WO2018051954A1 - マイカ製部材、電気化学反応単位、および、電気化学反応セルスタック - Google Patents
マイカ製部材、電気化学反応単位、および、電気化学反応セルスタック Download PDFInfo
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- WO2018051954A1 WO2018051954A1 PCT/JP2017/032715 JP2017032715W WO2018051954A1 WO 2018051954 A1 WO2018051954 A1 WO 2018051954A1 JP 2017032715 W JP2017032715 W JP 2017032715W WO 2018051954 A1 WO2018051954 A1 WO 2018051954A1
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- mica
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- intensity peak
- cell stack
- power generation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/42—Micas ; Interstratified clay-mica 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
-
- 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
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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
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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
- H01M8/2457—Grouping of fuel cells, e.g. stacking of fuel cells with both reactants being gaseous or vaporised
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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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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- 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 a mica member.
- a solid oxide fuel cell (hereinafter referred to as “SOFC”) is known as one type of fuel cell that generates electricity using an electrochemical reaction between hydrogen and oxygen.
- the fuel cell power generation unit that constitutes the SOFC includes a fuel cell 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, an air electrode side member, and a fuel electrode side member And comprising.
- the air electrode side member constitutes an air chamber facing the air electrode
- the fuel electrode side member constitutes a fuel chamber facing the fuel electrode.
- the air electrode side member and the fuel electrode side member are formed of mica (see Patent Documents 1 and 2).
- Some mica contains Si (silicon) binder.
- Si contained in the fuel electrode side member may be scattered around due to a temperature rise due to power generation operation.
- the scattered Si adheres to the surface of the oxygen ion conductive material constituting the fuel electrode, thereby reducing the three-phase interface as a reaction field and changing (decreasing) the power generation performance of the fuel cell power generation unit.
- a technique is known in which mica is heated in advance at a temperature lower than 850 (° C.) to disperse Si contained in the binder and then used as a fuel electrode side member (see Patent Document 3).
- the mica member disclosed in this specification is a mica member, and in X-ray crystal structure analysis (XRD), an intensity peak of KMg 3 (Si 3 Al) O 10 (OH) 2 , A crystal structure including an intensity peak of Mg 2 SiO 4 is provided.
- XRD X-ray crystal structure analysis
- the inventor of the present invention has found that a member made of mica has an intensity peak of KMg 3 (Si 3 Al) O 10 (OH) 2 (soft mica) and Mg 2 SiO 4 (forsterite) in X-ray crystal structure analysis (XRD).
- the ratio of the intensity peak of the Mg 2 SiO 4 (120) plane to the intensity peak of the KMg 3 (Si 3 Al) O 10 (OH) 2 (003) plane is 0.00. It is good also as a structure which is 001 or more. According to this mica member, the ratio of the intensity peak of the Mg 2 SiO 4 (120) plane to the intensity peak of the KMg 3 (Si 3 Al) O 10 (OH) 2 (003) plane is 0.001 or more. Therefore, the presence of Si in the form of Mg 2 SiO 4 can more reliably suppress the scattering of Si.
- the ratio of the intensity peak of the Mg 2 SiO 4 (120) plane to the intensity peak of the KMg 3 (Si 3 Al) O 10 (OH) 2 (003) plane is 0.00. It is good also as a structure which is 15 or less. According to this mica member, the ratio of the intensity peak of the Mg 2 SiO 4 (120) plane to the intensity peak of the KMg 3 (Si 3 Al) O 10 (OH) 2 (003) plane is 0.15 or less. Therefore, it can be said that Si is sufficiently present as KMg 3 (Si 3 Al) O 10 (OH) 2 , and it is possible to suppress degradation of the original characteristics of mica such as sealing properties.
- the ratio of the intensity peak of the Mg 2 SiO 4 (120) plane to the intensity peak of the KMg 3 (Si 3 Al) O 10 (OH) 2 (003) plane is 0.00. It is good also as a structure which is 003 or more. According to this mica member, the ratio of the intensity peak of the Mg 2 SiO 4 (120) plane to the intensity peak of the KMg 3 (Si 3 Al) O 10 (OH) 2 (003) plane is 0.003 or more. Therefore, the presence of Si in the form of Mg 2 SiO 4 can more reliably suppress the scattering of Si.
