WO2023203875A1 - Cellule électrochimique - Google Patents

Cellule électrochimique Download PDF

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Publication number
WO2023203875A1
WO2023203875A1 PCT/JP2023/006879 JP2023006879W WO2023203875A1 WO 2023203875 A1 WO2023203875 A1 WO 2023203875A1 JP 2023006879 W JP2023006879 W JP 2023006879W WO 2023203875 A1 WO2023203875 A1 WO 2023203875A1
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electrolyte
hydrogen electrode
concentration
electrode
mol
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PCT/JP2023/006879
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English (en)
Japanese (ja)
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隆平 小原
陽平 岡田
真司 藤崎
誠 大森
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日本碍子株式会社
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Publication of WO2023203875A1 publication Critical patent/WO2023203875A1/fr

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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
    • 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
    • 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
    • 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
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to an electrochemical cell.
  • a fuel cell is known as an example of an electrochemical cell (see, for example, Patent Document 1).
  • a fuel cell includes a hydrogen electrode, an oxygen electrode, and an electrolyte disposed between the hydrogen electrode and the oxygen electrode.
  • the hydrogen electrode is composed of nickel (Ni), which primarily functions as an electron conductor, and ceria-based oxide added with a rare earth element, which primarily functions as an oxygen ion conductor.
  • An object of the present invention is to provide an electrochemical cell that can improve the electronic conductivity of a hydrogen electrode.
  • the electrochemical cell according to the present invention includes a hydrogen electrode, an oxygen electrode, and an electrolyte disposed between the hydrogen electrode and the oxygen electrode.
  • the hydrogen electrode has a first portion that is within 10 ⁇ m from the electrolyte side surface and a second portion that is more than 10 ⁇ m from the electrolyte side surface.
  • the first portion includes a solid solution of ceria-based oxide and zirconia to which a rare earth element is added, and nickel.
  • the second portion includes a ceria-based oxide to which a rare earth element is added and nickel.
  • FIG. 1 is a perspective view of a fuel cell.
  • FIG. 2 is a cross-sectional view of the fuel cell.
  • FIG. 3 is a partially enlarged view of FIG. 2.
  • FIG. 1 is a perspective view of a fuel cell 10.
  • FIG. 2 is a cross-sectional view of the fuel cell 10 taken along a gas flow path 21, which will be described later.
  • the fuel cell 10 includes a support substrate 20 and a plurality of power generation element sections 30.
  • the support substrate 20 is formed into a flat plate shape.
  • the dimension in the length direction (x-axis direction) is longer than the dimension in the width direction (y-axis direction), but the dimension in the width direction may be longer than the length direction. .
  • the support substrate 20 has a first main surface S1 and a second main surface T1.
  • the first main surface S1 and the second main surface T1 face oppositely to each other in the thickness direction (z-axis direction) of the support substrate 20.
  • the first main surface S1 and the second main surface T1 support each power generation element section 30.
  • the support substrate 20 is made of a porous material that does not have electronic conductivity.
  • the support substrate 20 is made of, for example, CSZ (calcia stabilized zirconia).
  • the support substrate 20 may be composed of NiO (nickel oxide) and YSZ (yttria stabilized zirconia), or may be composed of NiO (nickel oxide) and Y 2 O 3 (yttria).
  • the porosity of the support substrate 20 can be, for example, 20% or more and 60% or less. In this specification, porosity is the ratio of the area of the gas phase to the total area of the solid phase and gas phase in cross-sectional observation using a SEM (scanning electron microscope).
  • a plurality of gas channels 21 are formed inside the support substrate 20.
  • Each gas flow path 21 is supplied with fuel gas such as hydrogen gas.
  • each gas flow path 21 extends in the length direction (x-axis direction) within the support substrate 20.
  • Each gas flow path 21 penetrates the support substrate 20. It is preferable that each gas flow path 21 is arranged at substantially equal intervals.
  • the support substrate 20 is covered with a dense layer 22.
  • the dense layer 22 covers a region of the surface of the support substrate 20 that is not covered by each power generation element section 30 .
  • the dense layer 22 suppresses the gas diffused within the support substrate 20 from being discharged to the outside.
