WO2024201576A1 - 電気化学セル - Google Patents

電気化学セル Download PDF

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Publication number
WO2024201576A1
WO2024201576A1 PCT/JP2023/011860 JP2023011860W WO2024201576A1 WO 2024201576 A1 WO2024201576 A1 WO 2024201576A1 JP 2023011860 W JP2023011860 W JP 2023011860W WO 2024201576 A1 WO2024201576 A1 WO 2024201576A1
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Prior art keywords
region
electrode layer
metal support
hydrogen electrode
layer
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English (en)
French (fr)
Japanese (ja)
Inventor
直哉 秋山
俊之 中村
誠 大森
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NGK Insulators Ltd
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NGK Insulators Ltd
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Priority to PCT/JP2023/011860 priority Critical patent/WO2024201576A1/ja
Priority to JP2024560951A priority patent/JP7692539B2/ja
Publication of WO2024201576A1 publication Critical patent/WO2024201576A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C25B1/042—Hydrogen or oxygen by electrolysis of water by electrolysis of steam
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • 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
    • 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

Definitions

  • the present invention relates to an electrochemical cell.
  • electrochemical cells electrolysis cells, fuel cells, etc.
  • a cell body disposed on a metal support are known (see, for example, Patent Document 1).
  • the metal support has a plurality of communication holes formed on its main surface.
  • the cell body is formed on the main surface of the metal support and has a first electrode layer covering the plurality of communication holes, a second electrode layer, and an electrolyte layer disposed between the first electrode layer and the second electrode layer.
  • the first electrode layer contains nickel as a metal for imparting electrical conductivity. The nickel contained in the first electrode layer becomes nickel oxide in an oxidizing atmosphere and becomes metallic nickel in a reducing atmosphere.
  • the first electrode layer expands/contracts due to the oxidation-reduction cycle. Specifically, when the first electrode layer is reduced before the operation of the electrochemical cell, nickel oxide becomes metallic nickel and the first electrode layer contracts, and when the operation of the electrochemical cell is stopped and the first electrode layer changes from a reducing atmosphere to an oxidizing atmosphere, metallic nickel becomes nickel oxide and the first electrode layer expands.
  • the objective of the present invention is to provide an electrochemical cell that can prevent the first electrode layer from peeling off from the metal support.
  • the electrochemical cell according to the first aspect of the present invention comprises a metal support having a plurality of through holes formed on a main surface, a first electrode layer formed on the main surface and covering the plurality of through holes, a second electrode layer, and a cell body having an electrolyte layer disposed between the first electrode layer and the second electrode layer.
  • the first electrode layer has a first region within 5 ⁇ m in the thickness direction from a first surface that contacts the metal support, a second region within 5 ⁇ m in the thickness direction from a second surface that contacts the electrolyte layer, and a third region between the first region and the second region.
  • Each of the first region, the second region, and the third region contains nickel and an oxide ion conductive material.
  • the nickel content in the first region is lower than the nickel content in the third region.
  • the electrochemical cell according to the second aspect of the present invention is the electrochemical cell according to the first aspect, in which the nickel content in the second region is lower than the nickel content in the third region.
  • the electrochemical cell according to the third aspect of the present invention is the electrochemical cell according to the first or second aspect, in which the nickel content in the second region is lower than the nickel content in the first region.
  • the electrochemical cell according to a fourth aspect of the present invention relates to the above-mentioned first to fourth aspects, and the first electrode layer has a fourth region disposed inside at least one of the plurality of communication holes.
  • the fourth region contains nickel and an oxide ion conductive material.
  • the nickel content in the fourth region is lower than the nickel content in the third region.
  • the present invention provides an electrochemical cell that can prevent the first electrode layer from peeling off from the metal support.
  • FIG. 1 is a plan view of an electrolysis cell according to an embodiment.
  • FIG. 2 is a cross-sectional view taken along line AA of FIG.
  • FIG. 3 is a partially enlarged view of FIG. 2 .
  • FIG. 4 is a cross-sectional view of an electrolysis cell 100 according to the first modification.
  • Fig. 1 is a plan view of an electrolytic cell 1 according to an embodiment.
  • Fig. 2 is a cross-sectional view taken along line AA in Fig. 1.
  • the electrolytic cell 1 is an example of the "electrochemical cell" according to the present invention.
