WO2024014454A1 - Cellule d'électrolyse à oxyde solide et système de cellule d'électrolyse à oxyde solide - Google Patents

Cellule d'électrolyse à oxyde solide et système de cellule d'électrolyse à oxyde solide Download PDF

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WO2024014454A1
WO2024014454A1 PCT/JP2023/025575 JP2023025575W WO2024014454A1 WO 2024014454 A1 WO2024014454 A1 WO 2024014454A1 JP 2023025575 W JP2023025575 W JP 2023025575W WO 2024014454 A1 WO2024014454 A1 WO 2024014454A1
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compound
metal
solid oxide
fuel electrode
oxide
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Japanese (ja)
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ハルディヤント 栗田
洋史 加賀
喜丈 戸田
秀雄 上杉
暁 留野
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Ａｇｃ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/23—Carbon monoxide or syngas
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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 a solid oxide electrolytic cell and a solid oxide electrolytic cell system.
  • SOEC solid oxide electrolysis cells
  • the basic unit is a cell (single cell) that has two electrodes (oxygen electrode and fuel electrode) and a solid electrolyte layer placed between the two electrodes.
  • a SOEC system is constructed by modularizing a multi-stack that is a combination of a plurality of these cell stacks.
  • Patent Document 1 a cerium-based composite oxide layer called an intermediate layer is arranged between an electrolyte layer and each electrode, and a multilayer structure of a catalyst layer and a current collecting layer is used as an oxygen electrode. It is proposed to do so.
  • the present invention has been made in view of this background, and an object of the present invention is to provide a SOEC that can suppress changes in operating voltage compared to conventional ones. Another object of the present invention is to provide a SOEC system including such a SOEC.
  • the present invention provides a solid oxide electrolysis cell having a fuel electrode, an oxygen electrode, and a solid electrolyte layer between the fuel electrode and the oxygen electrode, further comprising an intermediate layer between the solid electrolyte layer and the fuel electrode, the intermediate layer comprising cerium oxide;
  • the fuel electrode includes a metal or a metal oxide and a compound A, The ratio of the metal or the oxide of the metal to the entire fuel electrode is in the range of 40 vol% to 80 vol% in terms of metal volume ratio,
  • the metal includes at least one selected from the group consisting of nickel (Ni), copper (Cu), silver (Ag), tungsten (W), platinum (Pt), iron (Fe), and tin (Sn). including,
  • a solid oxide type electrolytic cell is provided in which the compound A includes a mayenite type compound and/or a perovskite type compound containing an alkaline earth metal element.
  • the present invention provides a solid oxide electrolytic cell system, comprising: a module comprising a plurality of solid oxide electrolytic cell stacks, each solid oxide electrolytic cell being a solid oxide electrolytic cell having the characteristics described above; a power supply device that supplies power to the module; a gas supply device that supplies water vapor and/or carbon dioxide to the module; a gas separation device that separates hydrogen and/or carbon monoxide generated from the module; a storage device that stores the hydrogen and/or carbon monoxide separated by the gas separation device;
  • a solid oxide electrolytic cell system is provided having the following.
  • the present invention provides a solid oxide electrolysis cell having a fuel electrode, an oxygen electrode, and a solid electrolyte layer between the fuel electrode and the oxygen electrode, further comprising an intermediate layer between the solid electrolyte layer and the fuel electrode, the intermediate layer comprising cerium oxide;
  • the fuel electrode includes a metal or a metal oxide and a compound A, The ratio of the metal or the oxide of the metal to the entire fuel electrode is in the range of 40 vol% to 80 vol% in terms of metal volume ratio,
  • the metal includes at least one selected from the group consisting of nickel (Ni), copper (Cu), silver (Ag), tungsten (W), platinum (Pt), iron (Fe), and tin (Sn).
  • the compound A contains an oxide containing an alkaline earth metal element and/or a rare earth element other than Sc and Y, and the ratio of the alkaline earth metal element and/or rare earth element other than Sc and Y to the metal is molar.
  • a solid oxide type electrolytic cell is provided in which the ratio is 1.0% or more.
