WO2019189911A1 - 電気化学素子の金属支持体、電気化学素子、電気化学モジュール、電気化学装置、エネルギーシステム、固体酸化物形燃料電池及び金属支持体の製造方法 - Google Patents
電気化学素子の金属支持体、電気化学素子、電気化学モジュール、電気化学装置、エネルギーシステム、固体酸化物形燃料電池及び金属支持体の製造方法 Download PDFInfo
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0232—Metals or alloys
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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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- 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
- C25B9/60—Constructional parts of cells
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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
- C25B9/75—Assemblies comprising two or more cells of the filter-press type having bipolar electrodes
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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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/669—Steels
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/74—Meshes or woven material; Expanded metal
- H01M4/742—Meshes or woven material; Expanded metal perforated material
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/75—Wires, rods or strips
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- H—ELECTRICITY
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1097—Fuel cells applied on a support, e.g. miniature fuel cells deposited on silica supports
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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
- H01M8/10—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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
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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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04858—Electric variables
- H01M8/04925—Power, energy, capacity or load
- H01M8/0494—Power, energy, capacity or load of fuel cell stacks
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
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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
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
- H01M8/1226—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material characterised by the supporting layer
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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
- H01M8/1286—Fuel cells applied on a support, e.g. miniature fuel cells deposited on silica supports
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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
- Y02E60/10—Energy storage using batteries
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a metal support for an electrochemical element.
- Patent Document 1 discloses a metal support structure of a metal support type SOFC.
- the metal support of Patent Document 1 has a structure in which a metal foil having a thickness of about 15 ⁇ m is laminated on a metal mesh having a thickness of 200 ⁇ m or more obtained by weaving metal wires.
- the present invention has been made in view of the above problems, and an electrode layer having a uniform thickness and suppressing surface defects such as cracking and peeling by using a metal support that suppresses warping as a metal support of an electrochemical element.
- An object of the present invention is to provide a metal support for an electrochemical element that can be laminated.
- the characteristic configuration of the metal support of the electrochemical device according to the present invention is as follows:
- the metal support has a plate-like surface and is plate-like as a whole, and the metal support has a plurality of through spaces penetrating from the front side surface to the back side surface with the surface on which the electrode layer is provided as the front side surface. Having a hole area in which the through space is formed on the front side surface, It is in the point which satisfies the following curvature. (Degree of warping)
- the least square value is calculated by the least square method using at least three points in the plate-like surface of the metal support, and the plus side maximum displacement value and the least square value to the plus side with respect to the least square value are calculated.
- the sum of the difference of each plus side maximum displacement value with respect to the least square value and minus side maximum displacement value is calculated among several points in the plate-shaped surface of a metal support body.
- the least square value is, for example, a straight line or a plane calculated from the plurality of points using the least square method.
- Da is obtained by adding, for example, the plus side maximum displacement value (plus side maximum displacement value) and the minus side maximum displacement value (minus side maximum displacement value) to the least square value composed of the straight line and the plane.
- the degree of warpage can be compared with a constant reference value. Then, the degree of warpage of the metal support is accurately calculated in this way, and the degree of warpage is 1.5 ⁇ 10 ⁇ 2 or less, so that the electrode layer formed on the metal support has a uniform thickness, It can be laminated with few surface defects such as peeling. If an electrode layer with such defects suppressed can be laminated, the electrolyte layer, counter electrode layer, etc. laminated thereon can be laminated with a uniform thickness and few surface defects such as cracking and peeling. For this reason, since it can laminate
- At least two points in the plate-like surface of the metal support are at least two points facing each other around the center of gravity in the plate-like surface of the metal support on at least one straight line passing through the center of gravity. In the point.
- the least square value is calculated using points located in directions away from each other with respect to the center of gravity within the plate-like surface. That is, the least square value is not calculated from points in the local region of the metal support, but from points dispersed in the plate-like surface. Therefore, the least square value is calculated as a value related to the shape of the plate-like surface of the metal support. And by using this least square value as a reference, Da serving as a reference for determining the degree of warpage of the metal support can be accurately calculated.
- a plurality of straight lines passing through the center of gravity of the metal support extend radially at predetermined angles with the center of gravity as the center. Therefore, the least square value is calculated based on the points dispersed almost throughout the metal support.
- Da serving as a reference for determining the degree of warpage of the metal support can be calculated with high accuracy.
- a plurality of straight lines passing through the center of gravity of the metal support is a straight line extending radially every 90 degrees or less around the center of gravity, Da can be calculated more accurately, and preferably every 60 degrees or less. More preferably, the straight line extends radially.
- a plurality of straight lines passing through the center of gravity of the metal support are straight lines extending radially at an angle of 30 degrees or more with the center of gravity as the center, because the measurement work of the degree of warpage becomes simple.
- the least square value is calculated using at least two points located in the region from the periphery of the metal support to the hole region, that is, the periphery of the metal support.
- the degree of warping of the metal support is generally greater at the periphery than at the center.
- the difference in the degree of warpage of the metal support does not appear large between the central part and the peripheral part, but when the area is large, the warp is greater at the peripheral part than at the central part. Therefore, by calculating Da based on the points located at the peripheral edge, Da can be calculated with high accuracy, and thus the degree of warpage of the metal support can be calculated with high accuracy.
- Da can be calculated with high accuracy by calculating Da based on the points located at the peripheral portion, and thus the degree of warpage of the metal support can be calculated with high accuracy.
- the least square value is a point that is a least square plane calculated by a least square method using at least four points in the plate-like surface of the metal support.
- the least square plane is calculated using at least four points in the plate-like plane.
- the degree of warpage can also be accurately determined by calculating Da based on the difference with respect to the least squares plane.
- the points located in directions away from the center of gravity in the plate-like surface are used as at least four points in the plate-like surface, the shape of the plate-like surface is approximated from the points dispersed in the plate-like surface. This is preferable because a least squares plane is calculated.
- the least square plane is calculated by the least square method using five or more points in the plate-like surface, a plurality of points in the plate-like surface are used, and Da can be calculated accurately, which is preferable. .
- the front side opening that is the opening on the front side of the through space is in a circular or substantially circular shape with a diameter of 10 ⁇ m to 60 ⁇ m.
- the front opening is preferably a circular shape or a substantially circular shape having a diameter of 10 ⁇ m or more, more preferably a circular shape or a substantially circular shape having a diameter of 15 ⁇ m or more, and a circular shape or a substantially circular shape having a diameter of 20 ⁇ m or more.
- a sufficient amount of fuel gas (or air) can be supplied to the electrode layer of the electrochemical element, and the performance as the electrochemical element can be further enhanced. Also.
- the front side opening is preferably a circular shape or a substantially circular shape having a diameter of 60 ⁇ m or less, more preferably a circular shape or a substantially circular shape having a diameter of 50 ⁇ m or less, and further preferably a circular shape or a substantially circular shape having a diameter of 40 ⁇ m or less.
- the back side opening part which is an opening part of the back side surface of the penetration space has a larger area or diameter than the front side opening part which is an opening part of the front side surface of the penetration space.
- the formation of the through space is further facilitated, and the workability and cost at the time of mass production can be improved. Further, since the ratio of the thickness of the entire metal support to the area of the front opening of the metal support can be increased, the structure of an electrochemical element such as an electrode layer on the metal support while having sufficient strength This is preferable because the element can be easily formed.
- the strength and performance of the metal support can be compatible with each other, which is preferable.
- interval of the said front side opening part is 0.05 mm or more, It is more preferable that it is 0.1 mm or more, It is still more preferable that it is 0.15 mm or more. By doing so, it is possible to further increase the strength as a metal support, and it becomes easier to form components of electrochemical elements such as electrode layers on the metal support having a plurality of through spaces. It is. Also.
- the distance between the front openings is preferably 0.3 mm or less, more preferably 0.25 mm or less, and further preferably 0.2 mm or less. By doing in this way, sufficient quantity of fuel gas (or air) can be supplied to the electrode layer of an electrochemical element by doing in this way, and the performance as an electrochemical element can be improved more. Because.
- the overall strength of the metal support can be sufficiently maintained while making the size of the through space appropriate, so that the workability during mass production can be improved and the material cost can be reduced. Therefore, it is preferable.
- the thickness of the metal support is preferably 0.1 mm or more, more preferably 0.15 mm or more, and further preferably 0.2 mm or more. By doing so, it is easier to handle during mass production while maintaining the strength as a metal support. Also.
- the thickness of the metal support is preferably 1.0 mm or less, more preferably 0.75 mm or less, and even more preferably 0.5 mm or less. By doing in this way, it is because the material cost of a metal support body can be reduced more, maintaining the intensity
- a further characteristic configuration of the metal support of the electrochemical device according to the present invention is that the material is an Fe—Cr alloy.
- the oxidation resistance and high temperature strength of the metal support can be improved.
- the thermal expansion coefficient can be made close to that of the constituent elements of the electrochemical element such as the electrode layer and the electrolyte layer formed on the metal support, an electrochemical element having excellent heat cycle durability can be realized. preferable.
- the characteristic configuration of the electrochemical device according to the present invention is as follows. It is that at least an electrode layer, an electrolyte layer, and a counter electrode layer are provided on the front side surface of the metal support.
- An electrochemical device in which at least an electrode layer, an electrolyte layer, and a counter electrode layer are provided on the front side surface of the metal support described above has improved workability and cost during mass production while ensuring sufficient performance. It is suitable.
- the components of electrochemical elements such as electrode layers and electrolyte layers are formed on a metal support with excellent strength, the components of electrochemical elements such as electrode layers and electrolyte layers are made thinner and thinner. Therefore, the material cost of the electrochemical element can be reduced, which is preferable.
- the electrochemical module is excellent in strength and reliability while suppressing material cost and processing cost and being compact and high-performance. Can be obtained.
- the characteristic configuration of the electrochemical device according to the present invention is as follows: It has the fuel supply part which has the said electrochemical module and a reformer at least, and supplies the fuel gas containing a reducing component with respect to the said electrochemical module.
- the fuel module includes the electrochemical module and the reformer and supplies the fuel gas containing the reducing component to the electrochemical module.
- the fuel supply infrastructure it is possible to realize an electrochemical device equipped with an electrochemical module having excellent durability, reliability and performance. Moreover, since it becomes easy to construct a system for recycling unused fuel gas discharged from the electrochemical module, a highly efficient electrochemical device can be realized.
- the electrical output obtained from the electrochemical module excellent in durability, reliability and performance can be boosted by an inverter or converted from direct current to alternating current. It is preferable because the electric output obtained in the above can be easily used.
- the above characteristic configuration because it has an electrochemical device and a waste heat utilization part that reuses the heat exhausted from the electrochemical device, it is excellent in durability, reliability, and performance, and also in energy efficiency.
- An energy system can be realized. It is also possible to realize a hybrid system with excellent energy efficiency in combination with a power generation system that generates power using the combustion heat of unused fuel gas discharged from an electrochemical device.
- the characteristic configuration of the solid oxide fuel cell according to the present invention is: The electrochemical element is provided and a power generation reaction is caused by the electrochemical element.
- a power generation reaction can be performed as a solid oxide fuel cell having an electrochemical element excellent in durability, reliability, and performance, a highly durable and high performance solid oxide form A fuel cell can be obtained.
- the raw fuel is converted to hydrogen in a fuel cell system using a hydrocarbon gas such as city gas as the raw fuel. It is more preferable because it is possible to construct a system that can cover the necessary heat with the exhaust heat of the fuel cell, so that the power generation efficiency of the fuel cell system can be increased.
- a solid oxide fuel cell that is operated in a temperature range of 900 ° C.
- a solid oxide fuel cell operated in the following temperature range is more preferable because the effect of suppressing Cr volatilization can be further enhanced.