  • the electrolytic cell 1 is formed in a plate shape extending in the X-axis and Y-axis directions.
  • the electrolytic cell 1 is formed in a rectangular shape extending in the Y-axis direction when viewed in a plan view from the Z-axis direction perpendicular to the X-axis and Y-axis directions.
  • the planar shape of the electrolytic cell 1 is not particularly limited, and may be a polygon other than a rectangle, an ellipse, a circle, etc.
  • the X-axis and Y-axis directions are the surface directions of the electrolytic cell 1, and the Z-axis direction is the thickness direction of the electrolytic cell 1.
  • the electrolysis cell 1 includes a metal support 10, a cell body 20, and a flow path member 30.
  • the metal support 10 supports the cell main body 20.
  • the metal support 10 is formed in a plate shape.
  • the metal support 10 may be in the shape of a flat plate or a curved plate.
  • the metal support 10 only needs to be able to support the electrolysis cell 1, and there are no particular limitations on its thickness, but it can be, for example, 0.1 mm or more and 2.0 mm or less.
  • the metal support 10 has a plurality of communication holes 11, a first main surface 12, and a second main surface 13.
  • Each communication hole 11 penetrates the metal support 10 from the first main surface 12 to the second main surface 13. Each communication hole 11 opens to the first main surface 12 and the second main surface 13. The opening of each communication hole 11 on the first main surface 12 side is covered by the hydrogen electrode layer 6. The opening of each communication hole 11 on the second main surface 13 side is connected to a flow path 30a described later.
  • Each communication hole 11 can be formed by mechanical processing (e.g., punching), laser processing, or chemical processing (e.g., etching).
  • each communication hole 11 is formed linearly along the Z-axis direction.
  • each communication hole 11 may be inclined with respect to the Z-axis direction, and may not be linear.
  • the communication holes 11 may be connected to each other.
  • the first main surface 12 is provided on the opposite side to the second main surface 13.
  • the cell main body 20 is disposed on the first main surface 12.
  • the flow path member 30 is bonded to the second main surface 13.
  • the metal support 10 is made of a metal material.
  • the metal support 10 is made of an alloy material containing Cr (chromium).
  • Examples of such metal materials include Fe-Cr alloy steel (stainless steel, etc.) and Ni-Cr alloy steel.
  • Cr content in the metal support 10 can be 4% by mass or more and 30% by mass or less.
  • the metal support 10 may contain Ti (titanium) and Zr (zirconium).
  • the Ti content in the metal support 10 is not particularly limited, but may be 0.01 mol% or more and 1.0 mol% or less.
  • the Al content in the metal support 10 is not particularly limited, but may be 0.01 mol% or more and 0.4 mol% or less.
  • the metal support 10 may contain Ti as TiO2 (titania) and Zr as ZrO2 (zirconia).
  • the metal support 10 may have an oxide film on its surface that is formed by oxidation of the constituent elements of the metal support 10.
  • a typical example of the oxide film is a chromium oxide film.
  • the chromium oxide film covers at least a portion of the surface of the metal support 10.
  • the chromium oxide film may also cover at least a portion of the inner wall surface of each communication hole 11.
  • the cell body 20 is disposed on the metal support 10.
  • the cell body 20 is supported by the metal support 10.
  • the cell body 20 has a hydrogen electrode layer 6 (cathode), an electrolyte layer 7, a reaction prevention layer 8, and an oxygen electrode layer 9 (anode).
  • the hydrogen electrode layer 6, electrolyte layer 7, reaction prevention layer 8, and oxygen electrode layer 9 are stacked in this order in the Z-axis direction from the metal support 10 side.
  • the hydrogen electrode layer 6, electrolyte layer 7, and oxygen electrode layer 9 are required components, while the reaction prevention layer 8 is optional.
  • the hydrogen electrode layer 6 is an example of a "first electrode layer” according to the present invention.
  • the hydrogen electrode layer 6 is disposed between the metal support 10 and the electrolyte layer 7.
  • the hydrogen electrode layer 6 is formed on the first main surface 12 of the metal support 10. In this embodiment, a portion of the hydrogen electrode layer 6 is disposed inside each of the communication holes 11 of the metal support 10. A detailed configuration of the hydrogen electrode layer 6 will be described later.
  • a source gas is supplied to the hydrogen electrode layer 6 through each of the communication holes 11.
  • the source gas contains at least H2O .
