria
- GDC gadolinium doped ceria
- perovskite oxide It is formed with solid oxides such as.
- the air electrode 114 is a substantially rectangular flat plate-shaped member, and is formed of, for example, a perovskite oxide (for example, LSCF (lanthanum strontium cobalt iron oxide), LSM (lanthanum strontium manganese oxide), LNF (lanthanum nickel iron)).
- LSCF larovskite oxide
- LSM lanthanum strontium manganese oxide
- LNF lanthanum nickel iron
- the fuel electrode 116 is a substantially rectangular flat plate-like member, and is formed of, for example, Ni (nickel), cermet made of Ni and ceramic particles, Ni-based alloy, or the like.
- the single cell 110 (power generation unit 102) of the present embodiment is a solid oxide fuel cell (SOFC) that uses a solid oxide as an electrolyte.
- SOFC solid oxide fuel cell
- the separator 120 is a frame-like member in which a substantially rectangular hole 121 penetrating in the vertical direction is formed near the center, and is made of, for example, metal.
- the peripheral part of the hole 121 in the separator 120 is opposed to the peripheral part of the surface of the electrolyte layer 112 on the air electrode 114 side.
- the separator 120 is bonded to the electrolyte layer 112 (single cell 110) by a bonding portion 124 formed of a brazing material (for example, Ag brazing) disposed in the facing portion.
- the separator 120 divides the air chamber 166 facing the air electrode 114 and the fuel chamber 176 facing the fuel electrode 116, and gas leaks from one electrode side to the other electrode side in the peripheral portion of the single cell 110. It is suppressed.
- the single cell 110 to which the separator 120 is bonded is referred to as “single cell with separator”.
- the air electrode side frame 130 is a frame-like member in which a substantially rectangular hole 131 penetrating in the vertical direction is formed near the center, and is formed of an insulator such as mica, for example.
- the hole 131 of the air electrode side frame 130 forms an air chamber 166 that faces the air electrode 114.
- the air electrode side frame 130 is in contact with the peripheral edge portion of the surface of the separator 120 opposite to the side facing the electrolyte layer 112 and the peripheral edge portion of the surface of the interconnector 150 facing the air electrode 114. .
- the pair of interconnectors 150 included in the power generation unit 102 is electrically insulated by the air electrode side frame 130.
- the air electrode side frame 130 has an oxidant gas supply communication hole 132 communicating the oxidant gas introduction manifold 161 and the air chamber 166, and an oxidant gas communicating the air chamber 166 and the oxidant gas discharge manifold 162.
- a discharge communication hole 133 is formed.
- the wall constituting the hole 131 of the air electrode side frame 130 is referred to as “inner peripheral wall 130A”, and the wall constituting the outer peripheral shape of the air electrode side frame 130 is referred to as “outer peripheral wall 130B”.
- the fuel electrode side frame 140 is a frame-like member in which a substantially rectangular hole 141 penetrating in the vertical direction is formed near the center, and is made of, for example, metal.
- the hole 141 of the fuel electrode side frame 140 forms a fuel chamber 176 that faces the fuel electrode 116.
- the fuel electrode side frame 140 is in contact with the peripheral portion of the surface of the separator 120 facing the electrolyte layer 112 and the peripheral portion of the surface of the interconnector 150 facing the fuel electrode 116.
- the fuel electrode side frame 140 has a fuel gas supply communication hole 142 that connects the fuel gas introduction manifold 171 and the fuel chamber 176, and a fuel gas discharge communication hole 143 that connects the fuel chamber 176 and the fuel gas discharge manifold 172. And are formed.
- the fuel electrode side current collector 144 is disposed in the fuel chamber 176.
- the fuel electrode side current collector 144 includes an interconnector facing portion 146, an electrode facing portion 145, and a connecting portion 147 that connects the electrode facing portion 145 and the interconnector facing portion 146.
- the electrode facing portion 145 is in contact with the surface of the fuel electrode 116 on the side opposite to the side facing the electrolyte layer 112, and the interconnector facing portion 146 is on the surface of the interconnector 150 on the side facing the fuel electrode 116. In contact.
- the interconnector facing portion 146 in the power generation unit 102 has a lower end plate. 106 is in contact. Since the fuel electrode side current collector 144 has such a configuration, the fuel electrode 116 and the interconnector 150 (or the end plate 106) are electrically connected. Note that a spacer 149 made of, for example, mica is disposed between the electrode facing portion 145 and the interconnector facing portion 146.
- the fuel electrode side current collector 144 follows the deformation of the power generation unit 102 due to the temperature cycle and the reaction gas pressure fluctuation, and the fuel electrode 116 and the interconnector 150 (or the end plate 106) via the fuel electrode side current collector 144.
- the electrical connection with is maintained well.
- the air electrode side current collector 134 is disposed in the air chamber 166.