- the ratio of the intensity peak of the Mg 2 SiO 4 (120) plane to the intensity peak of the KMg 3 (Si 3 Al) O 10 (OH) 2 (003) plane is 0.00.
- the configuration may be 029 or less.
- the ratio of the intensity peak of the Mg 2 SiO 4 (120) plane to the intensity peak of the KMg 3 (Si 3 Al) O 10 (OH) 2 (003) plane is 0.029 or less. Therefore, it can be said that Si is sufficiently present as KMg 3 (Si 3 Al) O 10 (OH) 2 , and it is possible to suppress degradation of the original characteristics of mica such as sealing properties.
- the structural member may be formed by the mica member described in (1) to (5) above. According to this electrochemical reaction unit, it is possible to suppress the performance of the electrochemical reaction unit from being deteriorated due to the scattering of Si into the air chamber or the fuel chamber.
- the electrochemical reaction cell stack including a plurality of electrochemical reaction units arranged in the first direction, wherein at least one of the plurality of electrochemical reaction units is the above It is good also as a structure characterized by being the electrochemical reaction unit of (6).
- the technology disclosed in the present specification can be realized in various forms, for example, mica-made members, structural members, electrochemical reaction single cells (fuel cell single cells or electrolytic cells), electrochemical It can be realized in the form of a reaction unit (fuel cell power generation unit), an electrochemical reaction cell stack (fuel cell stack or electrolytic cell stack) including a plurality of electrochemical reaction single cells, a manufacturing method thereof, and the like.
- FIG. 1 is a perspective view showing an external configuration of a fuel cell stack 100 in an 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. 6 is an explanatory diagram showing an X-ray diffraction pattern of Sample 2.
- FIG. 6 is an explanatory diagram showing an X-ray diffraction pattern of Sample 3.
- FIG. 6 is explanatory drawing which shows the X-ray-diffraction pattern of the sample 4.
- 6 is an explanatory diagram showing an X-ray diffraction pattern of Sample 5.
- 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 fuel cell stack corresponds to the electrochemical reaction cell stack in the claims.
- 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 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 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.
- (Configuration of power generation unit 102) 4 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. It is explanatory drawing which shows the YZ cross-section structure of the two electric power generation units.
- 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 power generation unit 102 corresponds to an electrochemical reaction unit in the claims.
- the interconnector 150 is a substantially rectangular flat plate-shaped conductive member, and is formed of, for example, ferritic stainless steel.
- 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.
- one interconnector 150 is shared by two adjacent power generation units 102. That is, 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.
- 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 and contains at least Zr.
- solid oxide such as YSZ (yttria stabilized zirconia), ScSZ (scandia stabilized zirconia), CaSZ (calcia stabilized zirconia), and the like. It is formed by things.
- 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 cobalt iron 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 passage 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 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 spacer 149 corresponds to a mica member or a structural member in the claims.
- 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 current collector elements 135 having a substantially quadrangular prism shape, and is formed of, for example, 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. Since 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 may be formed as an integral member.
- 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 fuel electrode 116 is connected via the fuel electrode side current collector 144.
- the other interconnector 150 is electrically connected.
- 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.
- spacer 149 In X-ray crystal structure analysis (XRD), the spacer 149 has an intensity peak (the peak of diffraction intensity) of KMg 3 (Si 3 Al) O 10 (OH) 2 (hereinafter referred to as “soft mica”), Mg 2 SiO 4 (hereinafter referred to as “forsterite”).
- the X-ray diffraction pattern obtained by analyzing the forming material of the spacer 149 by XRD includes a soft mica intensity peak and a forsterite intensity peak.
- the intensity peak ratio which is the ratio of the intensity peak on the face of the mirror index 120 of forsterite to the intensity peak on the face of the mirror index 003 of mica is 0.001 or more And it is preferable that it is 0.029 or less.
- a method of manufacturing the fuel cell stack 100 having the above-described configuration is, for example, as follows.
- the single cell 110 can be manufactured by a known method.