- the characteristic configuration of the method for producing a metal support according to the present invention is as follows: A manufacturing method for manufacturing the metal support, wherein a plurality of penetration spaces penetrating from the front side surface to the back side surface are formed by laser processing, punching processing, etching processing, or a combination thereof. is there.
- the formation of the through space is facilitated, and the workability and cost at the time of mass production can be improved.
- a metal support with a small curvature degree is obtained by smoothing process, it becomes easy to form an electrochemical element on a metal support, and it is preferable.
- the electrochemical element E is used, for example, as a component of a solid oxide fuel cell that generates electric power by receiving supply of a fuel gas containing hydrogen and air.
- the side of the counter electrode layer 6 as viewed from the electrolyte layer 4 is referred to as “upper” or “upper”, and the side of the electrode layer 2 is referred to as “lower” or “lower”.
- the surface of the metal support 1 on which the electrode layer 2 is formed is referred to as a front side surface 1a, and the opposite side surface is referred to as a back side surface 1b.
- the electrochemical element E includes a metal support 1, an electrode layer 2 formed on the metal support 1, an intermediate layer 3 formed on the electrode layer 2, and an intermediate layer. 3 and an electrolyte layer 4 formed on the substrate 3.
- the electrochemical element E further includes a reaction preventing layer 5 formed on the electrolyte layer 4 and a counter electrode layer 6 formed on the reaction preventing layer 5. That is, the counter electrode layer 6 is formed on the electrolyte layer 4, and the reaction preventing layer 5 is formed between the electrolyte layer 4 and the counter electrode layer 6.
- the electrode layer 2 is porous, and the electrolyte layer 4 is dense.
- the metal support 1 supports the electrode layer 2, the intermediate layer 3, the electrolyte layer 4, etc., and maintains the strength of the electrochemical element E. That is, the metal support 1 plays a role as a support for supporting the electrochemical element E.
- the metal support 1 has a warp degree of 1.5 ⁇ 10 ⁇ 2 or less, and the electrode layer 2 and the like are appropriately stacked on the metal support 1.
- the material of the metal support a material excellent in electron conductivity, heat resistance, oxidation resistance and corrosion resistance is used.
- ferritic stainless steel, austenitic stainless steel, nickel base alloy, or the like is used.
- an alloy containing chromium is preferably used.
- the metal support 1 uses an Fe—Cr alloy containing 18% by mass or more and 25% by mass or less of Cr, but an Fe—Cr alloy containing 0.05% by mass or more of Mn, Fe—Cr-based alloy containing 0.15 to 1.0% by mass of Ti, Fe—Cr-based alloy containing 0.15 to 1.0% by mass of Zr, Ti and Zr Fe—Cr alloy having a total content of Ti and Zr of 0.15% by mass or more and 1.0% by mass or less, Fe—Cr system containing Cu of 0.10% by mass or more and 1.0% by mass or less An alloy is particularly preferable.
- the metal support 1 is plate-shaped as a whole.
- the metal support 1 has a plurality of through spaces 1c penetrating from the front side surface 1a to the back side surface 1b with the surface on which the electrode layer 2 is provided as the front side surface 1a.
- the through space 1c has a function of transmitting gas from the back side surface 1b of the metal support 1 to the front side surface 1a.
- the shape of the plate-shaped surface (front side surface 1a) of the metal support 1 is not particularly limited, and may be, for example, a rectangular shape such as a square or a rectangle, a circular shape or an elliptical shape.
- a metal oxide layer 1 f as a diffusion suppression layer is provided on the surface of the metal support 1. That is, a diffusion suppression layer is formed between the metal support 1 and an electrode layer 2 described later.
- the metal oxide layer 1 f is provided not only on the surface exposed to the outside of the metal support 1 but also on the contact surface (interface) with the electrode layer 2. It can also be provided on the inner surface of the through space 1c.
- the metal oxide layer 1f element interdiffusion between the metal support 1 and the electrode layer 2 can be suppressed.
- the metal oxide layer 1f is mainly made of chromium oxide.
- the metal oxide layer 1f which has a chromium oxide as a main component suppresses that the chromium atom etc. of the metal support body 1 diffuses into the electrode layer 2 or the electrolyte layer 4.
- the thickness of the metal oxide layer 1f may be a thickness that can achieve both high diffusion prevention performance and low electrical resistance.
- the metal oxide layer 1f can be formed by various methods, a method of oxidizing the surface of the metal support 1 to form a metal oxide is preferably used.
- a metal oxide layer 1f is sprayed onto the surface of the metal support 1 (spraying method, aerosol deposition method, aerosol gas deposition method, powder jet deposition method, particle jet deposition method, cold spray method, etc.) Method), PVD method such as sputtering method or PLD method, CVD method or the like, or plating and oxidation treatment.
- the metal oxide layer 1f may include a spinel phase having high conductivity.
- the degree of warpage is an index of how much the metal support 1 is warped with respect to a flat surface.
- the center of gravity G of the metal support 1 is obtained.
- the center of gravity G is a point where the first moment around the center of gravity G becomes zero when it is assumed that the metal support 1 has no hole region g1 and the thickness and density are uniform.
- the shape of the plate-like surface (front side surface 1a) of the metal support 1 is a rectangular shape such as a square or a rectangle, it is the intersection of diagonal lines, and if it is circular, it is the center. This is a point corresponding to the intersection of the short axes.
- the straight lines L1 to L4 are a plurality of straight lines extending radially from the center of gravity G. Further, the straight lines L1 to L4 divide 360 ° by a predetermined angle with the center of gravity G as the center. In the case of FIG. 6, straight lines L1 to L4 are drawn so as to be separated every 45 °. Here, four straight lines L1 to L4 are drawn, but the number of straight lines L is not limited to this, and may be 1 to 3, or 5 or more. Moreover, the angle which divides
- a plurality of straight lines passing through the center of gravity G of the metal support 1 are straight lines extending radially every 90 degrees or less with the center of gravity G as the center, Da described below can be calculated with higher accuracy, A straight line extending radially every angle of 60 degrees or less is more preferable.
- the plurality of straight lines passing through the center of gravity G of the metal support 1 are straight lines extending radially every 30 degrees or more with the center of gravity G as the center because the warp measurement work becomes simple.
- each of the straight lines L1 to L4 two points P facing each other around the center of gravity G in the plate-like surface of the metal support 1 are extracted. Further, the two opposite points P are points existing in the region of the peripheral portion OP from the peripheral edge of the metal support 1 to the hole region g1 (FIG. 5).
- the points P1a and P1b are extracted for the straight line L1
- the points P2a and P2b are extracted for the straight line L2
- the points P3a and P3b are extracted for the straight line L3
- the eight points P4a and P4b are extracted for the straight line L4.
- two points P facing each other with the center of gravity G as the center are extracted for one straight line L, but three or more points P may be extracted for one straight line L.
- the size of the peripheral portion OP also varies depending on the metal support 1.
- the peripheral portion OP can be, for example, within about 20% from the peripheral edge of the metal support 1.
- the peripheral portion OP is within about 20% of the distance from the peripheral edge of the metal support 1. .
- it can be within about 10% from the periphery of the metal support 1, and further can be within about 5% from the periphery of the metal support 1.
- the metal support 1 layers such as the electrode layer 2, the intermediate layer 3, the electrolyte layer 4, the reaction preventing layer 5, and the counter electrode layer 6 are placed. It may be between any of the outer edges and the periphery of the metal support 1.
- a later-described least square plane ⁇ minimum square value that represents the shape of the metal support 1 can be obtained.
- the least square plane ⁇ is obtained by the least square method using the eight points P1a to P4b extracted above.
- the least square plane ⁇ is a plane that approximately represents the range in which the points P1a to P4b exist.
- the least square plane ⁇ is indicated by a plane having a cross section as shown in FIG.
- a positive maximum displacement value to the positive side (first side) and a negative maximum displacement value to the negative side (second side) are obtained.
- the point P3a farthest on the plus side with respect to the least square plane ⁇ is the plus side maximum displacement point
- the distance from the least square plane ⁇ to the point P3a is the plus side maximum displacement value N1.
- the point P2b farthest on the minus side with respect to the least square plane ⁇ is the minus maximum displacement point
- the distance from the least square plane ⁇ to the point P2b is the minus maximum displacement value N2.
- the first difference between the plus side maximum displacement point, which is the point P3a, and the least squares plane ⁇ is the plus side maximum displacement value N1.
- the second difference between the minus-side maximum displacement point that is the point P2b and the least-squares plane ⁇ is a minus-side maximum displacement value N2. From the sum of the first difference and the second difference, that is, the sum of the plus-side maximum displacement value N1 and the minus-side maximum displacement value N2, Da is obtained as a reference for determining the degree of warping of the metal support 1.
- Da / Lmax obtained by dividing Da by the maximum length Lmax on the plate-like surface of the metal support 1 is calculated as the degree of warpage.
- the lengths of two pairs of sides are Lx and Ly, respectively, and the maximum length Lmax is the sum of the square of Lx and the square of Ly. Is obtained from the square root of.
- the degree of warpage is preferably 1.5 ⁇ 10 ⁇ 2 or less. More preferably, the degree of warpage is 1.0 ⁇ 10 ⁇ 2 or less, and further preferably the degree of warpage is 5.0 ⁇ 10 ⁇ 3 or less. As the degree of warpage is smaller, the thickness of the electrode layer 2 and the like is uniform on the metal support 1 and there are few surface defects such as cracking and peeling, so that it can be laminated flat and with good adhesion.
- a smoothing process for example, a leveler process, an annealing process, etc. may be performed according to the degree of warping of the metal support 1.
- the metal support 1 having a degree of warpage of greater than 1.5 ⁇ 10 ⁇ 2 is smoothed.
- the pore region 1g is 5.0 ⁇ 10 2 mm 2 or more, preferably for easily suppress warpage of the metal support 1 by smoothing, pore region 1g is 2.5 ⁇ 10 3 mm 2 or more In this case, it is more preferable because the effect of suppressing the degree of warpage can be obtained more greatly.
- the least square plane ⁇ is calculated using the points P located in directions away from the center of gravity G in the plate-like surface of the metal support 1.
- the points P are points that are dispersed almost throughout the metal support 1. Therefore, the least square plane ⁇ is obtained as a plane approximating the shape of the plate-like surface of the metal support 1 from the points P dispersed in the plate-like surface. Therefore, by calculating Da based on the difference with respect to the least square plane ⁇ , it is possible to accurately determine the degree of warpage.
- the degree of warpage can be compared with a constant reference value even for metal supports 1 of different sizes.
- Da tends to increase, but when it is relatively small, Da tends to decrease. Therefore, it is preferable to divide Da by the maximum length Lmax so that the warp degree can be compared with a constant value even in the metal supports 1 having different sizes.
- the degree of warpage of the metal support 1 with high accuracy and setting the degree of warpage to 1.5 ⁇ 10 ⁇ 2 or less, a flat metal support 1 with less warpage can be obtained. Since the metal support 1 itself is flat, even when the electrode layer 2, the electrolyte layer 4, the counter electrode layer 6 and the like are formed on the metal support 1, these layers can also be formed flat. Therefore, peeling of these layers from the metal support 1, deterioration of adhesion between these layers, cracking, and the like can be suppressed. Further, when a cell is produced by laminating a plurality of layers including the electrode layer 2, the electrolyte layer 4, the counter electrode layer 6, and the like on the metal support 1, the metal support 1 and each layer are more closely attached.
- each layer is weighted by a press or the like.
- a weight is applied to the metal support 1 and each layer substantially uniformly. Therefore, when a load is applied to each layer with a press or the like, cracking and peeling of each layer and peeling from the metal support 1 are suppressed. As a result, a cell having a uniform thickness, few surface defects such as cracking and peeling, and high interlaminar adhesion can be produced. As a result, the electrochemical reaction between the layers is efficiently performed, and the performance of the electrochemical element E can be improved.