- the air electrode side current collector 134 is composed of a plurality of substantially square columnar current collector elements 135, and is formed of, for example, a metal containing Cr (chromium) such as ferritic stainless steel.
- the air electrode side current collector 134 is in contact with the surface of the air electrode 114 opposite to the side facing the electrolyte layer 112 and the surface of the interconnector 150 facing the air electrode 114.
- the air electrode side current collector 134 in the power generation unit 102 includes the upper end plate. 104 is in contact.
- the air electrode side current collector 134 has such a configuration, the air electrode 114 and the interconnector 150 (or the end plate 104) are electrically connected.
- the air electrode side current collector 134 and the interconnector 150 are formed as an integral member. That is, a flat plate-shaped portion perpendicular to the vertical direction (Z-axis direction) of the integral member functions as the interconnector 150 and is formed so as to protrude toward the air electrode 114 from the flat plate-shaped portion.
- the plurality of current collector elements 135 function as the air electrode side current collector 134.
- the surface of the air electrode side current collector 134 is covered with a conductive first coat 136.
- the first coat 136 includes, for example, a spinel oxide (for example, Mn 1.5 Co 1.5 O 4 , MnCo 2 O 4 , ZnCo 2 O 4 , ZnMnCoO 4 , CuMn 2 O 4 , MnFe 2 O 4 , ZnMn 2 O 4 , Cu 1.4 Mn 1.6 O 4 , CoFe 2 O 4 ).
- the air electrode side current collector 134 and the interconnector 150 are formed as an integral member.
- the interface with the interconnector 150 is not covered with the first coat 136.
- the coat (136, 137) constituting the first surface 151 of the interconnector 150 will be described later.
- the air electrode 114 and the air electrode side current collector 134 are joined by a conductive joining layer 138.
- the bonding layer 138 is formed of, for example, a spinel oxide (for example, Mn 1.5 Co 1.5 O 4 , MnCo 2 O 4 , ZnCo 2 O 4 , ZnMn 2 O 4 , ZnMnCoO 4 , CuMn 2 O 4 ).
- the bonding layer 138 is printed on a portion of the surface of the air electrode 114 facing the front end portion of each current collector element 135 constituting the air electrode side current collector 134. It is formed by firing under a predetermined condition in a state where the front end portion of the electric element 135 is pressed against the paste.
- the air electrode 114 and the air electrode side current collector 134 are electrically connected by the bonding layer 138. Although it has been described above that the air electrode side current collector 134 is in contact with the surface of the air electrode 114, more precisely, the air electrode side current collector 134 (covered by the first coat 136) and the air A bonding layer 138 is interposed between the electrode 114 and the electrode 114.
- the first coat 136 and the bonding layer 138 are formed of spinel oxides having the same main component elements.
- the main component element here refers to a metal element constituting a spinel oxide.
- the identification of the spinel oxide is realized by performing X-ray diffraction and elemental analysis.
- the oxidant gas OG is supplied through a gas pipe (not shown) connected to the branch portion 29 of the gas passage member 27 provided at the position of the oxidant gas introduction manifold 161. Then, the oxidant gas OG is supplied to the oxidant gas introduction manifold 161 through the branch portion 29 of the gas passage member 27 and the hole of the main body portion 28, and the oxidant gas introduction manifold 161 oxidizes each power generation unit 102. It is supplied to the air chamber 166 through the agent gas supply communication hole 132. Further, as shown in FIGS.
- the fuel gas FG is supplied through a gas pipe (not shown) connected to the branch portion 29 of the gas passage member 27 provided at the position of the fuel gas introduction manifold 171. Then, the fuel gas FG is supplied to the fuel gas introduction manifold 171 through the branch portion 29 of the gas passage member 27 and the hole of the main body portion 28, and the fuel gas supply communication of each power generation unit 102 from the fuel gas introduction manifold 171.
- the fuel chamber 176 is supplied through the hole 142.
- each power generation unit 102 When the oxidant gas OG is supplied to the air chamber 166 of each power generation unit 102 and the fuel gas FG is supplied to the fuel chamber 176, power is generated by an electrochemical reaction between the oxidant gas OG and the fuel gas FG in the single cell 110. Is called. This power generation reaction is an exothermic reaction.
- the air electrode 114 of the single cell 110 is electrically connected to one interconnector 150 via the air electrode side current collector 134 (and the first coat 136 and the bonding layer 138), and the fuel electrode. 116 is electrically connected to the other interconnector 150 via the fuel electrode side current collector 144.
- the plurality of power generation units 102 included in the fuel cell stack 100 are electrically connected in series.
- each power generation unit 102 electrical energy generated in each power generation unit 102 is taken out from the end plates 104 and 106 that function as output terminals of the fuel cell stack 100. Since SOFC generates power at a relatively high temperature (for example, 700 ° C. to 1000 ° C.), the fuel cell stack 100 is heated by a heater (after the start-up until the high temperature can be maintained by the heat generated by the power generation. (Not shown).