- a fuel electrode substrate layer green sheet, a fuel electrode active layer green sheet, and an electrolyte layer green sheet are prepared, a fuel electrode substrate layer green sheet, a fuel electrode active layer green sheet, and an electrolyte layer green sheet; And degrease at about 280 ° C. Further, firing is performed at about 1350 ° C. to obtain a laminate of the electrolyte layer 112 and the fuel electrode 116.
- the air electrode 114 is formed by spray-coating the liquid mixture which mixed the material for forming an air electrode on the surface of the electrolyte layer 112 in the said laminated body, and baking at 1100 degreeC. Through the above steps, the unit cell 110 having the above-described configuration is manufactured.
- the spacer 149 can be manufactured as follows. For example, a plate-shaped raw material member is formed by punching a mica sheet formed of soft mica (product number D581AK) having a thickness of 0.2 (mm) or more and 0.6 (mm) or less manufactured by Okabe Mica Industry Co., Ltd. Is made. Next, this raw material member is placed in a heating furnace and heated in the atmosphere at a temperature of 1000 (° C.) or higher for 4 hours or longer. Thereby, the spacer 149 having the above-described crystal structure can be manufactured.
- a plate-shaped raw material member is formed by punching a mica sheet formed of soft mica (product number D581AK) having a thickness of 0.2 (mm) or more and 0.6 (mm) or less manufactured by Okabe Mica Industry Co., Ltd. Is made. Next, this raw material member is placed in a heating furnace and heated in the atmosphere at a temperature of 1000 (° C.) or higher for 4 hours or longer. Thereby, the spacer 149 having the above-
- the spacer 149 is disposed between the electrode facing portion 145 and the interconnector facing portion 146 of the fuel electrode side current collector 144.
- the separator 120 to which the single cell 110 is brazed, and the air electrode side frame 130 are disposed. Thereby, the power generation unit 102 can be produced. Then, by performing the remaining assembly steps, the manufacture of the fuel cell stack 100 having the above-described configuration is completed.
- Performance evaluation of each sample Each performance performed using a plurality of samples 1 to 6 (spacers) produced by each of a plurality of production methods having different conditions for the heat treatment of the mica raw material member (hereinafter referred to as “mica heat treatment”). The evaluation will be described.
- the fuel cell stack 100 having the above-described configuration was assembled using each of the plurality of samples 1 to 6, and the durability deterioration rate (power generation deterioration rate) was measured.
- FIG. 6 is an explanatory diagram showing the results of performance evaluation for each sample.
- Samples 1 to 5 are spacers 149 having the above-described structure manufactured by the above-described manufacturing method, and sample 6 is a spacer manufactured by a manufacturing method having different mica heat treatment conditions from the above-described manufacturing method.
- X-ray diffraction patterns were obtained by XRD (powder X-ray diffraction method) for samples 1 to 5 prepared by the respective production methods. Specifically, the X-ray diffraction patterns of Samples 1 to 5 were obtained by irradiating and analyzing the plane part of the plate-like mica using an X-ray diffractometer.
- 7 to 11 are explanatory diagrams showing the X-ray diffraction patterns of the samples 1 to 5.
- FIG. The vertical axis represents the diffraction intensity (CPS), and the horizontal axis represents the diffraction angle 2 ⁇ (deg).
- Example 1 In the manufacturing method of Sample 1, the heating temperature in the mica heat treatment is 1000 (° C.), and the heating time is 30 hours.
- the X-ray diffraction pattern of Sample 1 is as shown in FIG.
- the X-ray diffraction pattern of Sample 1 was compared with a database of diffraction patterns of known substances (in this embodiment, for example, a PDF card (Powder Diffraction File)).
- the X-ray diffraction pattern of sample 1 shows, for example, intensities on the surfaces of the mirror indices 120, 211, and 221 of forsterite in addition to the intensity peak (see diffraction angle D2) on the surface of the soft mica mirror index 003. It was confirmed that peaks (diffraction angles D1, D3, D4) were included. Therefore, it can be judged that this sample 1 has soft mica crystals and forsterite crystals.
- the intensity peak ratio of sample 1 is 0.0012.
- Example 2 In the manufacturing method of Sample 2, the heating temperature in the mica heat treatment is 1100 (° C.), and the heating time is 5 hours.