  • the dense layer 22 is made of, for example, CSZ (calcia-stabilized zirconia), YSZ (8YSZ) (yttria-stabilized zirconia), LSGM (lanthanum gallate), MgO (magnesium oxide) and MgAlO 4 (magnesia alumina spinel), GDC (gadolinium-doped Ceria) or LaCrO 3 (lanthanum chromite).
  • the dense layer 22 is denser than the support substrate 20.
  • the porosity of the dense layer 22 can be, for example, 0% or more and 7% or less.
  • each power generation element section 30 is supported by the first main surface S1 or the second main surface T1 of the support substrate 20.
  • the number of power generation element sections 30 arranged on the first main surface S1 and the number of power generation element sections 30 arranged on the second main surface T1 may be the same or different.
  • the sizes of the power generating element sections 30 may be the same or different.
  • the power generation element sections 30 are arranged at intervals along the length direction (x-axis direction) in which the gas flow path 21 extends.
  • the power generation element sections 30 are electrically connected in series to each other by an electrical connection section 9, which will be described later.
  • the power generation element section 30 includes a first current collecting section 1 , a hydrogen electrode 2 , an electrolyte 3 , a reaction prevention layer 4 , an oxygen electrode 5 , a second current collecting section 6 , and an interconnector 7 .
  • the first current collector 1 is arranged within the recess 23 of the support substrate 20.
  • the first current collector 1 has a first recess 11 and a second recess 12 .
  • the hydrogen electrode 2 is placed inside the first recess 11 .
  • the interconnector 7 is arranged within the second recess 12 .
  • the first current collector 1 is made of a porous material having electron conductivity.
  • the first current collector 1 can be made of, for example, NiO (nickel oxide) and Y 2 O 3 (yttria).
  • the first current collector 1 may be composed of NiO (nickel oxide) and 8YSZ (yttria stabilized zirconia), or may be composed of NiO (nickel oxide) and CSZ (calcia stabilized zirconia). Good too.
  • the porosity of the first current collector 1 can be, for example, 10% or more and 50% or less.
  • the thickness of the first current collector 1 can be, for example, 50 ⁇ m or more and 500 ⁇ m or less.
  • the hydrogen electrode 2 is placed in the first recess 11 of the first current collector 1. Fuel gas is supplied to the hydrogen electrode 2 from the gas flow path 21 via the support substrate 20 and the first current collector 1 . At the hydrogen electrode 2, an electrode reaction expressed by the following formula (1) occurs.
  • the hydrogen electrode 2 is made of a porous material that has electronic conductivity and ionic conductivity.
  • the porosity of the hydrogen electrode 2 can be, for example, 10% or more and 50% or less.
  • the thickness of the hydrogen electrode 2 can be, for example, more than 10 ⁇ m and less than 100 ⁇ m. The configuration of the hydrogen electrode 2 will be described later.
  • the electrolyte 3 is arranged to cover the hydrogen electrode 2. Both ends of the electrolyte 3 in the length direction (x-axis direction) are connected to an interconnector 7 .
  • the electrolyte 3 is made of a dense material that has ionic conductivity and no electronic conductivity.
  • the porosity of the electrolyte 3 can be, for example, 0% or more and 7% or less.
  • the thickness of the electrolyte 3 can be, for example, 3 ⁇ m or more and 50 ⁇ m or less. The structure of the electrolyte 3 will be described later.
  • Reaction prevention layer 4 is arranged between electrolyte 3 and oxygen electrode 5.
  • the reaction prevention layer 4 is in contact with the electrolyte 3 and the oxygen electrode 5, respectively.
  • the reaction prevention layer 4 is arranged at a position corresponding to the hydrogen electrode 2 with the electrolyte 3 interposed therebetween.
  • the reaction prevention layer 4 is provided to prevent the constituent materials of the electrolyte 3 and the constituent materials of the oxygen electrode 5 from reacting to form a reaction layer with high electrical resistance.
  • the reaction prevention layer 4 can be made of an ion conductive material.
  • the porosity of the reaction prevention layer 4 can be, for example, 0.1% or more and 50% or less.