- the points P1a to P4b are located in the peripheral portion OP.
- the least square plane (alpha) is calculated
- the degree of warping of the metal support 1 is generally greater in the peripheral portion OP than in the central portion.
- the degree of warping of the metal support 1 is generally greater in the peripheral portion OP than in the central portion.
- the degree of warping of the metal support 1 is generally greater in the peripheral portion OP than in the central portion.
- the least square plane ⁇ is obtained using eight points P1a to P4b.
- the least square plane ⁇ can be obtained using at least four points located in the peripheral portion OP.
- the points P located in the direction away from the center of gravity G in the plate-like surface are used as at least four points in the plate-like surface
- the shape of the plate-like surface is determined from the points dispersed in the plate-like surface. Is preferred because a least squares plane ⁇ approximating is calculated.
- the least square plane ⁇ is calculated by the least square method using five or more points of the peripheral portion OP, a plurality of points in the plate-like surface of the metal support 1 are used, and Da is accurate.
- the least-squares plane ⁇ it is preferable because it can be calculated well. Moreover, it is preferable to calculate the least-squares plane ⁇ by the least-squares method using 12 points or less in the plate-like surface because the measurement work becomes simple. Further, the least square plane ⁇ may be obtained from any point located in the plate-like surface of the metal support 1 as well as the point P located in the peripheral portion OP.
- the metal support 1 is composed of a single metal plate. It is also possible to form the metal support 1 by stacking a plurality of metal plates. It is also possible to form the metal support 1 by stacking a plurality of metal plates having the same or substantially the same thickness. It is also possible to form the metal support 1 by stacking a plurality of metal plates having different thicknesses.
- examples of the structure of the metal support 1 and the through space 1c will be described with reference to the drawings. The illustration of the metal oxide layer 1f is omitted.
- the metal support 1 is a plate-shaped member having a thickness T, that is, a plate shape as a whole.
- the metal support 1 has a plurality of through spaces 1c that penetrate from the front side surface 1a to the back side surface 1b.
- the through space 1c is a hole having a circular cross section.
- the cross-sectional shape of the through space 1c may be a circle, a substantially circular shape, a rectangle, a triangle, a polygon, or the like. If the through space 1c can be formed, various shapes can be used as long as the function as the metal support 1 can be maintained. can do.
- This hole (through space 1c) is formed in the metal support 1 by laser processing, punching processing, etching processing, or a combination thereof.
- the central axis of this hole is orthogonal to the metal support 1.
- the central axis of the hole (through space 1 c) may be inclined with respect to the metal support 1.
- the opening on the front side surface 1a of the through space 1c is referred to as a front side opening 1d.
- the opening on the back side surface 1b of the through space 1c is referred to as a back side opening 1e. Since the cross section of the through space 1c is a circular hole, the front side opening 1d and the back side opening 1e are both circular.
- the front opening 1d and the back opening 1e may have the same size.
- the back side opening 1e may be larger than the front side opening 1d.
- the diameter of the front opening 1d is defined as a diameter D.
- a plurality of holes are formed at the positions of the lattice points of the orthogonal lattice at a pitch P (interval).
- P interval
- an arrangement mode of the plurality of holes in addition to the orthogonal lattice, an orthorhombic lattice and an equilateral triangular lattice are also possible, and in addition to the lattice point, an arrangement at a diagonal intersection is also possible.
- the through space can be formed, various arrangements can be made as long as the function as the metal support can be maintained.
- a region where the through space 1c is formed is referred to as a hole region 1g.
- the hole region 1g is provided in a range excluding the periphery of the outer periphery of the metal support 1.
- One hole region 1g may be provided in the metal support 1, or a plurality of hole regions 1g may be provided in the metal support 1.
- the metal support 1 is required to have sufficient strength to form the electrochemical element E as a support.
- the thickness T of the metal support 1 is preferably 0.1 mm or more, more preferably 0.15 mm or more, and still more preferably 0.2 mm or more.
- the thickness T of the metal support 1 is preferably 1.0 mm or less, more preferably 0.75 mm or less, and still more preferably 0.5 mm or less.
- the diameter D of the front side opening 1d is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, and further preferably 20 ⁇ m or more.
- the diameter D of the front opening 1d is preferably 60 ⁇ m or less, more preferably 50 ⁇ m or less, and even more preferably 40 ⁇ m or less.
- the pitch P of the arrangement of the through spaces 1c (holes) is preferably 0.05 mm or more, more preferably 0.1 mm or more, and further preferably 0.15 mm or more.
- the pitch P of the arrangement of the through spaces 1c (holes) is preferably 0.3 mm or less, more preferably 0.25 mm or less, and further preferably 0.2 mm or less.
- the area S of the front side opening 1d of the through space 1c is preferably 7.0 ⁇ 10 ⁇ 5 mm 2 or more, and preferably 3.0 ⁇ 10 ⁇ 3 mm 2 or less.
- the electrode layer 2 can be provided in a thin layer on a surface on the front side of the metal support 1 and larger than the region where the through space 1 c is provided.
- the thickness can be, for example, about 1 ⁇ m to 100 ⁇ m, preferably 5 ⁇ m to 50 ⁇ m. With such a thickness, it is possible to ensure sufficient electrode performance while reducing the amount of expensive electrode layer material used and reducing costs.
- the entire region where the through space 1 c is provided is covered with the electrode layer 2. That is, the through space 1c is formed inside the region of the metal support 1 where the electrode layer 2 is formed. In other words, all the through spaces 1 c are provided facing the electrode layer 2.
- the electrode layer 2 As a material for the electrode layer 2, for example, a composite material such as NiO-GDC, Ni-GDC, NiO-YSZ, Ni-YSZ, CuO-CeO 2 , Cu-CeO 2 can be used. In these examples, GDC, YSZ, and CeO 2 can be referred to as composite aggregates.
- the electrode layer 2 may be formed by a low-temperature baking method (for example, a wet method using a baking process in a low temperature range that does not perform a baking process in a high temperature range higher than 1100 ° C.) or a spray coating method (a thermal spraying method, an aerosol deposition method, an aerosol gas).
- It is preferably formed by a deposition method, a powder jet deposition method, a particle jet deposition method, a cold spray method or the like), a PVD method (such as a sputtering method or a pulse laser deposition method), a CVD method or the like.
- a deposition method a powder jet deposition method, a particle jet deposition method, a cold spray method or the like
- PVD method such as a sputtering method or a pulse laser deposition method
- CVD method or the like By these processes that can be used in a low temperature range, a good electrode layer 2 can be obtained without using firing in a high temperature range higher than 1100 ° C., for example. Therefore, it is preferable because the elemental interdiffusion between the metal support 1 and the electrode layer 2 can be suppressed without damaging the metal support 1 and an electrochemical element excellent in durability can be realized. Furthermore, it is more preferable to use a low-temperature firing method because handling of raw materials becomes easy.
- the electrode layer 2 has a plurality of pores inside and on the surface in order to impart gas permeability. That is, the electrode layer 2 is formed as a porous layer.
- the electrode layer 2 is formed, for example, so that the density thereof is 30% or more and less than 80%.
- As the size of the pores a size suitable for a smooth reaction to proceed during the electrochemical reaction can be appropriately selected.
- the fine density is the ratio of the material constituting the layer to the space, and can be expressed as (1-porosity), and is equivalent to the relative density.
- the intermediate layer 3 (insertion layer) can be formed in a thin layer on the electrode layer 2 while covering the electrode layer 2.
- the thickness can be, for example, about 1 ⁇ m to 100 ⁇ m, preferably about 2 ⁇ m to 50 ⁇ m, more preferably about 4 ⁇ m to 25 ⁇ m. With such a thickness, it is possible to ensure sufficient performance while reducing the cost by reducing the amount of expensive intermediate layer material used.
- Examples of the material of the intermediate layer 3 include YSZ (yttria-stabilized zirconia), SSZ (scandium-stabilized zirconia), GDC (gadolinium-doped ceria), YDC (yttrium-doped ceria), SDC (samarium-doped ceria). Ceria) or the like can be used. In particular, ceria-based ceramics are preferably used.
- the intermediate layer 3 is formed by a low-temperature baking method (for example, a wet method using a baking process in a low temperature range that does not perform a baking process in a high temperature range higher than 1100 ° C.) or a spray coating method (a thermal spraying method, an aerosol deposition method, an aerosol gas deposition). It is preferably formed by a method such as a method such as a powder jet deposition method, a particle jet deposition method, or a cold spray method), a PVD method (such as a sputtering method or a pulse laser deposition method), or a CVD method.
- a low-temperature baking method for example, a wet method using a baking process in a low temperature range that does not perform a baking process in a high temperature range higher than 1100 ° C.
- a spray coating method a thermal spraying method, an aerosol deposition method, an aerosol gas deposition. It is preferably formed by a method such as a method such as a powder
- the intermediate layer 3 can be obtained without firing in a high temperature region higher than 1100 ° C., for example. Therefore, elemental interdiffusion between the metal support 1 and the electrode layer 2 can be suppressed without damaging the metal support 1, and an electrochemical element E having excellent durability can be realized. Further, it is more preferable to use a low-temperature baking method because handling of raw materials becomes easy.
- the intermediate layer 3 preferably has oxygen ion (oxide ion) conductivity. Further, it is more preferable to have mixed conductivity of oxygen ions (oxide ions) and electrons. The intermediate layer 3 having these properties is suitable for application to the electrochemical element E.
- the electrolyte layer 4 is formed in a thin layer on the intermediate layer 3 while covering the electrode layer 2 and the intermediate layer 3. Moreover, it can also form in the state of a thin film whose thickness is 10 micrometers or less. Specifically, as shown in FIG. 1, the electrolyte layer 4 is provided over (straddling) the intermediate layer 3 and the metal support 1. By comprising in this way and joining the electrolyte layer 4 to the metal support body 1, it can be excellent in robustness as the whole electrochemical element.
- the electrolyte layer 4 is provided in a region that is a surface on the front side of the metal support 1 and is larger than a region in which the through space 1 c is provided. That is, the through space 1c is formed inside the region of the metal support 1 where the electrolyte layer 4 is formed.
- gas leakage from the electrode layer 2 and the intermediate layer 3 can be suppressed around the electrolyte layer 4.
- gas is supplied from the back side of the metal support 1 to the electrode layer 2 through the through space 1c when the SOFC is operated.
- gas leakage can be suppressed without providing another member such as a gasket.
- the entire periphery of the electrode layer 2 is covered with the electrolyte layer 4, but the electrolyte layer 4 may be provided above the electrode layer 2 and the intermediate layer 3, and a gasket or the like may be provided around the electrode layer 2.
- Examples of the material of the electrolyte layer 4 include YSZ (yttria stabilized zirconia), SSZ (scandium stabilized zirconia), GDC (gadolinium doped ceria), YDC (yttrium doped ceria), SDC (samarium doped ceria).
- LSGM sinrontium / magnesium-added lanthanum gallate
- zirconia ceramics are preferably used.
- the material of the electrolyte layer 4 is made of a material that can exhibit high electrolyte performance even in a high temperature range of about 650 ° C. or higher, such as YSZ.
- a highly efficient SOFC system that uses heat generated in the SOFC cell stack for raw fuel gas reforming Can be built.
- the electrolyte layer 4 is formed by a low temperature baking method (for example, a wet method using a baking process in a low temperature range in which a baking process is not performed in a high temperature range exceeding 1100 ° C.) or a spray coating method (a thermal spraying method, an aerosol deposition method, an aerosol gas deposition). It is preferably formed by a method such as a method such as a powder jet deposition method, a particle jet deposition method, or a cold spray method), a PVD method (such as a sputtering method or a pulse laser deposition method), or a CVD method.
- a low temperature baking method for example, a wet method using a baking process in a low temperature range in which a baking process is not performed in a high temperature range exceeding 1100 ° C.