- the X-ray diffraction pattern of Sample 2 is as shown in FIG.
- the X-ray diffraction pattern of Sample 2 is in addition to the intensity peak (see diffraction angle D2) on the surface of the soft mica Miller index 003 as in Sample 1.
- the intensity peaks (diffraction angles D1, D3, D4) on the surfaces of Forsterite's Miller indices 120, 211, 221 are included. Therefore, it can be judged that Sample 2 has soft mica crystals and forsterite crystals.
- the intensity peak ratio of sample 2 is 0.0031.
- Example 3 In the manufacturing method of Sample 3, the heating temperature in the mica heat treatment is 1100 (° C.), and the heating time is 30 hours.
- the X-ray diffraction pattern of Sample 3 is as shown in FIG.
- the X-ray diffraction pattern of sample 3 is the intensity peak on the surface of the soft mica mirror index 003 as in samples 1 and 2 (see diffraction angle D2).
- intensity peaks diffraction angles D1, D3, D4
- the intensity peak ratio of sample 3 is 0.0282.
- Example 4 In the manufacturing method of Sample 4, the heating temperature in the mica heat treatment is 1000 (° C.), and the heating time is 120 hours.
- the X-ray diffraction pattern of Sample 4 is as shown in FIG.
- the X-ray diffraction pattern of Sample 4 is the intensity peak on the surface of the soft mica Miller index 003 as in Samples 1 and 2 (see diffraction angle D2).
- intensity peaks diffraction angles D1, D3, D4
- the intensity peak ratio of Sample 4 is 0.1500.
- Example 5 In the manufacturing method of Sample 5, the heating temperature in the mica heat treatment is 850 (° C.), and the heating time is 5 hours.
- the X-ray diffraction pattern of Sample 5 is as shown in FIG.
- the X-ray diffraction pattern of Sample 5 is different from Samples 1 to 3 and is an intensity peak on the surface of soft mica with a Miller index of 003 (see diffraction angle D2). ), But almost no forsterite intensity peak was confirmed. Therefore, it can be determined that this sample 5 has soft mica crystals but no forsterite crystals.
- the intensity peak ratio of sample 5 is 0.0002.
- Example 6 In the manufacturing method of Sample 6, the heating temperature in the mica heat treatment is 1300 (° C.), and the heating time is 30 hours. As a result of performing the mica heat treatment under these conditions, the sample 6 was damaged, and thus qualitative analysis and performance evaluation could not be performed.
- the output voltage of the fuel cell stack 100 when the current density was 0.55 (A / cm 2 ) was measured, and the measured value was used as the initial voltage.
- the air electrode 114 is supplied with air as the oxidant gas OG, and the fuel electrode 116 is supplied with 4% water vapor and hydrogen as the fuel gas FG, and the rated power generation operation is started.
- the post-test voltage is the output voltage of the fuel cell stack 100 when the temperature is lower than that during the energization test, the voltage difference becomes significant, so that the voltage drop can be more clearly evaluated. And about each sample, it was set as "(circle)" when the voltage drop is less than determination voltage (for example, 65 (mV)), and set as "x" when it is more than determination voltage. Note that the initial voltage is measured for the fuel cell stack 100 within 1000 hours after the fuel cell stack 100 is shipped in a state where power generation is possible and rated power generation is performed.
- Si scattering amount For each of the fuel cell stacks 100 including the samples 1 to 5 for which the above-described (voltage drop) performance evaluation was performed, the surface of Si exposed to the fuel gas FG in the fuel electrode 116 of the single cell 110 of the fuel cell stack 100 was measured. The amount of adhesion was measured. By measuring this amount of adhesion, the amount of Si scattering in each of samples 1 to 5 can be obtained.
- the method for measuring the amount of scattered Si is as follows. A measurement sample including a surface exposed to the fuel gas FG in the fuel electrode 116 of the single cell 110 is prepared. The amount of Si adhering to the surface of the measurement sample exposed to the fuel gas FG is analyzed by secondary ion mass spectrometry (SIMS).