- the oxidant off-gas OOG discharged from the air chamber 166 of each power generation unit 102 is discharged to the oxidant gas discharge manifold 162 via the oxidant gas discharge communication hole 133 as shown in FIGS.
- the fuel cell stack 100 is connected to the branch portion 29 via a gas pipe (not shown) through the holes of the main body portion 28 and the branch portion 29 of the gas passage member 27 provided at the position of the agent gas discharge manifold 162. Is discharged outside.
- the fuel off-gas FOG discharged from the fuel chamber 176 of each power generation unit 102 is discharged to the fuel gas discharge manifold 172 via the fuel gas discharge communication hole 143, and further to the fuel gas.
- the gas passage member 27 provided at the position of the discharge manifold 172 passes through the body portion 28 and the branch portion 29 and passes through a gas pipe (not shown) connected to the branch portion 29 to the outside of the fuel cell stack 100. Discharged.
- Gas seal in the fuel cell stack 100 In the fuel cell stack 100, if the fuel gas FG (or fuel off gas FOG) leaks from each fuel gas flow path to the air chamber 166, the efficiency of the fuel cell stack 100 decreases, which is not preferable. Therefore, the fuel cell stack 100 is required to have high gas sealing properties. Hereinafter, the gas seal in the fuel cell stack 100 will be described.
- the air electrode side frame 130 included in each power generation unit 102 in the fuel cell stack 100 functions as a so-called compression seal.
- the air electrode side frame 130 is sandwiched between the separator 120 and the interconnector 150 and is compressed, thereby closely contacting the surfaces of the separator 120 and the interconnector 150.
- each of the fuel gas introduction manifold 171 and the fuel gas discharge manifold 172 is provided between the separator 120 and the interconnector 150 facing the separator 120 with the air electrode side frame 130 interposed therebetween.
- An annular glass seal 240 is provided so as to surround the periphery. The glass seal 240 is configured to prevent the fuel gas FG (or fuel off-gas FOG) from each fuel gas flow path from passing through the interface between the air electrode side frame 130 and the separator 120 and the interface between the air electrode side frame 130 and the interconnector 150. Suppress leaks. As shown in the enlarged view of FIG.
- the inner diameter D1 of the glass seal 240 is larger than the inner diameter D0 of the communication hole 108 (fuel chamber communication hole 108B).
- the glass seal 240 is disposed outside a welded portion (not shown) that joins the peripheral portion of the hole 141 of the fuel electrode side frame 140 and the separator 120. Further, since the glass seal 240 is an insulator, the provision of the glass seal 240 does not hinder electrical insulation between the pair of interconnectors 150 included in the power generation unit 102. In the present embodiment, the glass seal 240 is not provided around the oxidant gas introduction manifold 161 and the oxidant gas discharge manifold 162.
- the single cell 110, the separator 120, the fuel electrode side frame 140, the interconnector 150 positioned on the fuel electrode 116 side of the single cell 110, the fuel electrode side current collector 144, and the spacer 149 are claimed.
- an interconnector-electrochemical reaction single cell complex (hereinafter simply referred to as “complex 103”) is formed (see FIGS. 4 and 5).
- the air electrode side frame 130 and the glass seal 240 disposed between the two composite bodies 103 correspond to a seal member in the claims.
- a gas seal is secured between the fuel electrode side frame 140 included in each power generation unit 102 in the fuel cell stack 100 and the adjacent separator 120 or interconnector 150 by welding.
- the peripheral edge of the hole 141 of the fuel electrode side frame 140 and the separator 120 are joined by laser welding.
- first surface 151 of interconnector 150 Coat of first surface 151 of interconnector 150:
- second base material region 158 A region excluding the two second base material regions 158 (see FIG. 6) is referred to as a “first base material region 157”.
- first base material region 157 and the second base material region 158 are adjacent to each other.
- second surface region 153 two annular surface regions surrounding the entire circumference of the fuel chamber communication hole 108B in the first surface 151 of the interconnector 150 are referred to as “second surface region 153”.
- a region excluding the two second surface regions 153 is referred to as a “first surface region 152”.
- the first surface region 152 and the second surface region 153 are adjacent to each other.
- the outer diameter D2 of the second surface region 153 (the diameter of the boundary line between the first surface region 152 and the second surface region 153) is larger than the inner diameter D1 of the glass seal 240, and glass It is smaller than the outer diameter D3 of the seal 240.
- the first base material region 157 of the base material 156 is covered with the second coat 137, and the entire surface of the second coat 137 covering the first base material region 157 is the same as that of the first coat described above. Covered by a coat 136.