- a spray coating method a thermal spraying method, an aerosol deposition method, an aerosol gas deposition. It is preferably formed by a method such as a method such as a powder jet
- the electrolyte layer 4 having a high density and a high gas barrier property can be obtained without firing in a high temperature region exceeding 1100 ° C., for example. Therefore, damage to the metal support 1 can be suppressed, elemental interdiffusion between the metal support 1 and the electrode layer 2 can be suppressed, and an electrochemical element E excellent in performance and durability can be realized.
- a low-temperature firing method or a spray coating method because a low-cost element can be realized.
- it is more preferable to use a spray coating method because a dense electrolyte layer having a high gas tightness and gas barrier property can be easily obtained in a low temperature range.
- Electrolyte layer 4 is densely configured to shield gas leakage of anode gas and cathode gas and to exhibit high ionic conductivity.
- the density of the electrolyte layer 4 is preferably 90% or more, more preferably 95% or more, and further preferably 98% or more.
- the density is preferably 95% or more, and more preferably 98% or more.
- the electrolyte layer 4 is configured in a plurality of layers, it is preferable that at least a part thereof includes a layer (dense electrolyte layer) having a density of 98% or more, and 99% It is more preferable that the above layer (dense electrolyte layer) is included.
- the reaction preventing layer 5 can be formed on the electrolyte layer 4 in a thin layer state.
- the thickness can be, for example, about 1 ⁇ m to 100 ⁇ m, preferably about 2 ⁇ m to 50 ⁇ m, more preferably about 3 ⁇ m to 15 ⁇ m. With such a thickness, it is possible to secure sufficient performance while reducing the cost by reducing the amount of expensive reaction preventing layer material used.
- the material of the reaction preventing layer 5 may be any material that can prevent the reaction between the component of the electrolyte layer 4 and the component of the counter electrode layer 6. For example, a ceria-based material is used.
- the material for the reaction preventing layer 5 a material containing at least one element selected from the group consisting of Sm, Gd and Y is preferably used. Note that it is preferable that at least one element selected from the group consisting of Sm, Gd, and Y is contained, and the total content of these elements is 1.0% by mass or more and 10% by mass or less.
- low-temperature firing methods for example, wet methods using a firing treatment in a low temperature range that does not perform a firing treatment in a high temperature range exceeding 1100 ° C.
- spray coating methods thermal spraying method, aerosol deposition method, aerosol gas deposition method, powder
- a PVD method a sputtering method, a pulse laser deposition method, or the like
- CVD method or the like can be used as appropriate.
- it is preferable to use a low-temperature firing method or a spray coating method because a low-cost element can be realized.
- it is more preferable to use a low-temperature firing method because handling of raw materials becomes easy.
- the counter electrode layer 6 can be formed in a thin layer on the electrolyte layer 4 or the reaction preventing layer 5.
- the thickness can be, for example, about 1 ⁇ m to 100 ⁇ m, preferably 5 ⁇ m to 50 ⁇ m. With such a thickness, it is possible to secure sufficient electrode performance while reducing the cost by reducing the amount of expensive counter electrode layer material used.
- composite oxides such as LSCF and LSM, ceria-based oxides, and mixtures thereof can be used.
- the counter electrode layer 6 preferably includes a perovskite oxide containing two or more elements selected from the group consisting of La, Sr, Sm, Mn, Co, and Fe.
- the counter electrode layer 6 configured using the above materials functions as a cathode.
- the formation of the counter electrode layer 6 is appropriately performed using a method that can be formed at a processing temperature of 1100 ° C. or less, damage to the metal support 1 is suppressed, and the elements of the metal support 1 and the electrode layer 2 The interdiffusion can be suppressed, and an electrochemical element E excellent in performance and durability can be realized, which is preferable.
- low-temperature firing methods for example, wet methods using a firing treatment in a low temperature range that does not perform a firing treatment in a high temperature range exceeding 1100 ° C.
- spray coating methods thermal spraying method, aerosol deposition method, aerosol gas deposition method, powder
- a method such as a jet deposition method, a particle jet deposition method, or a cold spray method
- a PDV method a sputtering method, a pulse laser deposition method, etc.
- CVD method or the like
- it is preferable to use a low-temperature firing method or a spray coating method because a low-cost element can be realized.
- it is more preferable to use a low-temperature firing method because handling of raw materials becomes easy.
- the electrochemical element E can be used as a power generation cell of a solid oxide fuel cell.
- a fuel gas containing hydrogen is supplied to the electrode layer 2 from the back surface of the metal support 1 through the through space 1c, and air is supplied to the counter electrode layer 6 that is the counter electrode of the electrode layer 2, for example, 500 ° C. or higher. Operate at temperatures below 900 ° C. Then, oxygen O 2 contained in the air reacts with electrons e ⁇ in the counter electrode layer 6 to generate oxygen ions O 2 ⁇ . The oxygen ions O 2 ⁇ move through the electrolyte layer 4 to the electrode layer 2.
- the electrode layer 2 hydrogen H 2 contained in the supplied fuel gas reacts with oxygen ions O 2 ⁇ to generate water H 2 O and electrons e ⁇ . Due to the above reaction, an electromotive force is generated between the electrode layer 2 and the counter electrode layer 6.
- the electrode layer 2 functions as an SOFC fuel electrode (anode)
- the counter electrode layer 6 functions as an air electrode (cathode).
- the electrode layer 2 is formed as a thin film in a region wider than the region where the through space 1c on the front surface of the metal support 1 is provided.
- the through hole of the metal support 1 can be provided by laser processing or the like.
- the electrode layer 2 is formed by a low-temperature baking method (wet method in which baking is performed at a low temperature of 1100 ° C.
- a spray coating method (a thermal spraying method, an aerosol deposition method, an aerosol gas deposition method, A method such as a powder jet deposition method, a particle jet deposition method, or a cold spray method), a PVD method (such as a sputtering method or a pulse laser deposition method), or a CVD method can be used.
- a thermal spraying method a thermal spraying method, an aerosol deposition method, an aerosol gas deposition method, A method such as a powder jet deposition method, a particle jet deposition method, or a cold spray method
- a PVD method such as a sputtering method or a pulse laser deposition method
- CVD method a chemical vapor deposition method
- the electrode layer forming step is performed by a low temperature firing method, specifically, it is performed as in the following example.
- the material powder of the electrode layer 2 and a solvent (dispersion medium) are mixed to prepare a material paste, which is applied to the front surface of the metal support 1.
- the electrode layer 2 is compression-molded (electrode layer smoothing step) and fired at 1100 ° C. or lower (electrode layer firing step).
- the compression molding of the electrode layer 2 can be performed, for example, by CIP (Cold Isostatic Pressing) molding, roll pressing molding, RIP (Rubber Isostatic Pressing) molding, or the like.
- the electrode layer is preferably fired at a temperature of 800 ° C. or higher and 1100 ° C. or lower.
- the order of the electrode layer smoothing step and the electrode layer firing step can be interchanged.
- an electrode layer smoothing process and an electrode layer baking process are abbreviate
- the electrode layer smoothing step can also be performed by lapping, leveling, surface cutting / polishing, or the like.
- a metal oxide layer 1f (diffusion suppression layer) is formed on the surface of the metal support 1.
- the firing step includes a firing step in which the firing atmosphere is an atmospheric condition with a low oxygen partial pressure, a high-quality metal oxide layer 1f (diffusion restraint) having a high element interdiffusion suppression effect and a low resistance value. Layer) is preferable.
- a separate diffusion suppression layer forming step may be included, including the case where the electrode layer forming step is a coating method without firing. In any case, it is desirable to carry out at a processing temperature of 1100 ° C. or lower that can suppress damage to the metal support 1.
- the metal oxide layer 1f (diffusion suppression layer) may be formed on the surface of the metal support 1 during the firing step in the intermediate layer forming step described later.
- the intermediate layer 3 is formed in a thin layer on the electrode layer 2 so as to cover the electrode layer 2.
- the intermediate layer 3 is formed by a low-temperature baking method (wet method in which baking is performed in a low temperature region of 1100 ° C. or lower), a spray coating method (a thermal spraying method, an aerosol deposition method, an aerosol gas deposition method, A method such as a powder jet deposition method, a particle jet deposition method, or a cold spray method), a PVD method (such as a sputtering method or a pulse laser deposition method), or a CVD method can be used. Whichever method is used, it is desirable to carry out at a temperature of 1100 ° C. or lower in order to suppress the deterioration of the metal support 1.
- the intermediate layer forming step is performed by a low-temperature firing method, specifically, it is performed as in the following example.
- the material powder of the intermediate layer 3 and a solvent (dispersion medium) are mixed to prepare a material paste, which is applied to the front surface of the metal support 1.
- the intermediate layer 3 is compression-molded (intermediate layer smoothing step) and fired at 1100 ° C. or less (intermediate layer firing step).
- the rolling of the intermediate layer 3 can be performed by, for example, CIP (Cold Isostatic Pressing) molding, roll pressing molding, RIP (Rubber Isostatic Pressing) molding, or the like.
- the firing of the intermediate layer 3 is preferably performed at a temperature of 800 ° C. or higher and 1100 ° C.
- the intermediate layer 3 having high strength can be formed while suppressing damage and deterioration of the metal support 1 at such a temperature.
- middle layer 3 is performed at 1050 degrees C or less, and it is still more preferable when it is performed at 1000 degrees C or less.
- the electrochemical element E can be formed while further suppressing damage and deterioration of the metal support 1 as the firing temperature of the intermediate layer 3 is lowered.
- the order of the intermediate layer smoothing step and the intermediate layer firing step can be switched.
- the intermediate layer smoothing step can also be performed by lapping, leveling, surface cutting / polishing, or the like.
- the electrolyte layer 4 is formed in a thin layer on the intermediate layer 3 while covering the electrode layer 2 and the intermediate layer 3. Moreover, you may form in the state of a thin film whose thickness is 10 micrometers or less. As described above, the electrolyte layer 4 is formed by a low temperature firing method (wet method in which a firing process is performed at a low temperature of 1100 ° C.
- a spray coating method (a thermal spraying method, an aerosol deposition method, an aerosol gas deposition method, A method such as a powder jet deposition method, a particle jet deposition method, or a cold spray method), a PVD method (such as a sputtering method or a pulse laser deposition method), or a CVD method can be used.
- a thermal spraying method a thermal spraying method, an aerosol deposition method, an aerosol gas deposition method, A method such as a powder jet deposition method, a particle jet deposition method, or a cold spray method
- a PVD method such as a sputtering method or a pulse laser deposition method
- CVD method a chemical vapor deposition method
- electrolyte layer forming step In order to form a high-quality electrolyte layer 4 that is dense, airtight and has high gas barrier performance in a temperature range of 1100 ° C. or lower, it is desirable to perform the electrolyte layer forming step by a spray coating method. In that case, the material of the electrolyte layer 4 is sprayed toward the intermediate layer 3 on the metal support 1 to form the electrolyte layer 4.
- reaction prevention layer formation step In the reaction preventing layer forming step, the reaction preventing layer 5 is formed on the electrolyte layer 4 in a thin layer state.
- the reaction prevention layer 5 is formed by a low-temperature baking method (wet method in which baking is performed in a low temperature region of 1100 ° C. or lower), a spray coating method (a thermal spraying method, an aerosol deposition method, an aerosol gas deposition method). , Powder jet deposition methods, particle jet deposition methods, cold spray methods, etc.), PVD methods (sputtering methods, pulsed laser deposition methods, etc.), CVD methods, etc. can be used. Whichever method is used, it is desirable to carry out at a temperature of 1100 ° C.
- a leveling process or a surface cutting / polishing process may be performed after the formation of the reaction preventing layer 5, or a press working may be performed after the wet formation and before firing. Good.