  • the thickness of the reaction prevention layer 4 can be, for example, 1 ⁇ m or more and 50 ⁇ m or less.
  • the oxygen electrode 5 is placed on the reaction prevention layer 4.
  • Oxygen-containing gas for example, air
  • Oxygen-containing gas for example, air
  • an electrode reaction expressed by the following equation (2) occurs.
  • the oxygen electrode 5 is made of a porous material having electronic conductivity.
  • the porosity of the oxygen electrode 5 can be, for example, 10% or more and 50% or less.
  • the thickness of the oxygen electrode 5 can be, for example, 10 ⁇ m or more and 100 ⁇ m or less.
  • the second current collector 6 is connected to the oxygen electrode 5 and the interconnector 7.
  • the second current collector 6 is made of a porous material having electron conductivity.
  • the second current collector 6 may or may not have oxygen ion conductivity.
  • the second current collector 6 can be made of, for example, LSCF, LSC, Ag (silver), Ag-Pd (silver-palladium alloy), or the like.
  • the porosity of the second current collector 6 can be, for example, 25% or more and 50% or less.
  • the thickness of the second current collector 6 can be, for example, 50 ⁇ m or more and 500 ⁇ m or less.
  • the interconnector 7 is arranged within the second recess 12 of the first current collector 1 . Both ends of the interconnector 7 in the length direction (x-axis direction) are connected to the electrolyte 3 .
  • the interconnector 7 is made of a dense material that has electronic conductivity.
  • the interconnector 7 can be made of, for example, LaCrO 3 (lanthanum chromite), (Sr,La)TiO 3 (strontium titanate), or the like.
  • the porosity of the interconnector 7 can be, for example, 0% or more and 7% or less.
  • the thickness of the interconnector 7 can be, for example, 10 ⁇ m or more and 100 ⁇ m or less.
  • FIG. 3 is a partially enlarged view of FIG. 2.
  • the hydrogen electrode 2 has a first portion 101 and a second portion 102.
  • the first portion 101 is a region of the hydrogen electrode 2 on the electrolyte 3 side. Specifically, the first portion 101 is a region within 10 ⁇ m from the electrolyte side surface S2 of the hydrogen electrode 2. Therefore, the thickness of the first portion 101 is 10 ⁇ m.
  • the first part 101 is connected to the electrolyte 3.
  • the electrolyte side surface S2 of the hydrogen electrode 2 is in direct contact with the hydrogen electrode side surface S3 of the electrolyte 3.
  • the interface between the hydrogen electrode 2 and the electrolyte 3 (that is, the electrolyte side surface S2 of the hydrogen electrode 2 and the hydrogen electrode side surface S3 of the electrolyte 3) is defined as follows.
  • the interface between the reaction prevention layer 4 and the oxygen electrode 5 is identified by classifying the brightness of a cross-sectional SEM image parallel to the thickness direction (z-axis direction in FIG. 3) into 256 gradations.
  • a line having the same shape as the interface between the reaction prevention layer 4 and the oxygen electrode 5 (hereinafter referred to as the "reference line") is translated in parallel toward the hydrogen electrode 2 side.
  • the reference line is stopped at a position where it comes into contact with nickel (Ni) contained in the hydrogen electrode 2 for the first time.
  • the reference line at this time is the interface between the hydrogen electrode 2 and the electrolyte 3.
  • the first portion 101 includes a solid solution of ceria-based oxide and ZrO 2 (zirconia) to which a rare earth element is added, and Ni.
  • a solid solution of ceria-based oxide and zirconia to which a rare earth element is added has both ionic conductivity derived from the ceria-based oxide and electronic conductivity derived from ZrO 2 .
  • the three-phase interface (reaction field) can be increased. Reaction resistance can be reduced.
  • a solid solution is one in which a ceria-based oxide to which a rare earth element is added and ZrO 2 are dissolved together to form a uniform solid phase.
  • ceria-based oxides doped with rare earth elements include, but are not limited to, gadolinium-doped ceria (GDC), samarium-doped ceria (SDC), and yttrium-doped ceria (YDC).
  • the Ce (cerium) concentration in the first portion 101 can be 8.0 mol% or more and 30 mol% or less.