- each second base material region 158 of the base material 156 is covered with the second coat 137, and the surface of the second coat 137 covering the second base material region 158 is the first coat region 158. It is not covered with the coat 136 and is in contact with the glass seal 240 over the entire circumference.
- the first surface region 152 of the interconnector 150 is configured by the first coat 136
- the second surface region 153 is configured by the second coat 137.
- the surface region 154 see FIG.
- the second coat 137 is a chromium oxide film (chromia film) and has higher reduction resistance against the fuel gas FG than the first coat 136.
- the first coat 136 faces the air chamber 166 through which the oxidant gas OG flows, the oxidant gas introduction manifold 161, and the oxidant gas discharge manifold 162, and the second coat 137 is exposed.
- the second coat 137 faces the fuel gas flow path through which the fuel gas FG flows, and the first coat 136 is not exposed.
- the first coat 136 is preferably formed of a material having higher conductivity than the second coat 137 in order to cover the air electrode side current collector 134.
- the first coat 136 since the first coat 136 faces the air chamber 166, it is preferable that the first coat 136 is made of a material having higher oxidation resistance against the oxidant gas OG than the second coat 137.
- the base material 156 of the interconnector 150 is formed of a metal containing Cr, in order to suppress “Cr diffusion” in which Cr is released and diffused from the surface of the base material 156, Compared to the second coat 137, it is preferably made of a material having a higher effect of suppressing Cr diffusion.
- An example of a method for forming a coat on the first surface 151 of the interconnector 150 is as follows. First, a heat treatment is performed on the interconnector 150 to form a second coat 137 (chromia film) on the surface of the substrate 156 on the air electrode 114 side by Cr deposited from the substrate 156 of the interconnector 150. Note that the thickness of the second coat 137 can be adjusted by a firing temperature and a firing time in the heat treatment.
- the first coat 136 is formed by a known method such as spin coating, dip coating, plating, sputtering, or thermal spraying. Thereafter, the mask of each second surface region 153 is removed. Accordingly, it is possible to manufacture an interconnector 150 in which the first surface region 152 is configured by the first coat 136 and each second surface region 153 is configured by the second coat 137.
- the first coat 136 is formed on the entire surface of the second coat 137 formed on the surface of the base material 156 on the air electrode 114 side without using a mask, Then, the method of peeling the 1st coat 136 which covers the portion corresponding to each 2nd surface field 153 may be used.
- FIG. 8 to FIG. 10 are explanatory views showing the changing states 1 to 3 between the interconnector 150, the air electrode side frame 130, and the glass seal 240 in the composite body 103X of the comparative example.
- the entire first surface 151 ⁇ / b> X of the composite body 103 ⁇ / b> X of the comparative example is configured only by the first coat 136. For this reason, in the composite body 103X of the comparative example, the first coat 136 is exposed in the fuel gas flow path.
- the first coat 136 becomes porous by the reduction reaction between the fuel gas FG flowing in the fuel gas flow path and the first coat 136 (FIG. 9). Further, there is a possibility that the fuel gas flow path and the air chamber 166 penetrate and a leak path of the fuel gas FG is formed (see FIG. 10).
- Method for evaluating reduction resistance of first coat 136 and second coat 137 As described above, the second coat 137 has higher reduction resistance against the fuel gas FG than the first coat 136.
- An example of a method for evaluating the reduction resistance of the first coat 136 and the second coat 137 is as follows. First, a fuel cell stack 100 including one composite body 103 of the present embodiment and a fuel cell stack 100A including one composite body 103X of the comparative example are prepared. As described above, in the composite 103 of the present embodiment, the second coat 137 is exposed in the fuel gas flow path, and the first coat 136 is not exposed. On the other hand, in the fuel cell stack 100A of the comparative example, the first coat 136 is exposed in the fuel gas flow path.
- the air chamber 166 and the fuel gas flow path in a fuel gas FG atmosphere with a flow rate of 3 L / min and a pressure of 10 kpa The fuel gas FG is inspected for leaks. As a result, the direction in which the leak of the fuel gas FG of 10 ml or more is detected first is evaluated as having low reduction resistance. Since the chromia film that forms the second coat 137 has higher reduction resistance than the above-described material that forms the first coat 136, the fuel cell stack 100 ⁇ / b> A has a capacity of 10 ml or more prior to the fuel cell stack 100.
- the predetermined time is the time from the start of operation until the difference in the amount of leakage of the fuel gas FG between the fuel cell stack 100 and the fuel cell stack 100A starts, and is not always constant, It differs depending on the combination of the forming materials of the first coat 136 and the second coat 137.
- An example of the oxidation resistance evaluation method of the first coat 136 and the second coat 137 is an air chamber 166 in an oxidant gas OG (atmosphere) atmosphere as compared to the above-described reduction resistance evaluation method.
- the leak of the oxidant gas OG (air) between the fuel gas flow path and the fuel gas flow path is an evaluation method, the conditions regarding the gas flow rate, pressure, time, etc. are the same.