  • the present invention it is possible to provide a SOEC that can suppress changes in operating voltage compared to conventional ones. Furthermore, the present invention can provide a SOEC system including such a SOEC.
  • 1 is a cross-sectional view schematically showing an example of the configuration of a SOEC according to an embodiment of the present invention.
  • 1 is a diagram schematically showing an example of the configuration of a system including a SOEC module according to an embodiment of the present invention.
  • 1 is a flow diagram schematically showing an example of a method for manufacturing a SOEC according to an embodiment of the present invention.
  • 1 is a graph showing changes over time in electrolysis voltage measured in a SOEC according to an embodiment of the present invention (cell 1) and a conventional SOEC (cell 21).
  • a solid oxide electrolytic cell in one embodiment, includes a fuel electrode, an oxygen electrode, and a solid electrolyte layer between the fuel electrode and the oxygen electrode, further comprising an intermediate layer between the solid electrolyte layer and the fuel electrode, the intermediate layer comprising cerium oxide;
  • the fuel electrode includes a metal or a metal oxide and a compound A, The ratio of the metal or the oxide of the metal to the entire fuel electrode is in the range of 40 vol% to 80 vol% in terms of metal volume ratio,
  • the metal includes at least one selected from the group consisting of nickel (Ni), copper (Cu), silver (Ag), tungsten (W), platinum (Pt), iron (Fe), and tin (Sn).
  • a solid oxide type electrolytic cell is provided in which the compound A includes a mayenite type compound and/or a perovskite type compound containing an alkaline earth metal element.
  • a mayenite type compound has a C12A7 (12CaO.7Al 2 O 3 ) type crystal structure, and means a substance with a characteristic crystal structure having three-dimensionally connected cavities (cages). .
  • the skeleton that constitutes the cage of the mayenite-type compound is positively charged and includes 12 cage structures per unit cell.
  • 1/6 of this cage contains oxide ions inside to satisfy the electrical neutrality condition of the crystal.
  • the oxide ions in this cage are particularly called free oxide ions because they are chemically bonded more loosely than other oxide ions constituting the crystal skeleton.
  • Representative materials of the mayenite type compound are, for example, 12CaO.7Al 2 O 3 , 12SrO.7Al 2 O 3 , and 12MgO.7Al 2 O 3 . However, in these materials, some of the cations (Ca, Al, Sr, and Mg) may be replaced with other cations.
  • ⁇ -based mayenite-type compounds materials in which some of such cations are replaced with other cations are referred to as " ⁇ -based mayenite-type compounds.”
  • a material in which some of the Ca and/or Al sites are replaced with different cations is called a "12CaO.7Al 2 O 3 -based mayenite-type compound.”
  • a material in which some of the Sr and/or Al sites are replaced with different cations is called a "12SrO.7Al 2 O 3 -based mayenite-type compound”.
  • the fuel electrode includes compound A, that is, a mayenite-type compound and/or a perovskite-type compound containing an alkaline earth metal element, in addition to a metal or a metal oxide.
  • Such a compound A has a strong affinity for CO2 . Therefore, during the electrolytic treatment of SOEC according to an embodiment of the present invention, the reactive gas CO 2 is strongly adsorbed on the compound A. Therefore, during the reduction reaction at the fuel electrode, electrons are smoothly supplied to CO 2 at the three-phase interface between the metal and compound A (the reaction field where the reaction gas, electrons, and ions meet).
  • the fuel electrode contains, in addition to the metal or the oxide of the metal, an oxide containing compound A, that is, an alkaline earth metal element and/or a rare earth element other than Sc and Y.
  • the ratio of alkaline earth metal elements and/or rare earth elements excluding Sc and Y to the metal is 1.0% or more in terms of molar ratio.
  • Such a compound A has a strong affinity for CO2 . Therefore, during the electrolytic treatment of SOEC according to an embodiment of the present invention, the reactive gas CO 2 is strongly adsorbed on the compound A. Therefore, electrons are smoothly supplied to CO 2 during the reduction reaction at the fuel electrode.
  • compound A does not need to have oxide ion conductivity.