- the counter electrode layer 6 is formed in a thin layer on the reaction preventing layer 5.
- the counter electrode layer 6 is formed by a low temperature baking method (wet method in which baking is performed in a low temperature region of 1100 ° C. or lower), a spray coating method (a thermal spraying method, an aerosol deposition method, an aerosol gas deposition method). , Powder jet deposition methods, particle jet deposition methods, cold spray methods, etc.), PVD methods (sputtering methods, pulsed laser deposition methods, etc.), CVD methods, etc. can be used. Whichever method is used, it is desirable to carry out at a temperature of 1100 ° C. or lower in order to suppress the deterioration of the metal support 1.
- the electrochemical element E can be manufactured as described above.
- the intermediate layer 3 (insertion layer) and the reaction preventing layer 5 may be provided with either one or both. That is, a form in which the electrode layer 2 and the electrolyte layer 4 are formed in contact with each other, or a form in which the electrolyte layer 4 and the counter electrode layer 6 are formed in contact with each other is possible.
- the intermediate layer forming step and the reaction preventing layer forming step are omitted. Note that a step of forming another layer can be added, or a plurality of layers of the same type can be stacked. In any case, it is preferable to perform the step at a temperature of 1100 ° C. or lower.
- Example 1 A metal plate (metal support 1) according to Example 1 was produced by performing a leveler process for smoothing the same metal plate (metal support 1) as in Comparative Example 1.
- Example 2 A metal plate (metal support 1) according to Example 2 was produced by performing an annealing process for smoothing the same metal plate (metal support 1) as in Comparative Example 2.
- Example 3 A metal plate of craft 22APU having a thickness of 0.3 mm and a 40 mm square (40 mm ⁇ 40 mm) is provided with a plurality of through spaces 1c by laser processing in a 28 mm square (28 mm ⁇ 28 mm) region from the center, and the metal according to Example 3 A plate (metal support 1) was produced.
- the through space 1c was provided at a lattice point of the orthogonal lattice.
- the diameter of the front opening 1d is 25 ⁇ m, and the pitch P is 150 ⁇ m.
- the maximum length Lmax is 5.66 cm.
- the degree of warpage in the above comparative examples and examples was measured by the method described in the above embodiment.
- the metal support 1 in Example 3 8 points at a position 15% of the distance from the periphery of the metal support 1 were used.
- the result of whether or not the electrode layer 2 was laminated was determined.
- the warp degree of the metal support 1 is large, and when the electrode layer 2 is laminated, surface defects such as printing defects, peeling, and cracks occur.
- the electrode layer 2 that can be used for the chemical element E could not be laminated on the metal support 1.
- the degree of warping of the metal support 1 was 2.1 ⁇ 10 ⁇ 2 .
- the degree of warpage is small in any of the metal supports 1, and surface defects such as cracking and peeling are suppressed and used for the electrochemical element E.
- the electrode layer 2 that can be formed was able to be laminated. Among them, in Example 3 having the largest value of warpage, the warp degree of the metal support 1 was 1.1 ⁇ 10 ⁇ 2 .
- the electrode layer 2 is laminated on the metal support 1 while suppressing surface defects such as cracking and peeling. I understood that I could do it.
- Example 3 after the electrode layer 2 was laminated, the intermediate layer 3, the electrolyte layer 4, the reaction preventing layer 5, and the counter electrode layer 6 were laminated to produce an electrochemical element E.
- fuel gas humidity is supplied to the electrode layer 2 and air is supplied to the counter electrode layer 6 to provide OCV (one of the power generation performances as a solid oxide fuel cell).
- Open circuit voltage was measured at an operating temperature of 750 ° C. As a result, in the electrochemical element E of Example 3, it was 1.02V. From this result, it can be seen that in Example 3, the electrochemical element E has a large OCV (open circuit voltage).
- the electrochemical device E has a U-shaped member 7 attached to the back surface of the metal support 1, and the metal support 1 and the U-shaped member 7 support the tube. Forming the body.
- a plurality of electrochemical elements E are stacked with the current collecting member 26 interposed therebetween, so that an electrochemical module M is configured.
- the current collecting member 26 is joined to the counter electrode layer 6 of the electrochemical element E and the U-shaped member 7 to electrically connect them.
- the electrochemical module M has a gas manifold 17, a current collecting member 26, a termination member, and a current drawing portion.
- a plurality of stacked electrochemical elements E are supplied with gas from the gas manifold 17 with one open end of the cylindrical support connected to the gas manifold 17. The supplied gas flows through the inside of the cylindrical support and is supplied to the electrode layer 2 through the through space 1 c of the metal support 1.
- FIG. 3 shows an outline of the energy system Z and the electrochemical device Y.
- the energy system Z includes an electrochemical device Y and a heat exchanger 53 as an exhaust heat utilization unit that reuses the heat discharged from the electrochemical device Y.
- the electrochemical device Y includes an electrochemical module M, a desulfurizer 31 and a reformer 34, a fuel supply unit that supplies a fuel gas containing a reducing component to the electrochemical module M, and an electrochemical module. And an inverter 38 for extracting electric power from M.
- the electrochemical device Y includes a desulfurizer 31, a reforming water tank 32, a vaporizer 33, a reformer 34, a blower 35, a combustion unit 36, an inverter 38, a control unit 39, a storage container 40, and an electrochemical module M.
- a desulfurizer 31 a reforming water tank 32, a vaporizer 33, a reformer 34, a blower 35, a combustion unit 36, an inverter 38, a control unit 39, a storage container 40, and an electrochemical module M.
- the desulfurizer 31 removes (desulfurizes) sulfur compound components contained in hydrocarbon-based raw fuel such as city gas.
- hydrocarbon-based raw fuel such as city gas.
- the vaporizer 33 generates steam from the reformed water supplied from the reformed water tank 32.
- the reformer 34 steam-reforms the raw fuel desulfurized by the desulfurizer 31 using the steam generated by the vaporizer 33 to generate a reformed gas containing hydrogen.
- the electrochemical module M uses the reformed gas supplied from the reformer 34 and the air supplied from the blower 35 to generate an electrochemical reaction to generate power.
- the combustion unit 36 mixes the reaction exhaust gas discharged from the electrochemical module M and air, and combusts the combustible component in the reaction exhaust gas.
- the electrochemical module M has a plurality of electrochemical elements E and a gas manifold 17.
- the plurality of electrochemical elements E are arranged in parallel while being electrically connected to each other, and one end (lower end) of the electrochemical element E is fixed to the gas manifold 17.
- the electrochemical element E generates electricity by causing an electrochemical reaction between the reformed gas supplied through the gas manifold 17 and the air supplied from the blower 35.
- the inverter 38 adjusts the output power of the electrochemical module M to the same voltage and the same frequency as the power received from the commercial system (not shown).
- the control unit 39 controls the operation of the electrochemical device Y and the energy system Z.
- the vaporizer 33, the reformer 34, the electrochemical module M, and the combustion unit 36 are stored in the storage container 40.
- the reformer 34 performs the reforming process of the raw fuel using the combustion heat generated by the combustion of the reaction exhaust gas in the combustion unit 36.
- the raw fuel is supplied to the desulfurizer 31 through the raw fuel supply path 42 by the operation of the booster pump 41.
- the reforming water in the reforming water tank 32 is supplied to the vaporizer 33 through the reforming water supply path 44 by the operation of the reforming water pump 43.
- the raw fuel supply path 42 is downstream of the desulfurizer 31 and is joined to the reformed water supply path 44, and the reformed water and raw fuel merged outside the storage container 40 are stored in the storage container.
- the carburetor 33 provided in 40 is supplied.
- the reformed water is vaporized by the vaporizer 33 and becomes steam.
- the raw fuel containing the steam generated in the vaporizer 33 is supplied to the reformer 34 through the steam-containing raw fuel supply path 45.
- the raw fuel is steam-reformed by the reformer 34, and a reformed gas (first gas having a reducing component) containing hydrogen gas as a main component is generated.
- the reformed gas generated in the reformer 34 is supplied to the gas manifold 17 of the electrochemical module M through the reformed gas supply path 46.
- the reformed gas supplied to the gas manifold 17 is distributed to the plurality of electrochemical elements E, and is supplied to the electrochemical elements E from the lower end that is a connecting portion between the electrochemical elements E and the gas manifold 17.
- Hydrogen (reducing component) in the reformed gas is mainly used for electrochemical reaction in the electrochemical element E.
- the reaction exhaust gas containing the remaining hydrogen gas that has not been used for the reaction is discharged from the upper end of the electrochemical element E to the combustion section 36.
- the reaction exhaust gas is combusted in the combustion part 36 and is discharged as combustion exhaust gas from the combustion exhaust gas outlet 50 to the outside of the storage container 40.
- a combustion catalyst portion 51 (for example, a platinum-based catalyst) is disposed at the combustion exhaust gas outlet 50 to burn and remove reducing components such as carbon monoxide and hydrogen contained in the combustion exhaust gas.
- the combustion exhaust gas discharged from the combustion exhaust gas outlet 50 is sent to the heat exchanger 53 through the combustion exhaust gas discharge passage 52.
- the heat exchanger 53 exchanges heat between the flue gas generated by the combustion in the combustion unit 36 and the supplied cold water to generate hot water. That is, the heat exchanger 53 operates as an exhaust heat utilization unit that reuses the heat exhausted from the electrochemical device Y.
- reaction exhaust gas utilization part which utilizes the reaction exhaust gas discharged
- the reaction exhaust gas contains residual hydrogen gas that was not used for the reaction in the electrochemical element E.
- the remaining hydrogen gas is used to use heat by combustion, or to generate power by a fuel cell or the like, thereby effectively using energy.
- FIG. 4 shows another embodiment of the electrochemical module M.
- the electrochemical module M according to the third embodiment configures the electrochemical module M by laminating the above-described electrochemical element E with the inter-cell connection member 71 interposed therebetween.
- the inter-cell connection member 71 is a plate-like member that has conductivity and does not have gas permeability, and grooves 72 that are orthogonal to each other are formed on the front surface and the back surface.
- the inter-cell connection member 71 can be made of metal such as stainless steel or metal oxide.
- one groove 72 becomes the first gas flow path 72 a and supplies gas to the front side of the electrochemical element E, that is, the counter electrode layer 6.
- the other groove 72 becomes the second gas flow path 72b, and gas is supplied to the electrode layer 2 through the through space 1c from the back side of the electrochemical element E, that is, the back side surface of the metal support 1.
- this electrochemical module M When operating this electrochemical module M as a fuel cell, oxygen is supplied to the first gas channel 72a and hydrogen is supplied to the second gas channel 72b. Then, the reaction as a fuel cell proceeds in the electrochemical element E, and electromotive force / current is generated. The generated electric power is taken out of the electrochemical module M from the inter-cell connection members 71 at both ends of the stacked electrochemical element E.
- the grooves 72 that are orthogonal to each other are formed on the front and back surfaces of the inter-cell connection member 71.
- the grooves 72 that are parallel to each other are formed on the front and back surfaces of the inter-cell connection member 71. You can also.
- FIG. That is, instead of calculating the least square plane ⁇ representing the plurality of points P from the plurality of points P, a least square value ⁇ V represented by a straight line representing the plurality of points P may be calculated.
- the least square value ⁇ V includes, for example, a straight line and a plane (the least square plane ⁇ ) representing the plurality of points P, and the like.
- the warp degree is calculated by dividing Da by the maximum length Lmax so that the warp degree can be compared with a constant value. According to the above method, the curvature degree of the metal support body 1 can be calculated
- the minimum is obtained by the least square method using at least three points P facing each other in the plate-like surface of the metal support 1 around the center of gravity G.
- the square value ⁇ V may be calculated.
- the method of calculating the degree of warpage based on the least square value ⁇ V is the same as the method described above.