- the reduction resistance is higher than that of the first coat 136 between the first coat 136 constituting the first surface region 152 of the interconnector 150 and the fuel gas flow path.
- the second coat 137 is disposed over the entire circumference of each fuel chamber communication hole 108B. Thereby, it can suppress that the sealing performance of a fuel gas flow path falls due to the reductive reaction of the 1st coat
- a surface region 154 (see FIG. 7) surrounding the entire circumference of the air chamber communication hole 108A is constituted by the first coat 136. For this reason, even when the second coat 137 is formed of a material having lower oxidation resistance than the first coat 136, the second coat 137 is not exposed to the oxidant gas flow path. The oxidation reaction in the oxidant gas channel can be suppressed.
- each second surface region 153 is smaller than the outer diameter D3 of the glass seal 240.
- the contour line on the outer peripheral side of the second coat 137 is located inside the contour line on the outer peripheral side of the glass seal 240 over the entire periphery. For this reason, even when the second coat 137 is formed of a material having lower oxidation resistance and Cr diffusion suppressing effect than the first coat 136, the second coat 137 is formed in the air chamber 166. Since it is not exposed, oxidation reaction and Cr diffusion in the air chamber 166 can be suppressed.
- each second surface region 153 is larger than the inner diameter D1 of the glass seal 240.
- the contour line on the outer peripheral side of the second coat 137 is located outside the contour line on the inner peripheral side of the glass seal 240 over the entire circumference.
- region which comprises a fuel gas flow path among the 1st surface 151 of the interconnector 150 is comprised by the 2nd coat
- the inner diameter D2 of the first surface region 152 (the outer diameter D2 of the second surface region 153) is larger than the inner diameter D1 of the glass seal 240.
- the contour line on the inner peripheral side of the first coat 136 is located outside the contour line on the inner peripheral side of the glass seal 240 over the entire circumference, and the interconnector 150 and the seal member It is sandwiched between them. For this reason, compared with the case where the 1st coat 136 is exposed inside 240, it can control that the edge of the 1st coat 136 exfoliates.
- FIG. 11 is an explanatory diagram showing an XY cross-sectional configuration of the complex 103A in the second embodiment.
- the same components as those of the complex 103 of the first embodiment described above are denoted by the same reference numerals and description thereof is omitted.
- second substrate regions 158A two annular regions surrounding the entire circumference of the fuel chamber communication hole 108B in the surface on the air electrode 114 side of the substrate 156 are referred to as “second substrate regions 158A”, and the two second regions A region excluding the base material region 158A is referred to as a “first base material region 157A”.
- the first base region 157A and the second base region 158A are adjacent to each other.
- the two annular surface regions surrounding the entire circumference of the fuel chamber communication hole 108B in the first surface 151 of the interconnector 150 are referred to as “second surface region 153A”, and the two second surfaces.
- the region excluding the region 153A is referred to as “first surface region 152A”.
- the first surface region 152A and the second surface region 153A are adjacent to each other.
- the outer diameter D2A of the second surface region 153A (the diameter of the boundary line between the first surface region 152A and the second surface region 153A) is larger than the outer diameter D3 of the glass seal 240, and It is smaller than the distance D4 between the inner peripheral wall 130A and the outer peripheral wall 130B of the air electrode side frame 130.
- the first substrate region 157A of the substrate 156 is covered with the first coat 136 described above.
- each second base material region 158A of the base material 156 is covered with the second coat 137A and is in contact with the air electrode side frame 130 and the glass seal 240 over the entire circumference.
- the first surface region 152A of the interconnector 150 is configured by the first coat 136
- the second surface region 153A is configured by the second coat 137A.
- the second coat 137A is made of, for example, Ni (nickel) or Ni alloy, and has higher resistance to reduction against the fuel gas FG than the first coat 136.
- a chromia film similar to that of the first embodiment may be formed on the surface of the base material 156. Even with such a configuration, the same effect as in the first embodiment can be obtained.
- the air electrode side frame 130 and the glass seal 240 are exemplified as the seal member.
- the seal member is not limited to this, and may be configured only by the glass seal or compressed into a sealed state. It is good also as what was comprised only with the compression seal
- the inner diameter D1 of the glass seal 240 may be the same as the inner diameter D0 of the communication hole 108 (fuel chamber communication hole 108B).
- the composite 103 including the separator 120 is exemplified as the interconnector-electrochemical reaction single cell composite.
- the interconnector-electrochemical reaction single cell composite is not limited to this, and the separator 120 is not limited to this.
- the structure which is not provided may be sufficient.
- the interconnector-electrochemical reaction single cell composite may be not only the fuel electrode support type but also the air electrode support type or the electrolyte support type.
- the outer diameter D2 of each second surface region 153 is larger than the outer diameter D3 of the glass seal 240.