  • the hydrogen electrode layer 6 produces H 2 from the source gas in accordance with the electrochemical reaction of water electrolysis shown in the following formula (1).
  • Hydrogen electrode layer 6 H 2 O+2e ⁇ ⁇ H 2 +O 2 ⁇ (1)
  • the hydrogen electrode layer 6 produces H 2 , CO, and O 2 ⁇ from the source gas in accordance with the co-electrochemical reactions shown in the following formulas (2), (3), and (4).
  • Hydrogen electrode layer 6 CO 2 + H 2 O + 4e ⁇ ⁇ CO + H 2 + 2O 2 ⁇ (2) Electrochemical reaction of H 2 O: H 2 O + 2e ⁇ ⁇ H 2 + O 2 ⁇ (3) Electrochemical reaction of CO2 : CO2 + 2e- ⁇ CO + O2 -... (4)
  • the hydrogen electrode layer 6 is a porous body with electronic conductivity.
  • the hydrogen electrode layer 6 contains nickel (Ni) and an oxide ion conductive material.
  • Ni functions as an electronic conductor. In the case of co-electrolysis, Ni also functions as a thermal catalyst to promote the thermal reaction between the generated H2 and the CO2 contained in the feed gas to maintain an appropriate gas composition for methanation, reverse water gas shift reaction, etc.
  • Ni exists in the form of nickel oxide (NiO) in an oxidizing atmosphere and in the form of metallic Ni in a reducing atmosphere.
  • the hydrogen electrode layer 6 is exposed to an oxidizing atmosphere when the electrolytic cell 1 is stopped, and is exposed to a reducing atmosphere when the electrolytic cell 1 is in operation and during the reduction treatment carried out before the operation of the electrolytic cell 1.
  • the hydrogen electrode layer 6 expands/contracts with the oxidation/reduction of Ni.
  • oxide ion conductive materials examples include YSZ, CSZ, ScSZ, GDC, SDC, (La,Sr)(Cr,Mn) O3 , (La,Sr) TiO3 , Sr2 (Fe,Mo) 2O6 , ( La ,Sr) VO3 , (La,Sr) FeO3 , LDC (lanthanum doped ceria), LSGM (lanthanum gallate), and mixed materials of two or more of these.
  • the thickness of the hydrogen electrode layer 6 is not particularly limited, but can be, for example, 1 ⁇ m or more and 100 ⁇ m or less.
  • the method for forming the hydrogen electrode layer 6 is not particularly limited, and may be a sintering method, a spray coating method (thermal spraying, aerosol deposition, aerosol gas deposition, powder jet deposition, particle jet deposition, cold spray, etc.), a PVD method (sputtering, pulsed laser deposition, etc.), a CVD method, etc.
  • the electrolyte layer 7 is disposed between the hydrogen electrode layer 6 and the oxygen electrode layer 9.
  • the reaction prevention layer 8 is disposed between the electrolyte layer 7 and the oxygen electrode layer 9, so that the electrolyte layer 7 is sandwiched between the hydrogen electrode layer 6 and the reaction prevention layer 8.
  • the electrolyte layer 7 covers the hydrogen electrode layer 6 and also covers the area of the first main surface 12 of the metal support 10 that is exposed from the hydrogen electrode layer 6.
  • the electrolyte layer 7 transfers O 2- generated in the hydrogen electrode layer 6 to the oxygen electrode layer 9.
  • the electrolyte layer 7 is made of a dense material having oxide ion conductivity.
  • the electrolyte layer 7 can be made of, for example, YSZ (yttria-stabilized zirconia, e.g., 8YSZ), GDC (gadolinium-doped ceria), ScSZ (scandia-stabilized zirconia), SDC (samarium-doped ceria), LSGM (lanthanum gallate), or the like.
  • the porosity of the electrolyte layer 7 is not particularly limited, but can be, for example, 0.1% to 7%.
  • the thickness of the electrolyte layer 7 is not particularly limited, but can be, for example, 1 ⁇ m to 100 ⁇ m.
  • the method for forming the electrolyte layer 7 is not particularly limited, and methods such as baking, spray coating, PVD, and CVD can be used.
  • reaction prevention layer 8 The reaction prevention layer 8 is disposed between the electrolyte layer 7 and the oxygen electrode layer 9. The reaction prevention layer 8 is disposed on the opposite side of the electrolyte layer 7 to the hydrogen electrode layer 6. The reaction prevention layer 8 prevents the constituent elements of the electrolyte layer 7 from reacting with the constituent elements of the oxygen electrode layer 9 to form a layer with high electrical resistance.