  • electrolysis proceeds at a three-phase interface formed by the gas phase, the metal contained in the fuel electrode, and the cerium oxide as an intermediate layer.
  • Compound A existing near the three-phase interface adsorbs and activates CO 2 , and electrons are smoothly supplied to CO 2 .
  • current flows more easily, and deterioration of the reaction field due to this is suppressed.
  • FIG. 1 schematically shows a configuration example of a SOEC according to an embodiment of the present invention.
  • a SOEC (hereinafter referred to as "first cell") 100 includes a fuel electrode 110, an oxygen electrode 120, and a space between the fuel electrode 110 and the oxygen electrode 120. and a solid electrolyte layer 130 disposed in the solid electrolyte layer 130 .
  • the first cell 100 also has a first intermediate layer 150 between the fuel electrode 110 and the solid electrolyte layer 130, and a second intermediate layer between the oxygen electrode 120 and the solid electrolyte layer 130. It has 160.
  • the first intermediate layer 150 and the second intermediate layer 160 are provided to suppress solid phase reactions between the respective electrodes 110 and 120 and the solid electrolyte layer 130.
  • a more suitable three-phase interface is formed by the intermediate layer 150, the metal (for example, Ni) contained in the fuel electrode 110, and the gas phase, and the fuel electrode 110 is Electrolysis proceeds even if it is not included.
  • the second intermediate layer 160 may be omitted.
  • the fuel electrode 110 includes a metal or a metal oxide and a compound A.
  • compound A includes a mayenite type compound and/or a CaTiO 3 -based perovskite type compound.
  • the fuel electrode 110 has the role of electrolyzing water vapor and/or carbon dioxide at an operating temperature.
  • the fuel electrode 110 includes metal and compound A.
  • the fuel electrode 110 may be composed of a binder resin such as a green sheet, a powder of compound A, and a powder of a metal or a metal compound, and is a substrate formed by sintering these powders. Good too. If it is a substrate, it can be used as a fuel electrode support type SOEC using the substrate as a support. Further, the fuel electrode may be laminated on a porous support made of metal, ceramics, or a composite thereof.
  • the metal includes at least one selected from the group consisting of nickel (Ni), copper (Cu), silver (Ag), tungsten (W), platinum (Pt), iron (Fe), and tin (Sn). .
  • the metal is contained in a volume ratio of 40 vol % to 80 vol % in the entire fuel electrode 110 in terms of metal.
  • the metal may be provided in a metal oxide state as well as a metal state. This is because during the electrolysis of the first SOEC 100, the metal oxide is reduced to a metallic state.
  • the oxide is contained in a volume ratio of 40 vol % to 80 vol % based on the metal equivalent of the entire fuel electrode 110 .
  • the compound A contained in the fuel electrode 110 includes a mayenite type compound and/or a CaTiO 3 -based perovskite type compound.
  • the mayenite-type compound is a 12CaO.7Al2O3 - based mayenite-type compound, a 12SrO.7Al2O3 - based mayenite-type compound, or a 12MgO.7Al2O3 -based mayenite- type compound. There may be.
  • compound A when compound A contains a mayenite type compound, compound A may further contain another compound B.
  • Such other compounds B include lithium (Li), sodium (Na), potassium (K), barium (Ba), magnesium (Mg), strontium (Sr), titanium (Ti), yttrium (Y), cerium (Ce), lanthanum (La), and neodymium (Nd).
  • a part of element X may be introduced into the lattice sites of the mayenite-type compound.
  • Element X may be contained in the range of 0.1 mol% to 30 mol% in terms of oxide based on the entire compound A.
  • the perovskite type compound is not particularly limited . ) (here, 0 ⁇ x ⁇ 1), lanthanum-strontium-gallium-based oxide (La 1-x Sr x GaO 3 ) (here, 0 ⁇ x ⁇ 1), lanthanum-barium-gallium-based oxide ( In addition to La 1-x Bax GaO 3 ) (where 0 ⁇ x ⁇ 1) and solid solutions and/or mixtures based thereon, compounds that function as electrolytes can be applied.