- the outer contour line of the second coat 137 is It may be located outside the outer contour line.
- the outer contour line of the second coat 137 may be located outside the inner peripheral wall 130 ⁇ / b> A of the air electrode side frame 130.
- the inner diameter D2 of the first surface region 152 (the outer diameter D2 of the second surface region 153) may be smaller than the inner diameter D1 of the glass seal 240.
- the number of power generation units 102 included in the fuel cell stack 100 is merely an example, and the number of power generation units 102 is appropriately determined according to the output voltage required for the fuel cell stack 100 or the like.
- the nuts 24 are fitted on both sides of the bolt 22, but the bolt 22 has a head, and the nut 24 is fitted only on the opposite side of the head of the bolt 22. Also good.
- the end plates 104 and 106 function as output terminals.
- separate members for example, the end plate 104 connected to the end plates 104 and 106, respectively.
- 106 and the power generation unit 102 may function as output terminals.
- each manifold may be provided separately from each communication hole 108 into which each bolt 22 is inserted.
- one interconnector 150 is shared by two adjacent power generation units 102.
- Two power generation units 102 may be provided with respective interconnectors 150.
- the upper interconnector 150 of the uppermost power generation unit 102 in the fuel cell stack 100 and the lower interconnector 150 of the lowermost power generation unit 102 are omitted. These interconnectors 150 may be provided without being omitted.
- the air electrode side current collector 134 and the interconnector 150 adjacent thereto may be separate members.
- the fuel electrode side current collector 144 may have the same configuration as the air electrode side current collector 134, and the fuel electrode side current collector 144 and the adjacent interconnector 150 are an integral member. It may be.
- the fuel electrode side frame 140 instead of the air electrode side frame 130 may be an insulator.
- the air electrode side frame 130 and the fuel electrode side frame 140 may have a multilayer structure.
- each member in the above embodiment is merely an example, and each member may be formed of other materials.
- the interconnector 150 is formed of a metal containing Cr, but may be formed of other materials.
- the city gas is reformed to obtain the hydrogen-rich fuel gas FG
- the fuel gas FG may be obtained from other raw materials such as LP gas, kerosene, methanol, gasoline, Pure hydrogen may be used as the fuel gas FG.
- the fact that the member B and the member C are opposed to each other across the member (or a part having the member, the same applies hereinafter) A is not limited to the form in which the member A and the member B or the member C are adjacent to each other. It includes a form in which another component is interposed between member A and member B or member C. For example, even in a configuration in which another layer is provided between the electrolyte layer 112 and the air electrode 114, it can be said that the air electrode 114 and the fuel electrode 116 face each other with the electrolyte layer 112 interposed therebetween.
- the at least one composite body 103 included in the fuel cell stack 100 is caused by the reduction reaction between the first coat 136 and the fuel gas FG if such a configuration is adopted. As a result, it is possible to suppress a decrease in the sealing performance of the fuel gas passage.
- the SOFC that generates electricity using the electrochemical reaction between hydrogen contained in the fuel gas and oxygen contained in the oxidant gas is targeted.
- the present invention can be similarly applied to an electrolytic cell unit that is a minimum unit of a solid oxide electrolytic cell (SOEC) that generates hydrogen by using hydrogen, and an electrolytic cell stack including a plurality of electrolytic cell units.
- SOEC solid oxide electrolytic cell
- the configuration of the electrolytic cell stack is well known as described in, for example, Japanese Patent Application Laid-Open No. 2014-207120 and will not be described in detail here. However, the configuration is generally the same as that of the fuel cell stack 100 in the above-described embodiment. It is a configuration.
- the fuel cell stack 100 in the above-described embodiment may be read as an electrolytic cell stack, and the power generation unit 102 may be read as an electrolytic cell unit.
- a voltage is applied between the two electrodes so that the air electrode 114 is positive (anode) and the fuel electrode 116 is negative (cathode).
- Water vapor as a source gas is supplied.
- an electrolysis reaction of water occurs in each electrolysis cell unit, hydrogen gas is generated in the fuel chamber 176, and hydrogen is taken out of the electrolysis cell stack through the communication hole.
- the interconnector 150 in which the base material 156 is covered with the first coat 136 and the second coat 137 is provided for the composite as in the above embodiment. If the configuration is adopted, there is an effect that it is possible to suppress a decrease in the sealing performance of the fuel gas flow path due to the reduction reaction between the first coat 136 and the fuel gas FG.