  • the reaction prevention layer 8 is made of an oxide ion conductive material.
  • the reaction prevention layer 8 can be made of GDC, SDC, etc.
  • the porosity of the reaction prevention layer 8 is not particularly limited, but can be, for example, 0.1% to 50%.
  • the thickness of the reaction prevention layer 8 is not particularly limited, but can be, for example, 1 ⁇ m to 50 ⁇ m.
  • the method for forming the reaction prevention layer 8 is not particularly limited, and a baking method, a spray coating method, a PVD method, a CVD method, etc. can be used.
  • the oxygen electrode layer 9 is an example of a "second electrode layer” according to the present invention.
  • the oxygen electrode layer 9 is disposed on the opposite side of the hydrogen electrode layer 6 with respect to the electrolyte layer 7.
  • the reaction prevention layer 8 is disposed between the electrolyte layer 7 and the oxygen electrode layer 9, and therefore the oxygen electrode layer 9 is connected to the reaction prevention layer 8. If the reaction prevention layer 8 is not disposed between the electrolyte layer 7 and the oxygen electrode layer 9, the oxygen electrode layer 9 would be connected to the electrolyte layer 7.
  • the oxygen electrode layer 9 produces O 2 from O 2 ⁇ transferred from the hydrogen electrode layer 6 via the electrolyte layer 7 in accordance with the chemical reaction of the following formula (2).
  • Oxygen electrode layer 9 2O 2 ⁇ ⁇ O 2 +4e ⁇ (2)
  • the oxygen electrode layer 9 is made of a porous material having oxide ion conductivity and electron conductivity, and may be made of a composite material of one or more of (La,Sr)(Co,Fe) O3 , (La,Sr) FeO3 , La(Ni,Fe) O3 , (La,Sr) CoO3 , and (Sm,Sr) CoO3 and an oxide ion conductive material (such as GDC).
  • the porosity of the oxygen electrode layer 9 is not particularly limited, but can be, for example, 20% or more and 60% or less.
  • the thickness of the oxygen electrode layer 9 is not particularly limited, but can be, for example, 1 ⁇ m or more and 100 ⁇ m or less.
  • the method for forming the oxygen electrode layer 9 is not particularly limited, and a firing method, a spray coating method, a PVD method, a CVD method, etc. can be used.
  • the flow path member 30 is joined to the second main surface 13 of the metal support 10.
  • the flow path member 30 forms a flow path 30a between itself and the metal support 10.
  • a source gas is supplied to the flow path 30a.
  • the source gas supplied to the flow path 30a is supplied to the hydrogen electrode layer 6 of the cell main body 20 through each communication hole 11 of the metal support 10.
  • the flow path member 30 can be made of, for example, an alloy material.
  • the flow path member 30 may be made of the same material as the metal support 10. In this case, the flow path member 30 may be substantially integral with the metal support 10.
  • the flow path member 30 has a frame body 31 and an interconnector 32.
  • the frame body 31 is an annular member that surrounds the side of the flow path 30a.
  • the frame body 31 is joined to the second main surface 13 of the metal support body 10.
  • the interconnector 32 is a plate-shaped member for electrically connecting an external power source or another electrolysis cell in series with the electrolysis cell 1.
  • the interconnector 32 is joined to the frame body 31.
  • the frame body 31 and the interconnector 32 are separate members, but the frame body 31 and the interconnector 32 may be an integrated member.
  • FIG. 3 is a partially enlarged view of Fig. 2. As shown in Fig. 3, the hydrogen electrode layer 6 has a first region 61, a second region 62, a third region 63, and a fourth region 64.
  • the first region 61 is a region of the hydrogen electrode layer 6 within 5 ⁇ m in the Z-axis direction (thickness direction) from the first surface S1 that contacts the metal support 10.
  • the second region 62 is a region of the hydrogen electrode layer 6 within 5 ⁇ m in the Z-axis direction from the second surface S2 that contacts the electrolyte layer 7.
  • the third region 63 is a region of the hydrogen electrode layer 6 between the first region 61 and the second region 62.