  • CaTiO 3 , SrTiO 3 , BaTiO 3 , and solid solutions and/or mixtures based on these are preferred, and CaTiO 3 and solid solutions and/or mixtures based on these are particularly preferred.
  • the perovskite compound is CaTiO 3
  • a portion of Ca and/or Ti sites may be each substituted with another cation.
  • some Ti sites may be replaced with Al.
  • compound A may further contain another compound C.
  • Such another compound C may include a compound of aluminum (Al).
  • Al may be contained in the range of 0.1 mol % to 30 mol % based on the entire compound A in terms of oxide.
  • the compound A contained in the fuel electrode 110 may further include a cerium-based oxide.
  • cerium-based oxides include cerium oxide, cerium oxide doped with rare earth elements such as gadolinium (Gd) or samarium (Sm), and alkaline earth metal elements.
  • the doping amount of rare earth elements such as gadolinium or samarium or alkaline earth metal elements is, for example, in the range of 0 to 20 mol %.
  • the compound A may include an oxide containing an alkaline earth metal element and/or a rare earth element other than Sc and Y.
  • the ratio of the alkaline earth metal element and/or the rare earth element other than Sc and Y to the metal is 1.0% or more in terms of molar ratio.
  • the compound A preferably contains an alkaline earth metal element, more preferably contains Al, and is particularly preferably a mayenite type compound.
  • the oxygen electrode 120 is made of a material that can remove electrons from oxide ions and generate gaseous oxygen molecules.
  • the oxygen electrode 120 is made of lanthanum-strontium-cobalt-based oxide (La 1-x Sr x CoO 3 ) (where 0 ⁇ x ⁇ 1), lanthanum-strontium-cobalt-iron-based oxide (La 1- x Sr x Co 1-y Fe y O 3 ) (here, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), lanthanum-strontium-manganese oxide (La 1-x Sr x MnO 3 ) (here, , 0 ⁇ x ⁇ 1), ceria-based oxides, and mixtures thereof.
  • La 1-x Sr x CoO 3 lanthanum-strontium-cobalt-based oxide
  • La 1- x Sr x Co 1-y Fe y O 3 lanthanum-strontium-manganese oxide
  • La 1-x Sr x MnO 3 lanthanum-strontium-manganese oxide
  • a perovskite oxide containing two or more elements selected from the group consisting of La, Sr, Co, Fe, and Mn In the case of a fuel electrode supporting type, after forming the solid electrolyte layer, a paste containing powder for the oxygen electrode may be applied and fired to form the oxygen electrode. In the case of a solid electrolyte layer supporting type, the oxygen electrode may be formed by applying a paste containing powder for an oxygen electrode onto the solid electrolyte substrate and baking the paste. A ceria-based electrolyte may be formed as a reaction prevention layer between the solid electrolyte layer and the oxygen electrode.
  • Solid electrolyte layer 130 The solid electrolyte layer 130 is made of a material that has oxide ion conductivity at operating temperatures.
  • solid electrolyte layer 130 conventionally known materials may be used.
  • YSZ yttria-stabilized zirconia
  • ScSZ scandia-stabilized zirconia
  • La 1-x Sr x Ga 1-y Fe y O 3 lanthanum-strontium-gallium-magnesium oxide
  • any material other than the above compounds can be used as long as it has oxide ion conductivity.
  • First intermediate layer 150 is arranged between fuel electrode 110 and solid electrolyte layer 130. Further, the second intermediate layer 160 is arranged between the oxygen electrode 120 and the solid electrolyte layer 130.
  • the solid phase reaction between the fuel electrode 110 and the solid electrolyte layer 130 can be suppressed, and deterioration of the solid electrolyte layer 130 and the fuel electrode 110 can be prevented.
  • the first and second intermediate layers 150 and 160 are made of, for example, an oxide containing cerium. Oxides containing cerium are preferred because they have excellent ionic conductivity.
  • the cerium-containing oxide may be, for example, cerium oxide doped with a rare earth element such as gadolinium (Gd) or samarium (Sm), or an alkaline earth metal element.
  • a rare earth element such as gadolinium (Gd) or samarium (Sm)
  • the doping amount of rare earth elements such as Gd or samarium or alkaline earth metal elements is, for example, in the range of 0 to 20 mol %.