  • the rare earth element concentration in the first portion 101 can be 0.5 mol% or more and 10 mol% or less.
  • the Zr (zirconium) concentration in the first portion 101 can be 1.0 mol% or more and 20 mol% or less.
  • the Zr concentration in the first portion 101 is particularly preferably 5.0 mol% or more and 15 mol% or less. In the first portion 101, the Zr concentration may be lower than the Ce concentration.
  • the Ni concentration in the first portion 101 can be 12 mol% or more and 50 mol% or less.
  • the second portion 102 is a region of the hydrogen electrode 2 on the side opposite to the electrolyte 3. Specifically, the second portion 102 is a region of the hydrogen electrode 2 that is more than 10 ⁇ m from the electrolyte side surface S2. That is, the second portion 102 is a region of the hydrogen electrode 2 excluding the first portion 101. The second portion 102 is integrally formed with the first portion 101. The second portion 102 is connected to the first current collector 1 .
  • the second portion 102 includes a ceria-based oxide added with a rare earth element and Ni.
  • ceria-based oxides doped with rare earth elements include, but are not limited to, GDC, SDC, and YDC.
  • the rare earth element-added ceria-based oxide contained in the second portion 102 is preferably the same as the rare-earth element-added ceria-based oxide contained in the second portion 102, but may be different.
  • the Ce concentration in the second portion 102 can be 10 mol% or more and 35 mol% or less.
  • the rare earth element concentration in the second portion 102 can be 1.0 mol% or more and 15 mol% or less.
  • the Ni concentration in the second portion 102 can be 12 mol% or more and 50 mol% or less.
  • the second portion 102 preferably includes ZrO 2 forming a solid solution with a ceria-based oxide to which a rare earth element is added.
  • the Zr concentration in the second portion 102 can be 0.0 mol% or more and 15 mol% or less.
  • the Zr concentration in the first portion 101 is preferably higher than the Zr concentration in the second portion 102 .
  • the three-phase interface in the first portion 101 can be further increased, so that the reaction resistance of the hydrogen electrode 2 can be further reduced.
  • the Ce concentration, rare earth element concentration, Zr concentration, and Ni concentration in the first portion 101 and the second portion 102 are obtained by line analysis using an atomic concentration profile, that is, elemental mapping using an EPMA (Electron Probe Micro Analyzer). Specifically, concentration distribution data of each element is obtained by performing line analysis in the z-axis direction using EPMA in a cross section along the thickness direction (z-axis direction in FIG. 3). Note that EPMA is a concept that includes EDS (Energy Dispersive x-ray Spectroscopy).
  • the electrolyte 3 As shown in FIG. 3, the electrolyte 3 has a third portion 103 and a fourth portion 104.
  • the third portion 103 is a region of the electrolyte 3 on the hydrogen electrode 2 side. Specifically, the third portion 103 is a region within 3 ⁇ m from the hydrogen electrode side surface S3 of the electrolyte 3. Therefore, the thickness of the third portion 103 is 3 ⁇ m.
  • the third portion 103 is connected to the hydrogen electrode 2 .
  • the hydrogen electrode side surface S3 of the electrolyte 3 is in direct contact with the electrolyte side surface S2 of the hydrogen electrode 2.
  • the fourth portion 104 is a region of the electrolyte 3 on the side opposite to the hydrogen electrode 2. Specifically, the fourth portion 104 is a region of the electrolyte 3 that is more than 3 ⁇ m from the hydrogen electrode side surface S3. That is, the fourth portion 104 is a region of the electrolyte 3 excluding the third portion 103. The fourth portion 104 is integrally formed with the third portion 103. In this embodiment, the fourth portion 104 is connected to the reaction prevention layer 4 .
  • the third portion 103 and the fourth portion 104 each contain YSZ (yttria stabilized zirconia).
  • the Y (yttrium) concentration in the third portion 103 is preferably higher than the yttrium concentration in the fourth portion 104. This makes it possible to improve the ionic conductivity of the region of the electrolyte 3 that is connected to the hydrogen electrode 2, thereby reducing the resistance overvoltage associated with ionic conduction. Furthermore, by improving the ionic conductivity of the three-phase interface in the vicinity of the electrolyte 3 in the hydrogen electrode 2, the reaction overvoltage of the hydrogen electrode 2 can be reduced.