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Abstract
Description
A-1.構成:
(燃料電池スタック100の構成)
図1は、本実施形態における燃料電池スタック100の外観構成を示す斜視図であり、図2は、図1のII-IIの位置における燃料電池スタック100のXZ断面構成を示す説明図であり、図3は、図1のIII-IIIの位置における燃料電池スタック100のYZ断面構成を示す説明図である。各図には、方向を特定するための互いに直交するXYZ軸が示されている。本明細書では、便宜的に、Z軸正方向を「上方向」といい、Z軸負方向を「下方向」というものとするが、燃料電池スタック100は実際にはそのような向きとは異なる向きで設置されてもよい。図4以降についても同様である。
一対のエンドプレート104,106は、略矩形の平板形状の導電性部材であり、例えばステンレスにより形成されている。一方のエンドプレート104は、最も上に位置する発電単位102の上側に配置され、他方のエンドプレート106は、最も下に位置する発電単位102の下側に配置されている。一対のエンドプレート104,106によって複数の発電単位102が押圧された状態で挟持されている。上側のエンドプレート104は、燃料電池スタック100のプラス側の出力端子として機能し、下側のエンドプレート106は、燃料電池スタック100のマイナス側の出力端子として機能する。
図4は、図2に示す断面と同一の位置における互いに隣接する2つの発電単位102のXZ断面構成を示す説明図であり、図5は、図3に示す断面と同一の位置における互いに隣接する2つの発電単位102のYZ断面構成を示す説明図であり、図6は、図4のVI-VIの位置におけるインターコネクタ150のXY断面構成(基材156の空気極114側の表面)を示す説明図であり、図7は、図4のVII-VIIの位置におけるインターコネクタ150のXY断面構成を示す説明図である。
図2および図4に示すように、酸化剤ガス導入マニホールド161の位置に設けられたガス通路部材27の分岐部29に接続されたガス配管(図示せず)を介して酸化剤ガスOGが供給されると、酸化剤ガスOGは、ガス通路部材27の分岐部29および本体部28の孔を介して酸化剤ガス導入マニホールド161に供給され、酸化剤ガス導入マニホールド161から各発電単位102の酸化剤ガス供給連通孔132を介して、空気室166に供給される。また、図3および図5に示すように、燃料ガス導入マニホールド171の位置に設けられたガス通路部材27の分岐部29に接続されたガス配管(図示せず)を介して燃料ガスFGが供給されると、燃料ガスFGは、ガス通路部材27の分岐部29および本体部28の孔を介して燃料ガス導入マニホールド171に供給され、燃料ガス導入マニホールド171から各発電単位102の燃料ガス供給連通孔142を介して、燃料室176に供給される。
燃料電池スタック100において、各燃料ガス流路から空気室166への燃料ガスFG(または燃料オフガスFOG)のリークが発生すると、燃料電池スタック100の効率が低下するため、好ましくない。そのため、燃料電池スタック100には、高いガスシール性が求められる。以下、燃料電池スタック100におけるガスシールについて説明する。
以下、基材156の空気極114側の表面の内、燃料室連通孔108Bの全周を囲む環状の2つの領域(図6参照)を、「第2の基材領域158」といい、当該2つの第2の基材領域158を除く領域(図6参照)を、「第1の基材領域157」という。第1の基材領域157と第2の基材領域158とは隣接している。また、インターコネクタ150の第1の表面151の内、燃料室連通孔108Bの全周を囲む環状の2つの表面領域(図7参照)を、「第2の表面領域153」といい、当該2つの第2の表面領域153を除く領域(図4から図5、図7参照)を、「第1の表面領域152」という。第1の表面領域152と第2の表面領域153とは隣接している。本実施形態では、第2の表面領域153の外径D2(第1の表面領域152と第2の表面領域153との境界線の径)は、ガラスシール240の内径D1より大きく、かつ、ガラスシール240の外径D3より小さい。
図8から図10は、比較例の複合体103Xにおけるインターコネクタ150と空気極側フレーム130およびガラスシール240との間の変化状態1~3を示す説明図である。図8に示すように、比較例の複合体103Xの第1の表面151Xの全体は、第1のコート136だけで構成されている。このため、比較例の複合体103Xでは、燃料ガス流路に第1のコート136が露出している。この比較例の複合体103Xを備える燃料電池スタック100Aを運転すると、燃料ガス流路に流れる燃料ガスFGと第1のコート136との還元反応により、第1のコート136が多孔質化し(図9参照)、さらには、燃料ガス流路と空気室166とが貫通し、燃料ガスFGのリーク経路が形成されるおそれがある(図10参照)。