- SIMS secondary ion mass spectrometry
- a measurement sample is set in a SIMS device, and the surface of the measurement sample exposed to the fuel gas FG is irradiated with primary ions. Thereby, secondary ions jump out of the measurement sample surface, and the amount of Si deposited can be measured by mass analysis of the secondary ions.
- This Si adhesion amount is used as it is as the Si scattering amount of Samples 1 to 5.
- Samples 1 to 4 have soft mica crystals and forsterite crystals, so the intensity peak ratio of samples 1 to 4 is higher than that of sample 5.
- the intensity peak ratio is preferably 0.001 or more and 0.15 or less. If the intensity peak ratio is 0.001 or more, the scattering of Si can be more reliably suppressed. However, the higher the intensity peak ratio, the lower the inherent properties of mica such as sealing properties. For this reason, if intensity peak ratio is 0.15 or less, it can control that the original characteristic of mica falls.
- the intensity peak ratio is preferably 0.003 or more, and more preferably 0.025 or more. The intensity peak ratio is more preferably 0.029 or less.
- the intensity peak ratio increases and the voltage drop decreases as the heating temperature in the mica heat treatment increases. That is, the higher the heating temperature in the mica heat treatment, the more the raw material member can be made into a stable crystal structure in which Si is less likely to scatter.
- the heating temperature in the mica heat treatment is preferably less than 1300 (° C.).
- the longer the heating time the greater the intensity peak ratio and the smaller the voltage drop. That is, the longer the heating time in the mica heat treatment, the more the raw material member can be made into a stable crystal structure in which Si is less likely to scatter.
- the inventor of the present invention is that the member made of mica has an intensity peak of KMg 3 (Si 3 Al) O 10 (OH) 2 (soft mica) and Mg 2 SiO 4 (forsterite) in XRD.
- the spacer 149 has a crystal structure including an intensity peak of KMg 3 (Si 3 Al) O 10 (OH) 2 and an intensity peak of Mg 2 SiO 4 in XRD. Si scattering can be suppressed.
- the ratio of the intensity peak of the Mg 2 SiO 4 (120) plane to the intensity peak of the KMg 3 (Si 3 Al) O 10 (OH) 2 (003) plane is 0.001 or more, the Si Can be suppressed. Moreover, since the said ratio is 0.029 or less, it can suppress that the original characteristics of mica, such as a sealing performance, fall.
- the ratio of the intensity peak of the Mg 2 SiO 4 (120) plane to the intensity peak of the KMg 3 (Si 3 Al) O 10 (OH) 2 (003) plane is 0.003 or more, the Si is more reliably detected. Can be suppressed. Moreover, if the said ratio is 0.15 or less, it can suppress more effectively that the original characteristics of mica, such as a sealing performance, will fall.
- the spacer 149 is exemplified as the mica member or the structural member, but the present invention is not limited to this, and the present invention may be applied to the air electrode side frame 130 formed of mica. Further, the present invention may be applied to the fuel electrode side frame 140 as long as the fuel electrode side frame 140 is formed of mica. Moreover, you may apply this invention about the member made from mica used other than SOFC.
- the intensity peak ratio in the X-ray diffraction pattern of the spacer 149 is preferably 0.001 or more and 0.029 or less.
- the ratio may be 0.03 or more.
- it may be a member made of mica having a crystal structure including an intensity peak of KMg 3 (Si 3 Al) O 10 (OH) 2 and an intensity peak of Mg 2 SiO 4 at least in XRD.
- 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 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. Further, 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 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.
- all the single cells 110 included in the fuel cell stack 100 are configured to satisfy the above-described example range, but at least included in the fuel cell stack 100. If one power generation unit 102 has such a configuration, it is possible to achieve both improvement in power generation characteristics of the single cell 110 and maintenance of strength.
- 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. 2016-81813, and therefore will not be described in detail here. It is a configuration. That is, 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.
- the electrolysis cell stack when the electrolysis cell stack is operated, 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. As a result, 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 electrolytic cell unit and the electrolytic cell stack having such a configuration as in the above embodiment, if the fuel electrode 116 is configured in the above embodiment, the electrochemical reaction characteristics of the electrolytic cell and the strength can be maintained. Both can be achieved.