  • each of the third portion 103 and the fourth portion 104 contain YSZ as a main component.
  • containing YSZ as a main component means that the content of YSZ is 70 mol% or more.
  • the Y concentration in the third portion 103 can be 3.0 mol% or more and 8.0 mol% or less.
  • the Y concentration in the third portion 103 is particularly preferably 4.5 mol% or more and 7.0 mol% or less.
  • the Y concentration in the fourth portion 104 can be 2.0 mol% or more and 7.0 mol% or less.
  • the Y concentration in each of the third portion 103 and the fourth portion 104 can be adjusted by using a YSZ raw material containing a desired Y concentration.
  • the Zr concentration and Y concentration in the third portion 103 and the fourth portion 104 are obtained by line analysis using the atomic concentration profile described above.
  • a so-called horizontal striped fuel cell was described as an example of a fuel cell, but the electrochemical cell is not limited to this.
  • the present invention is applicable to an electrochemical cell in which a hydrogen electrode and an oxygen electrode are arranged on both sides of an electrolyte layer.
  • An electrochemical cell consists of an element with a pair of electrodes arranged so that an electromotive force is generated from the overall redox reaction, and an element that converts chemical energy into electrical energy. It is a generic term.
  • electrochemical cells include vertical striped fuel cells, flat plate fuel cells, cylindrical fuel cells, and hydrogen generation cells that utilize the electrolysis reaction of water.
  • An example is an electrolytic cell that performs this.
  • O 2 - (oxygen ions) are used as carriers, but OH - (hydroxide ions) or protons may be used as carriers.
  • a fuel cell of a comparative example was produced in the following manner.
  • 10 power generation element parts were formed on each main surface of the support substrate.
  • a slurry for forming a support substrate was prepared by mixing MgO powder, Y 2 O 3 powder, binder, pore-forming material, and dispersion material in a ball mill.
  • a molded body of a support substrate was created by extrusion molding and cutting the slurry for forming a support substrate.
  • a slurry for the first current collector was prepared by mixing NiO powder, Y 2 O 3 powder, binder, pore-forming material, and dispersion material in a ball mill. This slurry for the first current collector was applied by screen printing into the first recess of the molded body of the support substrate to form the molded body of the first current collector.
  • a slurry for a hydrogen electrode was prepared by mixing NiO powder, YSZ powder, binder, pore-forming material, and dispersing material in a ball mill. This hydrogen electrode slurry was applied to the second recess of the first current collector by screen printing to form a hydrogen electrode molded body.
  • a slurry for an interconnector was prepared by adding LaCrO 3 powder and a binder and mixing in a ball mill. This interconnector slurry was applied to the third recess of the first current collector by screen printing to form a molded interconnector.
  • an electrolyte slurry was prepared by mixing the YSZ powder and the binder in a ball mill. This electrolyte slurry was applied to cover the supporting substrate by screen printing to form an electrolyte molded body.
  • reaction prevention layer slurry was prepared by mixing the GDC powder and the binder in a ball mill. This reaction prevention layer slurry was applied onto the electrolyte molded body by screen printing to form a reaction prevention film molded body.
  • the laminate of each molded body was co-fired (1300°C, 5 hours) to produce a co-fired body of the support substrate, first current collector, hydrogen electrode, interconnector, electrolyte, and reaction prevention layer. .
  • a slurry for an oxygen electrode was prepared by mixing the LSCF powder, binder, pore forming material, and dispersing material in a ball mill. This oxygen electrode slurry was applied onto the reaction prevention film by screen printing to form a molded oxygen electrode.
  • a slurry for the second current collector was prepared by mixing the LSCF powder, binder, pore-forming material, and dispersing material in a ball mill. This slurry for forming a second current collector was applied from the oxygen electrode to the interconnector by a screen printing method to form a molded body of the second current collector.
  • Example 1 to 4 Fuel cells of Examples 1 to 4 were produced in the same steps as in the comparative example except that the hydrogen electrode had a two-layer structure.