  • the SOEC according to an embodiment of the present invention may be of any type, such as an electrolyte layer supported type, a fuel electrode supported type, or a porous substrate supported type.
  • SOEC system A SOEC according to an embodiment of the present invention is used as an SOEC system including a stack configured by laminating a plurality of SOECs and a module combining a plurality of these stacks.
  • FIG. 2 schematically shows an example of the configuration of such a SOEC system.
  • the SOEC system 201 includes a SOEC module 210, a power supply device 220, a gas supply device 230, a gas separation device 240, and a storage device 250.
  • the SOEC module 210 is constructed by stacking multiple SOECs in series.
  • the power supply device 220 has a role of supplying necessary power to the SOEC module 210.
  • the gas supply device 230 has the role of supplying a reactive gas such as water vapor and/or carbon dioxide to the SOEC module 210.
  • the gas separation device 240 has a role of separating the generated gas generated in the SOEC module 210.
  • the storage device 250 has a role of storing hydrogen and/or carbon monoxide separated by the gas separation device 240.
  • the SOEC module 210 When the SOEC system 201 is in operation, the SOEC module 210 is heated to the operating temperature by power from the power supply device 220.
  • the operating temperature is 700°C or higher, for example in the range of 700°C to 900°C.
  • a reaction gas is supplied from the gas supply device 230 to the high temperature SOEC module 210.
  • the reaction gas includes water vapor and/or carbon dioxide.
  • the reaction gas is supplied to the fuel electrode side of each SOEC that constitutes the SOEC module 210.
  • an electrolysis voltage is applied from the power supply device 220 to the SOEC module 210, and electrolysis is started in the SOEC module 210.
  • Electrolytic gas is generated in each SOEC included in the SOEC module 210 by electrolysis. That is, hydrogen and/or carbon monoxide is produced from the fuel electrode, and oxygen is produced from the oxygen electrode.
  • Hydrogen and/or carbon monoxide generated at the fuel electrode is separated by a gas separation device 240. Furthermore, hydrogen and/or carbon monoxide separated by the gas separation device 240 is stored in a storage device 250.
  • oxygen generated at the oxygen electrode may be recovered and stored by another device.
  • each SOEC configuring the SOEC module 210 uses a SOEC according to an embodiment of the present invention.
  • FIG. 3 schematically shows a flow of a SOEC manufacturing method according to an embodiment of the present invention.
  • the SOEC manufacturing method (hereinafter referred to as "first method") according to one embodiment of the present invention is as follows: (1) a step of installing a first intermediate layer on the first surface of the electrolyte layer (step S110); (2) a step of installing a fuel electrode on the first intermediate layer (step S120); (3) installing an oxygen electrode on the side of the electrolyte layer opposite to the first intermediate layer (step S130); has.
  • Step S110 First, a solid electrolyte layer 130 having a first surface and a second surface facing each other is prepared.
  • the shape of the solid electrolyte layer 130 is not particularly limited, and the solid electrolyte layer 130 may be plate-shaped or disc-shaped.
  • the solid electrolyte layer 130 may be made of YSZ or ScSZ, as described above.
  • a first intermediate layer 150 is formed on the first surface of the solid electrolyte layer 130. Further, if necessary, a second intermediate layer 160 may be formed on the second surface of the solid electrolyte layer 130.
  • the first intermediate layer 150 is formed as follows.
  • a first intermediate layer paste is installed on the first surface of the solid electrolyte layer 130.
  • the first intermediate layer paste includes, for example, a solvent, cerium-based oxide particles, and a binder.
  • the cerium-based oxide may be Gd-doped cerium oxide.
  • the method of installing the first intermediate layer paste is not particularly limited.
  • the first intermediate layer paste may be applied to the first surface of the solid electrolyte layer 130, for example, by brush coating, screen printing, or the like.
  • the firing temperature is, for example, in the range of 1200°C to 1400°C. As a result, the first intermediate layer 150 is formed.
  • the second intermediate layer 160 is also formed in a similar manner.
  • Step S120 Next, the fuel electrode 110 is formed on the first intermediate layer 150.