- the least square value ⁇ V is calculated using the points P located in directions away from the center of gravity G in the plate-like plane. That is, the least square value ⁇ V is not calculated from the points in the local region of the metal support 1, but is calculated from the points P dispersed in the plate-like surface. Therefore, the least square value ⁇ V is calculated as a value related to the shape of the plate-like surface of the metal support 1.
- Da serving as a reference for determining the degree of warping of the metal support 1 can be calculated with high accuracy.
- Da is divided by the maximum length Lmax so that the warp degree can be compared with a constant value even in the metal supports 1 having different sizes.
- Da may be divided by the area of the plate-like surface of the metal support 1 to obtain the degree of warpage. Also in this case, even in the metal supports 1 having different sizes, the degree of warpage can be determined by comparing with a certain value.
- the plurality of straight lines L passing through the center of gravity G of the metal support 1 are lines that divide 360 ° into predetermined angles.
- the plurality of straight lines L passing through the center of gravity G may be separated from each other by a random angle.
- the point P on the metal support 1 used for calculating Da is in the region from the periphery of the metal support 1 to the hole region 1g, that is, the peripheral portion OP of the metal support 1. Located in.
- the point P on the metal support 1 used for calculating Da may be an arbitrary point P on the metal support 1, and is not limited to the point P located at the peripheral portion OP.
- the electrochemical element E is used for a solid oxide fuel cell, but the electrochemical element E is used for a solid oxide electrolytic cell, an oxygen sensor using a solid oxide, or the like. You can also
- the electrode layer 2 is made of a composite material such as NiO—GDC, Ni—GDC, NiO—YSZ, Ni—YSZ, CuO—CeO 2 , Cu—CeO 2, and the like.
- a complex oxide such as LSCF or LSM was used.
- the electrochemical device E configured in this way supplies hydrogen gas to the electrode layer 2 to form a fuel electrode (anode), and supplies air to the counter electrode layer 6 to form an air electrode (cathode). It can be used as a fuel cell.
- the electrochemical element E can be configured such that the electrode layer 2 can be an air electrode and the counter electrode layer 6 can be a fuel electrode.
- a composite oxide such as LSCF or LSM is used as the material of the electrode layer 2, and NiO—GDC, Ni—GDC, NiO—YSZ, Ni—YSZ, CuO—CeO 2 , Cu is used as the material of the counter electrode layer 6, for example.
- a composite material such as CeO 2 .
- air is supplied to the electrode layer 2 to be an air electrode
- hydrogen gas is supplied to the counter electrode layer 6 to be a fuel electrode
- the electrochemical element E is in a solid oxide form. It can be used as a fuel cell.
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Abstract
Description
本発明に係る電気化学素子の金属支持体の特徴構成は、
前記金属支持体は板状面を有して全体として板状であり、前記金属支持体は、電極層が設けられる面を表側面として、前記表側面から裏側面へ貫通する複数の貫通空間を有し、前記表側面において前記貫通空間が形成されている領域を孔領域とし、
以下の反り度を満たす点にある。
(反り度)
前記金属支持体の板状面内の少なくとも3点を用いて最小二乗法により最小二乗値を算出し、前記最小二乗値に対してプラス側へのプラス側最大変位値と前記最小二乗値との第一差分と、前記最小二乗値に対して前記プラス側とは反対のマイナス側へのマイナス側最大変位値と前記最小二乗値との第二差分とを算出し、前記第一差分と第二差分との和であるDaを、重心を通る前記金属支持体の前記板状面での最大長さLmaxで割ったDa/Lmaxを前記反り度とし、前記反り度が1.5×10-2以下である。
上記の特徴構成によれば、さらにDaを金属支持体の最大長さLmaxで割ることにより、大きさが異なる金属支持体であっても一定の基準値で反り度を比較可能である。
そして、このように金属支持体の反り度を精度良く算出し、反り度を1.5×10-2以下とすることで、金属支持体上に形成される電極層を厚みが均一かつ割れや剥離等の表面欠陥が少なく積層できる。また、このような欠陥を抑制した電極層が積層できればその上に積層される電解質層、対極電極層等も厚みが均一かつ割れや剥離等の表面欠陥が少なく積層することができる。このため、各層間において密着性良く積層ができるため、性能の高い電気化学素子が得られる。
本発明に係る電気化学素子の金属支持体の更なる特徴構成は、
前記金属支持体の板状面内の少なくとも2点は、前記重心を通る少なくとも一本の直線上において、前記金属支持体の板状面内において前記重心を中心として互いに対向する少なくとも2点である点にある。
本発明に係る電気化学素子の金属支持体の更なる特徴構成は、
前記直線が複数本の直線である場合、前記複数の直線は、前記重心を中心として360°を所定角度ごとに分割している点にある。
本発明に係る電気化学素子の金属支持体の更なる特徴構成は、
前記金属支持体の板状面内において前記重心を中心として互いに対向する少なくとも2点は、前記金属支持体の周縁と前記孔領域との間に存在する点である点にある。
本発明に係る電気化学素子の金属支持体の更なる特徴構成は、
前記金属支持体の板状面内において前記重心を中心として互いに対向する少なくとも2点は、前記金属支持体の周縁と、前記金属支持体上に積層される前記電極層との間に存在する点であることにある。
本発明に係る電気化学素子の金属支持体の更なる特徴構成は、
前記最小二乗値は、前記金属支持体の板状面内の少なくとも4点を用いて最小二乗法により算出される最小二乗平面である点にある。
なお、板状面内の少なくとも4点として、板状面内において重心に対して互いに離れた方向に位置する点を用いると、板状面内に分散した点から板状面の形状を近似した最小二乗平面が算出されるので好ましい。また、板状面内の5点以上の点を用いて最小二乗法により最小二乗平面を算出すれば、板状面内のより複数の点を用いることになり、Daを精度良く算出できるため好ましい。また、板状面内の12点以下の点を用いて最小二乗法により最小二乗平面を算出すれば、反り度の測定作業が簡便になるため好ましい。
本発明に係る電気化学素子の金属支持体の更なる特徴構成は、
前記貫通空間の前記表側面の開口部である表側開口部が、直径が10μm以上60μm以下の円形又は略円形である点にある。
本発明に係る電気化学素子の金属支持体の更なる特徴構成は、
前記貫通空間の前記裏側面の開口部である裏側開口部が、前記貫通空間の前記表側面の開口部である表側開口部よりも大きい面積または直径を有する点にある。
本発明に係る電気化学素子の金属支持体の更なる特徴構成は、前記貫通空間の前記表側面の開口部である表側開口部の間隔が0.05mm以上0.3mm以下である点にある。
本発明に係る電気化学素子の金属支持体の更なる特徴構成は、厚さが0.1mm以上1.0mm以下である点にある。
本発明に係る電気化学素子の金属支持体の更なる特徴構成は、材料がFe-Cr系合金である点にある。
本発明に係る電気化学素子の特徴構成は、
上記金属支持体の前記表側面に、少なくとも電極層と電解質層と対極電極層とが設けられた点にある。
本発明に係る電気化学モジュールの特徴構成は、
上記電気化学素子が複数集合した状態で配置される点にある。
本発明に係る電気化学装置の特徴構成は、
上記電気化学モジュールと改質器とを少なくとも有し、前記電気化学モジュールに対して還元性成分を含有する燃料ガスを供給する燃料供給部を有する点にある。
本発明に係る電気化学装置の特徴構成は、
上記電気化学モジュールと、前記電気化学モジュールから電力を取り出すインバータとを少なくとも有する点にある。
本発明に係るエネルギーシステムの特徴構成は、
上記電気化学装置と、前記電気化学装置から排出される熱を再利用する排熱利用部とを有する点にある。
本発明に係る固体酸化物形燃料電池の特徴構成は、
上記電気化学素子を備え、前記電気化学素子で発電反応を生じさせる点にある。
本発明に係る金属支持体の製造方法の特徴構成は、
上記金属支持体を製造する製造方法であって、レーザー加工またはパンチング加工またはエッチング加工のいずれか、または、それらの組合せによって、前記表側面から裏側面へ貫通する複数の貫通空間を形成する点にある。
本発明に係る金属支持体の製造方法の特徴構成は、平滑化処理工程を含む点にある。
以下、図1を参照しながら、本実施形態に係る電気化学素子Eおよび固体酸化物形燃料電池(Solid Oxide Fuel Cell:SOFC)について説明する。電気化学素子Eは、例えば、水素を含む燃料ガスと空気の供給を受けて発電する固体酸化物形燃料電池の構成要素として用いられる。なお以下、層の位置関係などを表す際、例えば電解質層4から見て対極電極層6の側を「上」または「上側」、電極層2の側を「下」または「下側」という場合がある。また、金属支持体1における電極層2が形成されている側の面を表側面1a、反対側の面を裏側面1bという。
電気化学素子Eは、図1に示される通り、金属支持体1と、金属支持体1の上に形成された電極層2と、電極層2の上に形成された中間層3と、中間層3の上に形成された電解質層4とを有する。そして電気化学素子Eは、更に、電解質層4の上に形成された反応防止層5と、反応防止層5の上に形成された対極電極層6とを有する。つまり対極電極層6は電解質層4の上に形成され、反応防止層5は電解質層4と対極電極層6との間に形成されている。電極層2は多孔質であり、電解質層4は緻密である。