  • a slurry for the first portion was prepared by mixing NiO powder, YSZ powder, ZrO 2 powder, binder, pore-forming material, and dispersion material in a ball mill.
  • the Zr concentration in the first portion of the hydrogen electrode was adjusted as shown in Table 1 by changing the amount of ZrO 2 powder added for each example.
  • the slurry for the first portion was applied into the second recess of the first current collector by screen printing to form a molded body of the first portion of the hydrogen electrode.
  • a slurry for the second portion was prepared by mixing NiO powder, YSZ powder, binder, pore-forming material, and dispersing material in a ball mill. Then, the slurry for the second part was applied onto the molded body of the first part by a screen printing method to form a molded body of the second part of the hydrogen electrode.
  • Example 5 to 8 Fuel cells of Examples 5 to 8 were produced in the same steps as Examples 1 to 4 except that the electrolyte had a two-layer structure.
  • a slurry for the third portion was prepared by mixing YSZ powder and a binder in a ball mill.
  • the Y concentration in the third portion of the electrolyte was adjusted as shown in Table 1 by changing the Y concentration contained in the YSZ powder for each example.
  • the slurry for the third portion was applied by screen printing so as to cover the support substrate, thereby forming a molded body of the third portion of the electrolyte.
  • a slurry for the fourth portion was prepared by mixing the YSZ powder and the binder in a ball mill. At this time, by adjusting the Y concentration contained in the YSZ powder, as shown in Table 1, the Y concentration in the fourth part of Examples 5 to 8 was made the same as the Y concentration in the electrolyte of the comparative example. Then, the slurry for the fourth part was applied onto the molded body of the third part by a screen printing method to form a molded body of the fourth part of the electrolyte.
  • Example 9 Fuel cells of Examples 9 and 10 were produced in the same steps as Examples 5 to 8 except that ZrO 2 was also added to the second portion of the hydrogen electrode.
  • a slurry for the second portion was prepared by mixing NiO powder, YSZ powder, ZrO 2 powder, binder, pore-forming material, and dispersion material in a ball mill.
  • the Zr concentration in the second portion of the hydrogen electrode was adjusted as shown in Table 1 by changing the amount of ZrO 2 powder added for each example.
  • the slurry for the second part was applied onto the molded body of the first part of the hydrogen electrode by a screen printing method to form a molded body of the second part of the hydrogen electrode.
  • Example 11 A fuel cell of Example 11 was produced in the same process as Example 3 except that ZrO 2 was also added to the second portion of the hydrogen electrode.
  • a slurry for the second portion was prepared by mixing NiO powder, YSZ powder, ZrO 2 powder, binder, pore-forming material, and dispersion material in a ball mill. At this time, by adjusting the amount of ZrO 2 powder added, the Zr concentration in the second part of the hydrogen electrode was made the same as the Zr concentration in the first part, as shown in Table 1. Then, the slurry for the second part was applied onto the molded body of the first part of the hydrogen electrode by a screen printing method to form a molded body of the second part of the hydrogen electrode.
  • Reaction overvoltage suppression rate (%) of each example 100 ⁇ ((reaction overvoltage of comparative example) - (reaction overvoltage of each example)) / (reaction overvoltage of comparative example)... (3)
  • Table 1 shows the calculated reaction overvoltage suppression rate values and their evaluations. In Table 1, when the reaction overvoltage suppression rate is 25% or more, it is evaluated as "A”, when it is 20% or more and less than 25%, it is evaluated as "B", and when it is 10% or more and less than 20%, it is evaluated as "B”. The case where it was less than 10% was evaluated as "C”, and the case where it was less than 10% was evaluated as "D”.
  • Heat cycle test While maintaining a reducing atmosphere by supplying a mixed gas of Ar and hydrogen (hydrogen: 4% to Ar) to the hydrogen electrode, the temperature was raised from room temperature to 750°C in 2 hours, and then cooled down to room temperature in 4 hours. This step was repeated 10 times as one cycle.
  • the initial performance is improved compared to the comparative example. I was able to do it. This result was obtained because the three-phase interface (reaction field) could be increased in the first part.