  • the fourth region 64 is a region of the hydrogen electrode layer 6 that is disposed inside the communication hole 11 of the metal support 10. The fourth region 64 is engaged with the communication hole 11, thereby exerting an anchor effect on the metal support 10.
  • the first to third regions 61 to 63 are required components, while the fourth region 64 is optional.
  • the fourth region 64 only needs to be present inside at least one of the multiple communication holes 11 formed in the metal support 10. Therefore, the number of fourth regions 64 may be the same as the number of communication holes 11, or may be less than the number of communication holes 11.
  • the first surface S1 of the hydrogen electrode layer 6 contacts the first main surface 12 of the metal support 10.
  • an approximation line of the first surface S1 obtained by the least squares method is used in a cross section along the Z-axis direction.
  • the region of the surface of the hydrogen electrode layer 6 that contacts the first main surface 12 of the metal support 10 is approximated as a straight line by the least squares method, and the obtained approximation line is regarded as the first surface S1 of the hydrogen electrode layer 6.
  • the region of the surface of the hydrogen electrode layer 6 that contacts the first main surface 12 of the metal support 10 does not include the inner surface of the communication hole 11 of the metal support 10.
  • the second surface S2 of the hydrogen electrode layer 6 contacts the hydrogen electrode layer side surface S3 of the electrolyte layer 7.
  • an approximation line of the second surface S2 obtained by the least squares method is used in a cross section along the Z-axis direction. Specifically, the region of the surface of the hydrogen electrode layer 6 that contacts the hydrogen electrode layer side surface S3 of the electrolyte layer 7 is approximated as a straight line by the least squares method, and the obtained approximation line is regarded as the second surface S2 of the hydrogen electrode layer 6.
  • Each of the first to fourth regions 61 to 64 contains Ni and an oxide ion conductive material.
  • the Ni content in the first region 61 is lower than the Ni content in the third region 63. This reduces the expansion/contraction of the first region 61 caused by the redox cycle, and prevents the hydrogen electrode layer 6 from peeling off from the metal support 10. Furthermore, the third region 63 can improve electronic conductivity and catalytic performance. This makes it possible to both prevent peeling of the hydrogen electrode layer 6 and maintain electrode performance.
  • the Ni content in the second region 62 is preferably lower than the Ni content in the third region 63. This allows the expansion/contraction to be reduced not only in the first region 61 but also in the second region 62, making it possible to suppress the increase in internal resistance caused by the deterioration of adhesion between the hydrogen electrode layer 6 and the electrolyte layer 7 when oxidation-reduction cycles are repeated, while maintaining electrode performance.
  • the Ni content in the second region 62 is preferably lower than the Ni content in the first region 61. This makes the amount of reduction shrinkage in the second region 62 smaller than the amount of reduction shrinkage in the first region 61, improving the shrinkage balance in the entire hydrogen electrode layer 6. As a result, the hydrogen electrode layer 6 is prevented from warping in a protruding shape toward the metal support 10, and the hydrogen electrode layer 6 (particularly the outer periphery of the hydrogen electrode layer 6 in the surface direction) is prevented from peeling off from the metal support 10.
  • the Ni content in the fourth region 64 is preferably lower than the Ni content in the third region 63. This reduces the expansion/contraction of the fourth region 64 caused by the redox cycle, thereby suppressing changes in the shape of the fourth region 64. As a result, the anchoring effect of the fourth region 64 can be maintained.
  • Ni content in the first to fourth regions 61 to 64 is calculated using the same method, as described below.
  • the Ni content in the first region 61 is calculated by measuring the Ni content at five locations (randomly selected) spaced apart in the plane direction in the center of the thickness direction of the first region 61 in a cross section of the hydrogen electrode layer 6 along the Z-axis direction, and averaging the five measured values obtained.
  • the value of the Ni content in the first region 61 is not particularly limited, but can be 25 mol% or more and 45 mol% or less.
  • the Ni content in the second region 62 is calculated by measuring the Ni content at five locations (randomly selected) spaced apart in the plane direction in the center of the thickness direction of the second region 62 in a cross section of the hydrogen electrode layer 6 along the Z-axis direction, and averaging the five measured values obtained.
  • the value of the Ni content in the second region 62 is not particularly limited, but can be 20 mol% or more and 45 mol% or less.
  • the Ni content in the third region 63 is calculated by measuring the Ni content at four locations in a cross section of the hydrogen electrode layer 6 along the Z-axis direction, which divides the third region 63 into five equal parts in the Z-axis direction, and averaging the four measured values.