  • the fuel electrode 110 is formed as follows.
  • a fuel electrode paste is placed on the surface of the first intermediate layer 150.
  • the fuel electrode paste includes, for example, a solvent, mixed particles, and a binder.
  • ⁇ -terpineol and polyethylene glycol (PEG) can be used as the solvent.
  • PEG polyethylene glycol
  • Polyvinyl butyral (PVB), ethyl cellulose (EC), etc. can be used as the binder.
  • the mixed particles contain a metal or a metal oxide and a compound A.
  • the metal includes at least one selected from the group consisting of nickel (Ni), copper (Cu), silver (Ag), tungsten (W), platinum (Pt), iron (Fe), and tin (Sn). .
  • the ratio of the metal or metal oxide to the entire mixed particles is in the range of 40 vol% to 80 vol% in terms of metal volume ratio.
  • compound A includes a mayenite type compound and/or a CaTiO 3 -based perovskite type compound.
  • the mayenite-type compound may be a 12CaO.7Al 2 O 3 -based mayenite-type compound, a 12SrO.7Al 2 O 3 -based mayenite-type compound, or a 12MgO.7Al 2 O 3 -based mayenite-type compound.
  • compound A may have a mayenite type compound and another compound B.
  • another compound B is lithium (Li), sodium (Na), potassium (K), barium (Ba), magnesium (Mg), strontium (Sr), titanium (Ti), yttrium (Y), cerium (Ce), lanthanum (La), and neodymium (Nd). This increases ionic conductivity and/or affinity with CO 2 and suppresses an increase in electrolytic voltage.
  • Such another compound B may be added in an amount of 0.1 mol % to 30 mol % based on the entire compound A in terms of oxide.
  • compound A may include a perovskite-type compound and another compound C.
  • Such another compound C may include a compound of aluminum (Al), such as aluminum oxide.
  • Another compound C may be added in an amount of 0.1 mol % to 30 mol % based on the entire compound A in terms of oxide.
  • compound A may further contain a cerium-based oxide.
  • the content of the cerium-based oxide relative to the compound A is, for example, 80 vol% or less in volume ratio.
  • the method of installing the fuel electrode paste is not particularly limited.
  • the fuel electrode paste may be applied onto the first intermediate layer 150 by, for example, brushing, screen printing, or the like.
  • the firing temperature varies depending on the mixed particles contained in the fuel electrode paste, but is, for example, in the range of 1100°C to 1300°C.
  • the fuel electrode 110 is formed.
  • Step S130 Next, the oxygen electrode 120 is formed on the second surface of the solid electrolyte layer 130 (the second intermediate layer 160, if present; the same applies hereinafter).
  • the oxygen electrode 120 is formed as follows.
  • an oxygen electrode paste is placed on the second surface of the solid electrolyte layer 130.
  • the oxygen electrode paste includes, for example, a solvent, mixed particles, and a binder.
  • the solvent and binder for example, the solvent and binder used in the above-mentioned fuel electrode paste can be used.
  • the mixed particles may be composed of materials that constitute conventional oxygen electrodes.
  • the mixed particles may be, for example, lanthanum-strontium-cobalt-based oxide (La 1-z Sr z CoO 3 ) (where 0 ⁇ z ⁇ 1).
  • the method of installing the oxygen electrode paste is not particularly limited.
  • the oxygen electrode paste may be applied onto the second surface of the solid electrolyte layer 130, for example, by brush coating, screen printing, or the like.
  • the oxygen electrode paste is dried and further subjected to a firing process.
  • the firing temperature varies depending on the mixed particles contained in the oxygen electrode paste, but is, for example, in the range of 900°C to 1100°C.
  • the oxygen electrode 120 is formed.
  • a SOEC according to an embodiment of the present invention can be manufactured.
  • the SOEC according to one embodiment of the present invention may be manufactured by another method. That is, the SOEC according to an embodiment of the present invention may be manufactured by any method as long as a fuel electrode having the above-described characteristics can be obtained.
  • Examples of the present invention will be described below. In the following description, Examples 1 to 20 and Examples 31 to 35 are examples, and Examples 21 and 22 are comparative examples.