  • the existence of the ceria - based oxide containing rare earth elements and a solid solution of ZrO 2 in the first part was confirmed by elemental mapping by area analysis using EDX (energy dispersive X-ray spectrometer). was confirmed by being observed at the same position.
  • Example 1 to 4 in Examples 2 and 3 in which the zirconium concentration in the first portion was 5.0 mol% or more and 15 mol% or less, the initial performance could be further improved.
  • the durability in the thermal cycle test is improved compared to the comparative example. I was able to do that. This result was obtained because the addition of ZrO 2 strengthened the ceria-based oxide skeleton in the second portion.
  • the existence of the rare earth element-doped ceria-based oxide and ZrO 2 solid solution in the second part is confirmed by the fact that Zr and CeO 2 are observed at the same position in elemental mapping by area analysis using EDX. confirmed.
  • Example 10 in which the zirconium concentration in the first part was higher than that in the second part among Examples 9 and 10, the initial performance was able to be further improved compared to Example 9. This result was obtained because the three-phase interface in the first portion could be further increased.
  • Example 5 to 10 in which the electrolyte has a two-layer structure and the Y concentration in the third part is higher than that in the fourth part, the initial performance is further improved compared to Examples 1 to 4, and 11. I was able to do that. These results were obtained by improving the ionic conductivity of the third part of the electrolyte connected to the hydrogen electrode, and by improving the ionic conductivity of the three-phase interface near the electrolyte in the hydrogen electrode. This is because it was done.
  • Fuel cell 20 Support substrate 30 Power generation element section 1 First current collector 2 Hydrogen electrode 101 First section 102 Second section 3 Electrolyte 103 Third section 104 Fourth section 4 Reaction prevention layer 5 Oxygen electrode 6 Second current collector Part 7 Interconnector

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Abstract

Une cellule électrochimique de batterie (10) comprend une électrode à hydrogène (2), une électrode à oxygène (5) et un électrolyte (3). L'électrode à hydrogène (2) a une première partie (101) qui se trouve à moins de 10 µm d'une surface côté électrolyte (S2), et une seconde partie (102) qui se trouve à plus de 10 µm de la surface côté électrolyte (S2). La première partie (101) comprend une solution solide de zircone et un oxyde de cérium auquel un élément de terres rares est ajouté, et du nickel. La seconde partie (102) comprend un oxyde de cérium auquel un élément de terres rares est ajouté, et du nickel.
PCT/JP2023/006879 2022-04-18 2023-02-24 Cellule électrochimique WO2023203875A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0757746A (ja) * 1993-08-06 1995-03-03 Fujikura Ltd 固体電解質型燃料電池の電極構造
JPH08213029A (ja) * 1995-02-06 1996-08-20 Fujikura Ltd 固体電解質型燃料電池の燃料電極
JP2004362913A (ja) * 2003-06-04 2004-12-24 Nissan Motor Co Ltd 固体酸化物形燃料電池用電解質及びその製造方法
JP2010027457A (ja) * 2008-07-22 2010-02-04 Mitsubishi Heavy Ind Ltd 固体電解質型燃料電池の発電膜及びこれを備えた固体電解質型燃料電池、並びに固体電解質型燃料電池の発電膜の製造方法
JP2013101907A (ja) * 2011-10-14 2013-05-23 Ngk Insulators Ltd 燃料電池セル

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0757746A (ja) * 1993-08-06 1995-03-03 Fujikura Ltd 固体電解質型燃料電池の電極構造
JPH08213029A (ja) * 1995-02-06 1996-08-20 Fujikura Ltd 固体電解質型燃料電池の燃料電極
JP2004362913A (ja) * 2003-06-04 2004-12-24 Nissan Motor Co Ltd 固体酸化物形燃料電池用電解質及びその製造方法
JP2010027457A (ja) * 2008-07-22 2010-02-04 Mitsubishi Heavy Ind Ltd 固体電解質型燃料電池の発電膜及びこれを備えた固体電解質型燃料電池、並びに固体電解質型燃料電池の発電膜の製造方法
JP2013101907A (ja) * 2011-10-14 2013-05-23 Ngk Insulators Ltd 燃料電池セル

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