金属支持体1は、電極層2、中間層3および電解質層4等を支持して電気化学素子Eの強度を保つ。つまり金属支持体1は、電気化学素子Eを支持する支持体としての役割を担う。本実施形態では、金属支持体1は反り度が1.5×10-2以下であり、金属支持体1上に、電極層2などの積層が適切に行われる。
金属酸化物層1fは種々の手法により形成されうるが、金属支持体1の表面を酸化させて金属酸化物とする手法が好適に利用される。また、金属支持体1の表面に、金属酸化物層1fをスプレーコーティング法(溶射法やエアロゾルデポジション法、エアロゾルガスデポジッション法、パウダージェットデポジッション法、パーティクルジェットデポジション法、コールドスプレー法などの方法)、スパッタリング法やPLD法等のPVD法、CVD法などにより形成しても良いし、メッキと酸化処理によって形成しても良い。更に、金属酸化物層1fは導電性の高いスピネル相などを含んでも良い。
図6に示す金属支持体1において、金属支持体1の重心Gを求める。重心Gは金属支持体1に孔領域g1がなく、厚みと密度が均一であると仮定した際に、重心Gのまわりの一次モーメントが0になる点である。例えば金属支持体1の板状面(表側面1a)の形状が正方形または長方形等の矩形状である場合は、対角線の交点であり、円形状であれば中心、楕円形状であれば長軸と短軸の交点に相当する点である。
なお、上記では、一本の直線Lについて重心Gを中心として対向する2点Pを抽出したが、一本の直線Lについて3個以上の点Pを抽出してもよい。
金属支持体1のうち、このような周縁部OPに位置する点Pを用いることで、金属支持体1の形状をより代表する後述の最小二乗平面α(最小二乗値)を求めることができる。
ここで、金属支持体1の反り度に応じて平滑化処理(例えばレベラー処理、焼鈍処理など)を施してもよい。なお、反り度が1.5×10-2より大きい金属支持体1に対して平滑化処理を施すと好適である。
また、孔領域1gが5.0×102mm2以上の場合、平滑化処理により金属支持体1の反り度を抑制しやすくなるため好ましく、孔領域1gが2.5×103mm2以上の場合、反り度の抑制効果がより大きく得られるのでより好ましい。
また、電極層2、電解質層4及び対極電極層6等を含む複数の層を金属支持体1上に積層してセルを作製する際に、金属支持体1及び、各層間をより密着させるため、プレス等で各層に加重を掛ける場合がある。上記の通り、金属支持体1の反りが小さく平坦であることにより、金属支持体1及び各層に概ね均一に加重が加わる。よって、プレス等で各層に加重をかけた際、各層の割れや剥離、及び、金属支持体1からの剥離等が抑制される。これにより、厚みが均一で割れや剥離等の表面欠陥が少なく、層間密着性の高いセルが作製できる。ひいては、各層間での電気化学反応が効率よく行われ、電気化学素子Eの性能を高めることができる。
また、周縁部OPの5点以上の点を用いて最小二乗法により最小二乗平面αを算出すれば、金属支持体1の板状面内のより複数の点を用いることになり、Daを精度良く算出できるため好ましい。また、板状面内の12点以下の点を用いて最小二乗法により最小二乗平面αを算出すれば、測定作業が簡便になるため好ましい。
また、最小二乗平面αは、周縁部OPに位置する点Pだけでなく、金属支持体1の板状面内に位置するいずれの点から求められてもよい。
図1の例では、金属支持体1が1枚の金属の板により構成されている。金属支持体1を、金属板を複数重ねて形成することも可能である。金属支持体1を、同一または略同一の厚さの金属板を複数重ねて形成することも可能である。金属支持体1を、厚さの異なる金属板を複数重ねて形成することも可能である。以下、金属支持体1および貫通空間1cの構造の例について図面を参照しながら説明する。なお金属酸化物層1fについては図示を省略する。
電極層2は、図1に示すように、金属支持体1の表側の面であって貫通空間1cが設けられた領域より大きな領域に、薄層の状態で設けることができる。薄層とする場合は、その厚さを、例えば、1μm~100μm程度、好ましくは、5μm~50μmとすることができる。このような厚さにすると、高価な電極層材料の使用量を低減してコストダウンを図りつつ、十分な電極性能を確保することが可能となる。貫通空間1cが設けられた領域の全体が、電極層2に覆われている。つまり、貫通空間1cは金属支持体1における電極層2が形成された領域の内側に形成されている。換言すれば、全ての貫通空間1cが電極層2に面して設けられている。
すなわち電極層2は、多孔質な層として形成される。電極層2は、例えば、その緻密度が30%以上80%未満となるように形成される。細孔のサイズは、電気化学反応を行う際に円滑な反応が進行するのに適したサイズを適宜選ぶことができる。なお緻密度とは、層を構成する材料の空間に占める割合であって、(1-空孔率)と表すことができ、また、相対密度と同等である。
中間層3(挿入層)は、図1に示すように、電極層2を覆った状態で、電極層2の上に薄層の状態で形成することができる。薄層とする場合は、その厚さを、例えば、1μm~100μm程度、好ましくは2μm~50μm程度、より好ましくは4μm~25μm程度とすることができる。このような厚さにすると、高価な中間層材料の使用量を低減してコストダウンを図りつつ、十分な性能を確保することが可能となる。中間層3の材料としては、例えば、YSZ(イットリア安定化ジルコニア)、SSZ(スカンジウム安定化ジルコニア)やGDC(ガドリウム・ドープ・セリア)、YDC(イットリウム・ドープ・セリア)、SDC(サマリウム・ドープ・セリア)等を用いることができる。特にセリア系のセラミックスが好適に用いられる。
電解質層4は、図1に示すように、電極層2および中間層3を覆った状態で、中間層3の上に薄層の状態で形成される。また、厚さが10μm以下の薄膜の状態で形成することもできる。詳しくは電解質層4は、図1に示すように、中間層3の上と金属支持体1の上とにわたって(跨って)設けられる。このように構成し、電解質層4を金属支持体1に接合することで、電気化学素子全体として堅牢性に優れたものとすることができる。
反応防止層5は、電解質層4の上に薄層の状態で形成することができる。薄層とする場合は、その厚さを、例えば、1μm~100μm程度、好ましくは2μm~50μm程度、より好ましくは3μm~15μm程度とすることができる。このような厚さにすると、高価な反応防止層材料の使用量を低減してコストダウンを図りつつ、十分な性能を確保することが可能となる。反応防止層5の材料としては、電解質層4の成分と対極電極層6の成分との間の反応を防止できる材料であれば良いが、例えばセリア系材料等が用いられる。また反応防止層5の材料として、Sm、GdおよびYからなる群から選ばれる元素のうち少なくとも1つを含有する材料が好適に用いられる。なお、Sm、GdおよびYからなる群から選ばれる元素のうち少なくとも1つを含有し、これら元素の含有率の合計が1.0質量%以上10質量%以下であるとよい。反応防止層5を電解質層4と対極電極層6との間に導入することにより、対極電極層6の構成材料と電解質層4の構成材料との反応が効果的に抑制され、電気化学素子Eの性能の長期安定性を向上できる。反応防止層5の形成は、1100℃以下の処理温度で形成できる方法を適宜用いて行うと、金属支持体1の損傷を抑制し、また、金属支持体1と電極層2との元素相互拡散を抑制でき、性能・耐久性に優れた電気化学素子Eを実現できるので好ましい。例えば、低温焼成法(例えば1100℃を越える高温域での焼成処理をしない低温域での焼成処理を用いる湿式法)、スプレーコーティング法(溶射法やエアロゾルデポジション法、エアロゾルガスデポジッション法、パウダージェットデポジッション法、パーティクルジェットデポジション法、コールドスプレー法などの方法)、PVD法(スパッタリング法、パルスレーザーデポジション法など)、CVD法などを適宜用いて行うことができる。特に、低温焼成法やスプレーコーティング法などを用いると低コストな素子が実現できるので好ましい。更に、低温焼成法を用いると、原材料のハンドリングが容易になるので更に好ましい。
対極電極層6は、電解質層4もしくは反応防止層5の上に薄層の状態で形成することができる。薄層とする場合は、その厚さを、例えば、1μm~100μm程度、好ましくは、5μm~50μmとすることができる。このような厚さにすると、高価な対極電極層材料の使用量を低減してコストダウンを図りつつ、十分な電極性能を確保することが可能となる。対極電極層6の材料としては、例えば、LSCF、LSM等の複合酸化物、セリア系酸化物およびこれらの混合物を用いることができる。特に対極電極層6が、La、Sr、Sm、Mn、CoおよびFeからなる群から選ばれる2種類以上の元素を含有するペロブスカイト型酸化物を含むことが好ましい。以上の材料を用いて構成される対極電極層6は、カソードとして機能する。
以上のように電気化学素子Eを構成することで、電気化学素子Eを固体酸化物形燃料電池の発電セルとして用いることができる。例えば、金属支持体1の裏側の面から貫通空間1cを通じて水素を含む燃料ガスを電極層2へ供給し、電極層2の対極となる対極電極層6へ空気を供給し、例えば、500℃以上900℃以下の温度で作動させる。そうすると、対極電極層6において空気に含まれる酸素O2が電子e-と反応して酸素イオンO2-が生成される。その酸素イオンO2-が電解質層4を通って電極層2へ移動する。電極層2においては、供給された燃料ガスに含まれる水素H2が酸素イオンO2-と反応し、水H2Oと電子e-が生成される。以上の反応により、電極層2と対極電極層6との間に起電力が発生する。この場合、電極層2はSOFCの燃料極(アノード)として機能し、対極電極層6は空気極(カソード)として機能する。
次に、電気化学素子Eの製造方法について説明する。
電極層形成ステップでは、金属支持体1の表側の面の貫通空間1cが設けられた領域より広い領域に電極層2が薄膜の状態で形成される。金属支持体1の貫通孔はレーザー加工等によって設けることができる。電極層2の形成は、上述したように、低温焼成法(1100℃以下の低温域での焼成処理を行う湿式法)、スプレーコーティング法(溶射法やエアロゾルデポジション法、エアロゾルガスデポジッション法、パウダージェットデポジッション法、パーティクルジェットデポジション法、コールドスプレー法などの方法)、PVD法(スパッタリング法、パルスレーザーデポジション法など)、CVD法などの方法を用いることができる。いずれの方法を用いる場合であっても、金属支持体1の劣化を抑制するため、1100℃以下の温度で行うことが望ましい。
まず、電極層2の材料粉末と溶媒(分散媒)とを混合して材料ペーストを作成し、金属支持体1の表側の面に塗布する。そして電極層2を圧縮成形し(電極層平滑化工程)、1100℃以下で焼成する(電極層焼成工程)。電極層2の圧縮成形は、例えば、CIP(Cold Isostatic Pressing 、冷間静水圧加圧)成形、ロール加圧成形、RIP(Rubber Isostatic Pressing)成形などにより行うことができる。また、電極層の焼成は、800℃以上1100℃以下の温度で行うと好適である。また、電極層平滑化工程と電極層焼成工程の順序を入れ替えることもできる。
なお、中間層3を有する電気化学素子を形成する場合では、電極層平滑化工程や電極層焼成工程を省いたり、電極層平滑化工程や電極層焼成工程を後述する中間層平滑化工程や中間層焼成工程に含めることもできる。
なお、電極層平滑化工程は、ラップ成形やレベリング処理、表面の切削・研磨処理などを施すことによって行うことでもできる。
上述した電極層形成ステップにおける焼成工程時に、金属支持体1の表面に金属酸化物層1f(拡散抑制層)が形成される。なお、上記焼成工程に、焼成雰囲気を酸素分圧が低い雰囲気条件とする焼成工程が含まれていると元素の相互拡散抑制効果が高く、抵抗値の低い良質な金属酸化物層1f(拡散抑制層)が形成されるので好ましい。電極層形成ステップを、焼成を行わないコーティング方法とする場合を含め、別途の拡散抑制層形成ステップを含めても良い。いずれにおいても、金属支持体1の損傷を抑制可能な1100℃以下の処理温度で実施することが望ましい。また、後述する中間層形成ステップにおける焼成工程時に、金属支持体1の表面に金属酸化物層1f(拡散抑制層)が形成されても良い。
中間層形成ステップでは、電極層2を覆う形態で、電極層2の上に中間層3が薄層の状態で形成される。中間層3の形成は、上述したように、低温焼成法(1100℃以下の低温域での焼成処理を行う湿式法)、スプレーコーティング法(溶射法やエアロゾルデポジション法、エアロゾルガスデポジッション法、パウダージェットデポジッション法、パーティクルジェットデポジション法、コールドスプレー法などの方法)、PVD法(スパッタリング法、パルスレーザーデポジション法など)、CVD法などの方法を用いることができる。いずれの方法を用いる場合であっても、金属支持体1の劣化を抑制するため、1100℃以下の温度で行うことが望ましい。