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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。なお、燃料電池スタックは、特許請求の範囲における電気化学反応セルスタックに相当する。
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。
スペーサー149は、X線結晶構造解析(XRD)において、KMg3(Si3Al)O10(OH)2(以下、「軟質マイカ」という)の強度ピーク(回折強度の頂点)と、Mg2SiO4(以下、「フォルステライト」という)の強度ピークとを含む結晶構造を備える。換言すれば、スペーサー149の形成材料をXRDで分析して得られるX線回折パターンは、軟質マイカの強度ピークと、フォルステライトの強度ピークとを含む。また、スペーサー149の形成材料のX線回折パターンにおいて、マイカのミラー指数003の面における強度ピークに対する、フォルステライトのミラー指数120の面における強度ピークの比率である強度ピーク比は、0.001以上、かつ、0.029以下であることが好ましい。
上述した構成の燃料電池スタック100の製造方法は、例えば、以下の通りである。単セル110は、公知の方法により作製することができる。例えば、燃料極基板層用グリーンシートと燃料極活性層用グリーンシートと電解質層用グリーンシートとを準備し、燃料極基板層用グリーンシートと燃料極活性層用グリーンシートと電解質層用グリーンシートとを貼り付けて約280℃で脱脂する。さらに、約1350℃にて焼成を行い、電解質層112と燃料極116との積層体を得る。また、空気極を形成するための材料を混合した混合液を、上記積層体における電解質層112の表面に噴霧塗布し、1100℃で焼成することによって空気極114が形成される。以上の工程により、上述した構成の単セル110が製造される。
上述のマイカの原料部材の加熱処理(以下、「マイカ加熱処理」という)の条件が互いに異なる複数の作製方法のそれぞれによって作製された複数のサンプル1~6(スペーサー)を用いて行った各性能評価について説明する。各サンプルについての性能評価では、複数のサンプル1~6のそれぞれを用いて、上述した構成の燃料電池スタック100を組み立て、耐久劣化率(発電劣化率)を測定した。図6は、各サンプルについての性能評価の結果を示す説明図である。
サンプル1~5は、上述の作製方法により作製された上記構成のスペーサー149であり、サンプル6は、上述の作製方法とはマイカ加熱処理の条件が異なる作製方法により作製されたスペーサーである。それぞれの作製方法により作成されたサンプル1~5について、XRD(粉末X線回折法)により、X線回折パターンを得た。具体的には、X線回折装置を用いて、板状のマイカの平面部分にX線を照射して分析することによって、各サンプル1~5のX線回折パターンを得た。図7から図11は、各サンプル1~5のX線回折パターンを示す説明図である。縦軸は回折強度(CPS)であり、横軸は回折角度2θ(deg)である。
サンプル1の作製方法では、マイカ加熱処理における加熱温度が1000(℃)であり、加熱時間が30時間である。サンプル1のX線回折パターンは、図7に示す通りである。このサンプル1のX線回折パターンと、既知物質の回折パターンのデータベース(本実施形態では、例えばPDFカード(Powder Diffraction File))とを対比した。その結果、サンプル1のX線回折パターンは、軟質マイカのミラー指数003の面における強度ピーク(回折角度D2参照)に加えて、例えばフォルステライトのミラー指数120,211,221の面のそれぞれにおける強度ピーク(回折角度D1,D3,D4)を含むことが確認された。したがって、このサンプル1は、軟質マイカの結晶とフォルステライトの結晶とを有すると判断できる。また、サンプル1の上記強度ピーク比は、0.0012である。
サンプル2の作製方法では、マイカ加熱処理における加熱温度が1100(℃)であり、加熱時間が5時間である。サンプル2のX線回折パターンは、図8に示す通りである。このサンプル2のX線回折パターンとPDFカードとを対比した結果、サンプル2のX線回折パターンは、サンプル1と同様、軟質マイカのミラー指数003の面における強度ピーク(回折角度D2参照)に加えて、例えばフォルステライトのミラー指数120,211,221の面のそれぞれにおける強度ピーク(回折角度D1,D3,D4)を含むことが確認された。したがって、このサンプル2は、軟質マイカの結晶とフォルステライトの結晶とを有すると判断できる。また、サンプル2の上記強度ピーク比は、0.0031である。