  • the value of the Ni content in the third region 63 is not particularly limited, but can be 30 mol% or more and 50 mol% or less.
  • the Ni content in the fourth region 64 is calculated by measuring the Ni content at five locations (randomly selected) spaced apart in the plane direction in the center of the thickness direction of the fourth region 64 in a cross section of the hydrogen electrode layer 6 along the Z-axis direction, and averaging the five measured values obtained.
  • the value of the Ni content in the fourth region 64 is not particularly limited, but can be 20 mol% or more and 45 mol% or less.
  • the Ni content is calculated using the following method. First, a Ni composition mapping image on the cross section is obtained at 5,000 to 10,000 times magnification using an SEM device (FE-SEM JSM-7900F, manufactured by JEOL Ltd.) and an EDS device (JED-2300) attached to the SEM device. Next, Ni particle portions are identified in the Ni composition mapping image by performing binarization processing using image analysis using image analysis software Image-Pro manufactured by MEDIACYBERNETICS. The Ni content is then calculated by dividing the total area of the Ni particle portions by the total area of the backscattered electron image.
  • SEM device FE-SEM JSM-7900F, manufactured by JEOL Ltd.
  • JED-2300 EDS device
  • the first main surface 12 of the metal support 10 is not planar (for example, if the metal support 10 is made of a porous metal), it is difficult to identify the first surface S1 of the hydrogen electrode layer 6 using the first main surface 12 of the metal support 10.
  • Figure 4 is a cross section of the electrolysis cell 100 along the Z-axis direction (thickness direction).
  • the electrolysis cell 100 has the same configuration as the electrolysis cell 1 according to the above embodiment, except that the metal support 110 is made of a porous metal.
  • the metal support 110 has metal particles 111 connected in a three-dimensional mesh pattern and a plurality of interconnected communication holes 112.
  • the first main surface 113 of the metal support 10 has projections and recesses formed along the outer edges of the metal particles 111.
  • the second surface S2 of the hydrogen electrode layer 6 is identified by the hydrogen electrode layer side surface S3 of the electrolyte layer 7.
  • the intersection P where it intersects with the metal particles 111 is identified.
  • the intersection P is identified for each cluster of metal particles 111 that are separated on the cross section.
  • the metal particles 111 are divided into three clusters, so intersections P1 to P3 are identified in Figure 4.
  • the lines sequentially connecting the intersections P1 to P3 with straight lines are defined as the first surface S1 of the hydrogen electrode layer 6.
  • the first surface S1 of the hydrogen electrode layer 6 can be identified based on the hydrogen electrode layer side surface S3 of the electrolyte layer 7.
  • the hydrogen electrode layer 6 has the fourth region 64 , but it is not essential that the hydrogen electrode layer 6 has the fourth region 64 .
  • the electrolysis cell 1 has been described as an example of an electrochemical cell, but the electrochemical cell is not limited to the electrolysis cell.
  • An electrochemical cell is a general term for an element in which a pair of electrodes are arranged so that an electromotive force is generated from an overall oxidation-reduction reaction in order to convert electrical energy into chemical energy, and an element for converting chemical energy into electrical energy. Therefore, the electrochemical cell includes, for example, a fuel cell that uses oxide ions or protons as a carrier.
  • Comparative Example 1 An electrolytic cell according to Comparative Example 1 was prepared as follows.
  • a slurry for the hydrogen electrode layer was prepared by mixing GDC powder, NiO powder, butyral resin, polymethyl methacrylate beads as a pore-forming material, a plasticizer, a dispersant, and a solvent.
  • the slurry for the hydrogen electrode layer was then printed on the first main surface of the metal support by the doctor blade method to form a hydrogen electrode layer compact.
  • a slurry for the electrolyte layer was prepared by mixing YSZ powder, butyral resin, plasticizer, dispersant, and solvent.
  • the electrolyte slurry was then printed using a doctor blade method to cover the green body of the hydrogen electrode layer, forming a green body for the electrolyte layer.
  • a slurry for the reaction prevention layer was prepared by mixing GDC powder, polyvinyl alcohol, and a solvent.
  • the slurry for the reaction prevention layer was then printed on the electrolyte layer compact by the doctor blade method to form a reaction prevention layer compact.