  • an intermediate layer was formed on each surface of the solid electrolyte layer by the following procedure.
  • a YSZ substrate manufactured by Tosoh, thickness 500 ⁇ m was used for the solid electrolyte layer.
  • a paste-like composition (referred to as "first paste") was prepared by kneading at a mass ratio of: :50.
  • the first paste was applied to the first surface of the YSZ substrate.
  • the YSZ substrate was turned over, and the first paste was also applied to the second surface using the same procedure.
  • the YSZ substrate was heated to 1400°C. As a result, a first intermediate layer with a diameter of 12 mm ⁇ was formed on the first surface of the YSZ substrate, and a second intermediate layer with a diameter of 12 mm ⁇ was formed on the second surface.
  • a paste-like composition (hereinafter referred to as "second paste") was prepared by adding a solvent (polyethylene glycol PEG400, manufactured by Kokusan Kagaku) to this mixed powder and kneading it.
  • a solvent polyethylene glycol PEG400, manufactured by Kokusan Kagaku
  • a masking tape was applied to the first intermediate layer except for a 10 mm diameter area approximately at the center, and then a second paste was applied onto the first intermediate layer.
  • the second paste was then dried at 230°C.
  • NiO paste (NiO-AFL; manufactured by Kceracell) was applied thereon as a current collecting member. After drying the NiO paste at 140°C, the assembly was fired at 1300°C to form the fuel electrode and current collector member thereon.
  • a paste-like composition (hereinafter referred to as "third paste") was prepared.
  • the third paste is a paste containing powder with a composition of (La 0.60 Sr 0.40 ) 0.95 (Co 0.20 Fe 0.80 )O 3 (LSCF-1; manufactured by Fuel Cell Materials). .
  • Cell 1 The obtained SOEC is referred to as "Cell 1".
  • Example 2 to Example 4 A SOEC was produced in the same manner as in Example 1.
  • Example 4 the composition of the fuel electrode was changed from that in Example 1.
  • a mixture of 12CaO.7Al 2 O 3 mayenite powder and ceria powder GDC standard product for test and research, manufactured by AGC Seimi Chemical
  • the amount of Al 2 O 3 was adjusted as follows.
  • the other cell configurations are the same as in Example 1.
  • Example 21 A SOEC was produced in the same manner as in Example 1.
  • the fuel electrode was composed of a mixture of NiO and YSZ.
  • the mixing ratio of NiO and YSZ was 50:50 (volume ratio) in terms of Ni metal.
  • the other cell configurations are the same as in Example 1.
  • cell 21 The obtained SOEC is referred to as "cell 21".
  • Table 1 summarizes the composition of the fuel electrode in each cell.
  • a single cell evaluation device for solid oxide fuel cells BEL-SOFC (manufactured by Microtrack Bell Co., Ltd.), was used.
  • the hydrogen feed rate was 10 ml/min
  • the argon feed rate was 70 ml/min
  • the water vapor feed rate was 10 ml/min
  • the carbon dioxide feed rate was 10 ml/min.
  • pure oxygen was supplied to the oxygen electrode side at a supply rate of 100 ml/min.
  • the electrolytic current density was 0.1 A/cm 2 .
  • FIG. 4 also shows changes over time in the electrolytic voltage measured in cell 1 and cell 21.
  • the electrolysis voltage on the vertical axis was a value normalized to the initial voltage V 0 of each cell.
  • cell 1 the electrolytic voltage hardly changes with respect to the operating time. From this, it was found that cell 1 allows more stable electrolysis than cell 21.
  • Table 2 summarizes the voltage change rates after 10 hours of electrolysis obtained in each cell.
  • Example 5 the voltage change rate of a cell having a fuel electrode containing Compound A with a predetermined composition was estimated.
  • Powder of compound A was prepared in the same manner as in Example 1.
  • a predetermined amount of LiCO 3 manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • the amount of CaCO3 was adjusted accordingly.
  • Other manufacturing conditions are the same as in Example 1.