上述したように、第2のコート137は、第1のコート136に比べて、燃料ガスFGに対して耐還元性が高い。これらの第1のコート136および第2のコート137の耐還元性の評価方法の一例は次の通りである。まず、本実施形態の複合体103を1つ備える燃料電池スタック100と、上記比較例の複合体103Xを1つ備える燃料電池スタック100Aとを準備する。上述したように、本実施形態の複合体103では、燃料ガス流路に第2のコート137が露出しており、第1のコート136は露出していない。一方、比較例の燃料電池スタック100Aでは、燃料ガス流路に第1のコート136が露出している。
本実施形態の複合体103によれば、インターコネクタ150の第1の表面領域152を構成する第1のコート136と燃料ガス流路との間に、第1のコート136より耐還元性が高い第2のコート137が各燃料室連通孔108Bの全周に亘って配置されている。これにより、第1のコート136と燃料ガスFGとの還元反応に起因して燃料ガス流路のシール性が低下することを抑制することができる。
図11は、第2実施形態における複合体103AのXY断面構成を示す説明図である。第2実施形態の複合体103Aの構成の内、上述した第1実施形態の複合体103と同一の構成については、同一符号を付すことによって、その説明を省略する。
本明細書で開示される技術は、上述の実施形態に限られるものではなく、その要旨を逸脱しない範囲において種々の形態に変形することができ、例えば次のような変形も可能である。
Claims (8)
- 電解質層と前記電解質層を挟んで第1の方向に互いに対向する空気極および燃料極とを含む電気化学反応単セルと、燃料ガス流路を構成する第1の貫通孔が形成されており、前記電気化学反応単セルの前記燃料極側に配置されたインターコネクタと、を備えるインターコネクタ-電気化学反応単セル複合体において、
前記インターコネクタは、前記インターコネクタの前記燃料極側とは反対側の第1の表面を構成するコートを含み、
前記コートは、
前記インターコネクタの前記第1の表面の一部の領域であって、前記第1の貫通孔から離間した第1の表面領域を構成する第1のコートと、
前記インターコネクタの前記第1の表面の一部の領域であって、前記第1の貫通孔を囲み、かつ、前記第1のコートと前記第1の貫通孔との間の第2の表面領域を構成し、前記第1のコートより耐還元性が高い第2のコートと、を備えることを特徴とする、インターコネクタ-電気化学反応単セル複合体。 - 請求項1に記載のインターコネクタ-電気化学反応単セル複合体において、
前記インターコネクタには、酸化剤ガス流路を構成する第2の貫通孔が形成されており、
前記第1の表面領域は、前記第2の貫通孔を囲む表面領域を含むことを特徴とする、インターコネクタ-電気化学反応単セル複合体。 - 請求項1または請求項2に記載のインターコネクタ-電気化学反応単セル複合体において、
前記第2のコートは、クロミアを含むことを特徴とする、インターコネクタ-電気化学反応単セル複合体。 - 請求項1から請求項3までのいずれか一項に記載のインターコネクタ-電気化学反応単セル複合体において、
前記電解質層は、固体酸化物であることを特徴とする、インターコネクタ-電気化学反応単セル複合体。 - 前記第1の方向に並べて配列された複数のインターコネクタ-電気化学反応単セル複合体と、前記複数のインターコネクタ-電気化学反応単セル複合体の内、互いに隣り合う一方のインターコネクタ-電気化学反応単セル複合体が備えるインターコネクタと他方のインターコネクタ-電気化学反応単セル複合体との間に配置され、前記燃料ガス流路を構成するシール部材と、を備える電気化学反応セルスタックにおいて、
前記複数のインターコネクタ-電気化学反応単セル複合体の少なくとも1つは、請求項1から請求項4までのいずれか一項に記載のインターコネクタ-電気化学反応単セル複合体であり、
前記第1の方向視で、前記第2のコートの外周側の輪郭線は、前記シール部材の外周側の輪郭線の内側に位置していることを特徴とする、電気化学反応セルスタック。 - 請求項5に記載の電気化学反応セルスタックにおいて、
前記第1の方向視で、前記第1のコートの内周側の輪郭線は、前記シール部材の内周側の輪郭線の外側に位置していることを特徴とする、電気化学反応セルスタック。 - 前記第1の方向に並べて配列された複数のインターコネクタ-電気化学反応単セル複合体と、前記複数のインターコネクタ-電気化学反応単セル複合体の内、互いに隣り合う一方のインターコネクタ-電気化学反応単セル複合体が備えるインターコネクタと他方のインターコネクタ-電気化学反応単セル複合体との間に配置され、前記燃料ガス流路を構成するシール部材と、を備える電気化学反応セルスタックにおいて、
前記複数のインターコネクタ-電気化学反応単セル複合体の少なくとも1つは、請求項1から請求項4までのいずれか一項に記載のインターコネクタ-電気化学反応単セル複合体であり、
前記第1の方向視で、前記第1のコートの内周側の輪郭線は、前記シール部材の内周側の輪郭線の外側に位置していることを特徴とする、電気化学反応セルスタック。 - 請求項5から請求項7までのいずれか一項に記載の電気化学反応セルスタックにおいて、
前記複数のインターコネクタ-電気化学反応単セル複合体のそれぞれに含まれる電気化学反応単セルは、燃料電池単セルであることを特徴とする、電気化学反応セルスタック。
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