  • the molded bodies of the hydrogen electrode layer, electrolyte layer, and reaction prevention layer arranged in sequence on the metal support were fired in air (1050°C, 1 hour) to form the hydrogen electrode layer, electrolyte layer, and reaction prevention layer.
  • a slurry for the oxygen electrode layer was prepared by mixing (La, Sr) (Co, Fe) O3 powder, polyvinyl alcohol, and a solvent.
  • the slurry for the oxygen electrode layer was then printed on the reaction prevention layer by a doctor blade method to form a compact for the oxygen electrode layer.
  • the oxygen electrode layer compact was sintered in air (1000°C, 1 hour) to form the oxygen electrode.
  • the slurry for the first region was prepared by mixing GDC powder, NiO powder, butyral resin, polymethyl methacrylate beads as a pore-forming material, a plasticizer, a dispersant, and a solvent.
  • the Ni content in the first region was changed as shown in Table 1 by adjusting the amount of NiO powder added.
  • the slurry for the first region was printed on the first main surface of the metal support by the doctor blade method to form a molded body of the first region of the hydrogen electrode layer.
  • a slurry for the third region was prepared by mixing GDC powder, NiO powder, butyral resin, polymethyl methacrylate beads as a pore-forming material, a plasticizer, a dispersant, and a solvent.
  • the Ni content in the third region was changed as shown in Table 1 by adjusting the amount of NiO powder added.
  • the slurry for the third region was printed on the molded body of the first region by the doctor blade method to form a molded body of the third region of the hydrogen electrode layer.
  • a slurry for the second region was prepared by mixing GDC powder, NiO powder, butyral resin, polymethylmethacrylate beads as a pore-forming material, a plasticizer, a dispersant, and a solvent.
  • the Ni content in the second region was changed as shown in Table 1 by adjusting the amount of NiO powder added.
  • the slurry for the second region was printed on the molded body of the third region by the doctor blade method to form a molded body of the second region of the hydrogen electrode layer.
  • one oxidation-reduction cycle was carried out in which a process of supplying a mixed gas of water vapor and hydrogen (mixing ratio 90:10) to the hydrogen electrode layer for 10 hours, a process of supplying a mixed gas of water vapor and hydrogen (mixing ratio 98:2) to the hydrogen electrode layer for 10 hours, and a process of supplying a mixed gas of water vapor and hydrogen (mixing ratio 90:10) to the hydrogen electrode layer for 10 hours were carried out.
  • Examples 1 to 9 in which the Ni content in the first region of the hydrogen electrode layer was lower than the Ni content in the third region, interfacial peeling in the initial evaluation was suppressed compared to Comparative Example 1. This result was obtained because the expansion/contraction of the first region caused by the redox cycle was reduced. Furthermore, in Examples 1 to 9, the electrolytic cell performance in the initial evaluation was improved compared to Comparative Example 2. This result was obtained because the electronic conductivity and catalytic performance in the third region were improved. In this way, Examples 1 to 9 were able to achieve both suppression of peeling and maintenance of electrode performance.
  • Electrolysis cell 10
  • Metal support 11 Through hole 12
  • First main surface 13
  • Second main surface 20
  • Cell body 6
  • Hydrogen electrode layer 61
  • First region 62
  • Second region 63
  • Third region 64
  • Fourth region 7
  • Electrolyte layer 8
  • Reaction prevention layer 9
  • Oxygen electrode layer 30
  • Flow path member 30a Flow path

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  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011036729A1 (ja) * 2009-09-28 2011-03-31 株式会社 東芝 固体酸化物型燃料電池
JP2016066616A (ja) * 2014-09-19 2016-04-28 大阪瓦斯株式会社 電気化学素子、固体酸化物形燃料電池セル、およびこれらの製造方法
WO2017014069A1 (ja) * 2015-07-17 2017-01-26 住友電気工業株式会社 燃料電池用電解質層－アノード複合部材およびその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011036729A1 (ja) * 2009-09-28 2011-03-31 株式会社 東芝 固体酸化物型燃料電池
JP2016066616A (ja) * 2014-09-19 2016-04-28 大阪瓦斯株式会社 電気化学素子、固体酸化物形燃料電池セル、およびこれらの製造方法
WO2017014069A1 (ja) * 2015-07-17 2017-01-26 住友電気工業株式会社 燃料電池用電解質層－アノード複合部材およびその製造方法

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