まず、中間層3の材料粉末と溶媒(分散媒)とを混合して材料ペーストを作成し、金属支持体1の表側の面に塗布する。そして中間層3を圧縮成形し(中間層平滑化工程)、1100℃以下で焼成する(中間層焼成工程)。中間層3の圧延は、例えば、CIP(Cold Isostatic Pressing 、冷間静水圧加圧)成形、ロール加圧成形、RIP(Rubber Isostatic Pressing)成形などにより行うことができる。また、中間層3の焼成は、800℃以上1100℃以下の温度で行うと好適である。このような温度であると、金属支持体1の損傷・劣化を抑制しつつ、強度の高い中間層3を形成できるためである。また、中間層3の焼成を1050℃以下で行うとより好ましく、1000℃以下で行うと更に好ましい。これは、中間層3の焼成温度を低下させる程に、金属支持体1の損傷・劣化をより抑制しつつ、電気化学素子Eを形成できるからである。また、中間層平滑化工程と中間層焼成工程の順序を入れ替えることもできる。
なお、中間層平滑化工程は、ラップ成形やレベリング処理、表面の切削・研磨処理などを施すことによって行うことでもできる。
電解質層形成ステップでは、電極層2および中間層3を覆った状態で、電解質層4が中間層3の上に薄層の状態で形成される。また、厚さが10μm以下の薄膜の状態で形成されても良い。電解質層4の形成は、上述したように、低温焼成法(1100℃以下の低温域での焼成処理を行う湿式法)、スプレーコーティング法(溶射法やエアロゾルデポジション法、エアロゾルガスデポジッション法、パウダージェットデポジッション法、パーティクルジェットデポジション法、コールドスプレー法などの方法)、PVD法(スパッタリング法、パルスレーザーデポジション法など)、CVD法などの方法を用いることができる。いずれの方法を用いる場合であっても、金属支持体1の劣化を抑制するため、1100℃以下の温度で行うことが望ましい。
反応防止層形成ステップでは、反応防止層5が電解質層4の上に薄層の状態で形成される。反応防止層5の形成は、上述したように、低温焼成法(1100℃以下の低温域での焼成処理を行う湿式法)、スプレーコーティング法(溶射法やエアロゾルデポジション法、エアロゾルガスデポジッション法、パウダージェットデポジッション法、パーティクルジェットデポジション法、コールドスプレー法などの方法)、PVD法(スパッタリング法、パルスレーザーデポジション法など)、CVD法などの方法を用いることができる。いずれの方法を用いる場合であっても、金属支持体1の劣化を抑制するため、1100℃以下の温度で行うことが望ましい。なお反応防止層5の上側の面を平坦にするために、例えば反応防止層5の形成後にレベリング処理や表面を切削・研磨処理を施したり、湿式形成後焼成前に、プレス加工を施してもよい。
対極電極層形成ステップでは、対極電極層6が反応防止層5の上に薄層の状態で形成される。対極電極層6の形成は、上述したように、低温焼成法(1100℃以下の低温域での焼成処理を行う湿式法)、スプレーコーティング法(溶射法やエアロゾルデポジション法、エアロゾルガスデポジッション法、パウダージェットデポジッション法、パーティクルジェットデポジション法、コールドスプレー法などの方法)、PVD法(スパッタリング法、パルスレーザーデポジション法など)、CVD法などの方法を用いることができる。いずれの方法を用いる場合であっても、金属支持体1の劣化を抑制するため、1100℃以下の温度で行うことが望ましい。
<比較例1>
厚さ0.3mm、120mm角(120mm×120mm)のcrofer22APUの金属板に対して、中心から98mm角(98mm×98mm)の領域にレーザー加工により貫通空間1cを複数設け、比較例1に係る金属板(金属支持体1)を作製した。貫通空間1cは、直交格子の格子点に設けた。なお、表側開口部1dの直径は20μm、ピッチPは200μmである。最大長さLmaxは、16.97cmである。
比較例1と同様にして、表側開口部1dのピッチPが150μm(表側開口部1dの直径は25μm)である比較例2に係る金属板(金属支持体1)を作製した。
比較例1と同様の金属板(金属支持体1)に対して平滑化するためのレベラー処理を行うことで、実施例1に係る金属板(金属支持体1)を作製した。
比較例2と同様の金属板(金属支持体1)に対して平滑化するための焼鈍処理を行うことで、実施例2に係る金属板(金属支持体1)を作製した。
<実施例3>
厚さ0.3mm、40mm角(40mm×40mm)のcrofer22APUの金属板に対して、中心から28mm角(28mm×28mm)の領域にレーザー加工により貫通空間1cを複数設け、実施例3に係る金属板(金属支持体1)を作製した。貫通空間1cは、直交格子の格子点に設けた。なお、表側開口部1dの直径は25μm、ピッチPは150μmである。最大長さLmaxは、5.66cmである。
一方、実施例(実施例1、2、3)においては、いずれの金属支持体1においても反り度が小さく、割れや剥離等の表面欠陥を抑制して電気化学素子Eとしての使用に供することのできる電極層2を積層することができた。このうち最も反り度の値が大きい実施例3では、金属支持体1の反り度が1.1×10-2であった。
図2・図3を用いて、第2実施形態に係る電気化学素子E、電気化学モジュールM、電気化学装置YおよびエネルギーシステムZについて説明する。
エネルギーシステムZは、電気化学装置Yと、電気化学装置Yから排出される熱を再利用する排熱利用部としての熱交換器53とを有する。
電気化学装置Yは、電気化学モジュールMと、脱硫器31と改質器34とを有し電気化学モジュールMに対して還元性成分を含有する燃料ガスを供給する燃料供給部と、電気化学モジュールMから電力を取り出すインバータ38とを有する。
図4に、電気化学モジュールMの他の実施形態を示す。第3実施形態に係る電気化学モジュールMは、上述の電気化学素子Eを、セル間接続部材71を間に挟んで積層することで、電気化学モジュールMを構成する。
(1)上記実施形態では、金属支持体1の重心Gを通る複数本の直線L上において、重心Gを中心として金属支持体1の板状面内において互いに対向する少なくとも4点Pを用いて最小二乗法により最小二乗平面αを算出している。そして、最小二乗平面αからの互いに対向するプラス側最大変位値からマイナス側最大変位値までの値Daに基づいて反り度を算出している。しかし、以下の方法によっても反り度を算出可能である。
金属支持体1の板状面内のランダムに配置された少なくとも3点Pを用いて最小二乗法により求めた最小二乗値αVを算出してもよい。つまり、複数点Pから、複数点Pを代表する最小二乗平面αを算出するのではなく、複数点Pを代表する直線等で表される最小二乗値αVを算出してもよい。なお、本実施形態及びその他の実施形態においては、最小二乗値αVは、例えば、その複数点Pを代表する直線及び平面(最小二乗平面α)等を含むものとする。
以上の方法によれば、上記実施形態と同様に金属支持体1の反り度を精度良く求めることができる。
また、金属支持体1の重心Gを通る少なくとも一本の直線L上において、重心Gを中心として金属支持体1の板状面内において互いに対向する少なくとも3点Pを用いて最小二乗法により最小二乗値αVを算出してもよい。最小二乗値αVに基づいて反り度を算出する方法は上述した方法と同様である。
また、金属支持体1の重心Gを通る少なくとも一本の直線L上において、重心Gを中心として金属支持体1の板状面内において互いに対向する位置にある点Pのうち、プラス側最大変位値とマイナス側最大変位値との差分Da1を求めてもよい。そして、前述と同様に、Da1を最大長さLmaxで割って反り度を算出する。
この場合、差分Da1の算出に、一本の直線Lにおける複数点Pを用いてもよいし、複数の直線Lにおける複数点Pを用いてもよい。
1a 表側面
1b 裏側面
1c 貫通空間
1d 表側開口部
1e 裏側開口部
1f 金属酸化物層
1g 孔領域
1h 単位領域
T 厚さ
D 内径、直径、孔径
P ピッチ、間隔
S 面積(表側開口部)
A 開口率
10 第1金属板
10a 第1表側面
10b 第1裏側面
10c 第1貫通空間
10d 第1表側開口部
10e 第1裏側開口部
10g 第1孔領域
10h 第1単位領域
T1 厚さ
D1 内径、直径、孔径
P1 ピッチ、間隔
S1 面積(表側開口部)
A1 開口率
20 第2金属板
20a 第2表側面
20b 第2裏側面
20c 第2貫通空間
20d 第2表側開口部
20e 第2裏側開口部
T2 厚さ
D2 内径、直径、孔径
P2 ピッチ、間隔
G 重心
Y 電気化学装置
Z エネルギーシステム
α 最小二乗平面
αV 最小二乗値
Claims (19)
- 電気化学素子の金属支持体であって、
前記金属支持体は板状面を有して全体として板状であり、前記金属支持体は、電極層が設けられる面を表側面として、前記表側面から裏側面へ貫通する複数の貫通空間を有し、前記表側面において前記貫通空間が形成されている領域を孔領域とし、
以下の反り度を満たす金属支持体。
(反り度)
前記金属支持体の板状面内の少なくとも3点を用いて最小二乗法により最小二乗値を算出し、前記最小二乗値に対してプラス側へのプラス側最大変位値と前記最小二乗値との第一差分と、前記最小二乗値に対して前記プラス側とは反対のマイナス側へのマイナス側最大変位値と前記最小二乗値との第二差分とを算出し、前記第一差分と第二差分との和であるDaを、重心を通る前記金属支持体の前記板状面での最大長さLmaxで割ったDa/Lmaxを前記反り度とし、前記反り度が1.5×10-2以下である。 - 前記金属支持体の板状面内の少なくとも2点は、前記重心を通る少なくとも一本の直線上において、前記金属支持体の板状面内において前記重心を中心として互いに対向する少なくとも2点である、請求項1に記載の金属支持体。
- 前記直線が複数本の直線である場合、前記複数の直線は、前記重心を中心として360°を所定角度ごとに分割している、請求項2に記載の金属支持体。
- 前記金属支持体の板状面内において前記重心を中心として互いに対向する少なくとも2点は、前記金属支持体の周縁と前記孔領域との間に存在する点である、請求項2又は3に記載の金属支持体。
- 前記金属支持体の板状面内において前記重心を中心として互いに対向する少なくとも2点は、前記金属支持体の周縁と、前記金属支持体上に積層される前記電極層との間に存在する点である、請求項2~4のいずれか1項に記載の金属支持体。
- 前記最小二乗値は、前記金属支持体の板状面内の少なくとも4点を用いて最小二乗法により算出される最小二乗平面である、請求項1~5のいずれか1項に記載の金属支持体。
- 前記貫通空間の前記表側面の開口部である表側開口部が、直径が10μm以上60μm以下の円形又は略円形である、請求項1~6のいずれか1項に記載の金属支持体。
- 前記貫通空間の前記裏側面の開口部である裏側開口部が、前記貫通空間の前記表側面の開口部である表側開口部よりも大きい面積または直径を有する、請求項1~7のいずれか1項に記載の金属支持体。
- 前記貫通空間の前記表側面の開口部である表側開口部の間隔が0.05mm以上0.3mm以下である、請求項1~8のいずれか1項に記載の金属支持体。
- 厚さが0.1mm以上1.0mm以下である、請求項1~9のいずれか1項に記載の金属支持体。
- 材料がFe-Cr系合金である、請求項1~10のいずれか1項に記載の金属支持体。
- 請求項1から11のいずれか1項に記載の金属支持体の前記表側面に、少なくとも電極層と電解質層と対極電極層とが設けられた、電気化学素子。
- 請求項12に記載の電気化学素子が複数集合した状態で配置される電気化学モジュール。
- 請求項13に記載の電気化学モジュールと改質器とを少なくとも有し、前記電気化学モジュールに対して還元性成分を含有する燃料ガスを供給する燃料供給部を有する電気化学装置。
- 請求項13に記載の電気化学モジュールと、前記電気化学モジュールから電力を取り出すインバータとを少なくとも有する電気化学装置。
- 請求項14または15に記載の電気化学装置と、前記電気化学装置から排出される熱を再利用する排熱利用部とを有するエネルギーシステム。
- 請求項12に記載の電気化学素子を備え、前記電気化学素子で発電反応を生じさせる固体酸化物形燃料電池。
- 請求項1から11のいずれか1項に記載の金属支持体を製造する製造方法であって、レーザー加工またはパンチング加工またはエッチング加工のいずれか、または、それらの組合せによって、前記表側面から裏側面へ貫通する複数の貫通空間を形成する、金属支持体の製造方法。
- 平滑化処理工程を含む請求項18に記載の金属支持体の製造方法。
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EP19777817.8A EP3790092A4 (en) | 2018-03-30 | 2019-03-29 | METAL SUPPORT FOR ELECTROCHEMICAL ELEMENT, ELECTROCHEMICAL ELEMENT, ELECTROCHEMICAL MODULE, ELECTROCHEMICAL DEVICE, POWER SYSTEM, SOLID OXIDE FUEL CELL AND METHOD OF PRODUCTION FOR METAL SUPPORT |
CN201980023977.6A CN111919320B (zh) | 2018-03-30 | 2019-03-29 | 电化学元件的金属支撑体、电化学元件、电化学模块、电化学装置、能源系统 |
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