サンプル3の作製方法では、マイカ加熱処理における加熱温度が1100(℃)であり、加熱時間が30時間である。サンプル3のX線回折パターンは、図9に示す通りである。このサンプル3のX線回折パターンとPDFカードとを対比した結果、サンプル3のX線回折パターンは、サンプル1,2と同様、軟質マイカのミラー指数003の面における強度ピーク(回折角度D2参照)に加えて、例えばフォルステライトのミラー指数120,211,221の面のそれぞれにおける強度ピーク(回折角度D1,D3,D4)を含むことが確認された。したがって、このサンプル3は、軟質マイカの結晶とフォルステライトの結晶とを有すると判断できる。また、サンプル3の上記強度ピーク比は、0.0282である。
サンプル4の作製方法では、マイカ加熱処理における加熱温度が1000(℃)であり、加熱時間が120時間である。サンプル4のX線回折パターンは、図10に示す通りである。このサンプル4のX線回折パターンとPDFカードとを対比した結果、サンプル4のX線回折パターンは、サンプル1,2と同様、軟質マイカのミラー指数003の面における強度ピーク(回折角度D2参照)に加えて、例えばフォルステライトのミラー指数120,211,221の面のそれぞれにおける強度ピーク(回折角度D1,D3,D4)を含むことが確認された。したがって、このサンプル4は、軟質マイカの結晶とフォルステライトの結晶とを有すると判断できる。また、また、サンプル4の上記強度ピーク比は、0.1500である。
サンプル5の作製方法では、マイカ加熱処理における加熱温度が850(℃)であり、加熱時間が5時間である。サンプル5のX線回折パターンは、図11に示す通りである。このサンプル5のX線回折パターンとPDFカードとを対比した結果、サンプル5のX線回折パターンは、サンプル1~3とは異なり、軟質マイカのミラー指数003の面における強度ピーク(回折角度D2参照)を含むことは確認できたが、フォルステライトの強度ピークを含むことはほとんど確認できなかった。したがって、このサンプル5は、軟質マイカの結晶を有するが、フォルステライトの結晶を有しないと判断できる。また、サンプル5の上記強度ピーク比は、0.0002である。
サンプル6の作製方法では、マイカ加熱処理における加熱温度が1300(℃)であり、加熱時間が30時間である。この条件でマイカ加熱処理を行った結果、サンプル6が破損したため、定性分析や性能評価を行うことができなかった。
(電圧低下)
各サンプル1~5を備えるそれぞれの燃料電池スタック100(つまり、4台の燃料電池スタック100)について、まず、850(℃)で、空気極114に酸化剤ガスOGとして空気を供給し、燃料極116に燃料ガスFGとして40%の水蒸気と水素とを供給しつつ、400時間、通電試験を行った。この通電試験によれば、燃料電池スタック100の温度が定格発電運転時より高いため、燃料電池スタック100内を、Si(シリコン)が飛散し易い環境下にすることができる。また、この通電試験開始時において、電流密度が0.55(A/cm2)のときの燃料電池スタック100の出力電圧を測定し、その測定値を、初期電圧とした。その後、約700(℃)で、空気極114に酸化剤ガスOGとして空気を供給し、燃料極116に燃料ガスFGとして4%の水蒸気と水素とを供給しつつ、定格発電運転を開始し、電流密度が0.55(A/cm2)であるときの燃料電池スタック100の出力電圧(試験後電圧)を測定し、初期電圧と試験後電圧との差である電圧低下(mV)を算出した。電圧低下が大きいほど、発電劣化率が大きいことを意味する。試験後電圧は、通電試験時より温度が低いときの燃料電池スタック100の出力電圧であることによって電圧差が顕著になるため、電圧低下をより明確に評価することができる。そして、各サンプルについて、電圧降下が判定電圧(例えば65(mV))未満である場合「○」とし、判定電圧以上である場合「×」とした。なお、初期電圧とは、燃料電池スタック100が発電可能な状態で出荷され、定格発電が行われてから1000時間以内の燃料電池スタック100について測定するものとする。
上述の(電圧低下)の性能評価を行ったサンプル1~5を備えるそれぞれの燃料電池スタック100について、燃料電池スタック100の単セル110の燃料極116における燃料ガスFGに晒された表面のSiの付着量を測定した。この付着量を測定することで、各サンプル1~5におけるSi飛散量とすることができる。Siの飛散量の測定方法は次の通りである。単セル110の燃料極116における燃料ガスFGに晒された表面を含む測定サンプルを準備する。この測定用サンプルに対し、二次イオン質量分析法(SIMS)により、測定用サンプルの燃料ガスFGに晒された表面に付着したSiの付着量を分析する。具体的には、SIMSの装置に測定用サンプルをセットして、測定用サンプルにおける燃料ガスFGに晒された表面に対し、一次イオンを照射する。これにより、測定用サンプル表面から二次イオンが飛び出し、この二次イオンを質量分析することでSiの付着量を測定することができる。このSiの付着量をそのまま、サンプル1~5のSi飛散量とする。
まず、サンプル1~5の評価結果について検討する。図6に示すように、電圧降下の評価では、サンプル1~4の判定結果は「〇」であるのに対し、サンプル5の判定結果は「×」であった。また、サンプル1~4のSiの飛散量は600~690(ppm)であるのに対し、サンプル5のSiの飛散量は900(ppm)であり、サンプル1~4では、サンプル5に比べて、Siの飛散量が抑制されていることが確認できる。また、上述したように、サンプル1~4は、軟質マイカの結晶とフォルステライトの結晶とを有するのに対し、サンプル5は、軟質マイカの結晶を有するが、フォルステライトの結晶を有しない。
上述したように、本件の発明者は、マイカ製部材が、XRDにおいて、KMg3(Si3Al)O10(OH)2(軟質マイカ)の強度ピークと、Mg2SiO4(フォルステライト)の強度ピークとを含む結晶構造を備える場合、XRDにおいて、KMg3(Si3Al)O10(OH)2の強度ピークのみを有する純粋な軟質マイカに比べて、Siの飛散を抑制することができることを実験等によって見出した。そこで、本実施形態によれば、スペーサー149は、XRDにおいて、KMg3(Si3Al)O10(OH)2の強度ピークと、Mg2SiO4の強度ピークとを含む結晶構造を備えるため、Siの飛散を抑制することができる。
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 (7)
- マイカ製部材であって、
X線結晶構造解析(XRD)において、KMg3(Si3Al)O10(OH)2の強度ピークと、Mg2SiO4の強度ピークとを含む結晶構造を備えることを特徴とする、マイカ製部材。 - 請求項1に記載のマイカ製部材において、
前記KMg3(Si3Al)O10(OH)2(003)面の強度ピークに対する、前記Mg2SiO4(120)面の強度ピークの比率は、0.001以上であることを特徴とするマイカ製部材。 - 請求項1または請求項2に記載のマイカ製部材において、
前記KMg3(Si3Al)O10(OH)2(003)面の強度ピークに対する、前記Mg2SiO4(120)面の強度ピークの比率は、0.15以下であることを特徴とするマイカ製部材。 - 請求項1から請求項3までのいずれか一項に記載のマイカ製部材において、
前記KMg3(Si3Al)O10(OH)2(003)面の強度ピークに対する、前記Mg2SiO4(120)面の強度ピークの比率は、0.003以上であることを特徴とするマイカ製部材。 - 請求項1から請求項4までのいずれか一項に記載のマイカ製部材において、
前記KMg3(Si3Al)O10(OH)2(003)面の強度ピークに対する、前記Mg2SiO4(120)面の強度ピークの比率は、0.029以下であることを特徴とするマイカ製部材。 - 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単セルと、前記空気極に面する空気室または前記燃料極に面する燃料室に面する構造部材と、を備える電気化学反応単位において、
前記構造部材は、請求項1から請求項5までのいずれか一項に記載のマイカ製部材により形成されていることを特徴とする、電気化学反応単位。 - 前記第1の方向に並べて配置された複数の電気化学反応単位を備える電気化学反応セルスタックにおいて、
前記複数の電気化学反応単位の少なくとも1つは、請求項6に記載の電気化学反応単位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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