  • Example 6 to Example 16 Powders of various compounds A were prepared in the same manner as in Example 5. However, in Examples 6 to 16, instead of Li 2 CO 3 , Na 2 CO 3 (manufactured by Kanto Kagaku), K 2 CO 3 (manufactured by Fuji Film Wako Pure Chemical), MgO (manufactured by Fuji Film Wako Pure Chemical), SrCO 3 (manufactured by Fuji Film Wako Pure Chemical), BaCO 3 (manufactured by Fuji Film Wako Pure Chemical), Y 2 O 3 (manufactured by Shin-Etsu Chemical), La 2 O 3 (manufactured by Junsei Chemical), CeO 2 (manufactured by Kanto Chemical) , Nd 2 O 3 (manufactured by Shin-Etsu Chemical), and TiO 2 (manufactured by Kojundo Kagaku) were added.
  • Na 2 CO 3 manufactured by Kanto Kagaku
  • K 2 CO 3 manufactured by Fuji Film Wako Pure Chemical
  • Na 2 CO 3 , K 2 CO 3 , MgO, SrCO 3 , and BaCO 3 were added in an amount of 5 mol % in terms of Na 2 O, K 2 O, MgO, SrO, and BaO.
  • Y 2 O 3 , La 2 O 3 , and Nd 2 O 3 were added in an amount of 3 mol % in terms of Y 2 O 3 , La 2 O 3 , and Nd 2 O 3 .
  • CeO 2 and TiO 2 were added in amounts of 11 mol % and 14 mol %, respectively, in terms of CeO 2 and TiO 2 .
  • Other manufacturing conditions are the same as in Example 1.
  • the obtained mixed powder was kept in the atmosphere at high temperature for 2 hours to dry it.
  • the treatment temperature was 140°C. This yielded a dry mixed powder from which the solvent had been removed.
  • the treatment temperature was 1400°C and the treatment time was 10 hours.
  • the obtained treated body was pulverized in a mortar to produce powder of CaTiO 3 and aluminum oxide as compound A.
  • a mixed powder was prepared by mixing nickel oxide (NiO, manufactured by Kojundo Kagaku Kenkyusho) powder and the powder of the above compound A at a volume ratio of 50:50 in terms of Ni metal.
  • cell 17 The obtained SOEC is referred to as "cell 17".
  • Example 18 to Example 19 A SOEC was produced in the same manner as in Example 17.
  • Example 18 a mixed powder was prepared by mixing strontium carbonate powder, titanium oxide powder, and ⁇ -alumina powder, respectively.
  • the amount of Al contained in the mixed powder was 14 mol % in terms of Al 2 O 3 .
  • Example 19 a mixed powder was prepared by mixing barium carbonate powder, titanium oxide powder, and ⁇ -alumina powder, respectively.
  • the amount of Al contained in the mixed powder was 14 mol % in terms of Al 2 O 3 .
  • Example 20 A SOEC was produced in the same manner as in Example 1. However, in this example 20, when forming the fuel electrode, nickel oxide powder and 12CaO.7Al2O3 mayenite powder as compound A were mixed at a volume ratio of 70:30 in terms of Ni metal, A mixed powder was prepared.
  • Table 3 shows the composition of the fuel electrode containing Compound A assumed in each example.
  • Table 4 summarizes the estimated cell voltage change rates after 10 hours of electrolysis in each example.
  • Example 22 A SOEC was produced in the same manner as in Example 1. However, in this Example 22, CSZ (CaO stabilized zirconia, manufactured by Kojundo Kagaku Co., Ltd.) was used as the compound A, the volume ratio of Ni in terms of metal was 75%, and the sintering temperature of the fuel electrode was 1100°C.
  • CSZ CaO stabilized zirconia, manufactured by Kojundo Kagaku Co., Ltd.
  • Example 31 A SOEC was produced in the same manner as in Example 1. However, in this Example 31, the volume ratio of Ni in terms of metal was 75%, and the sintering temperature of the fuel electrode was 1100°C.
  • Example 32 A SOEC was produced in the same manner as in Example 1. However, in this Example 32, the weighed value during the preparation of Compound A was changed so that the final composition was Ca 3 Al 2 O 6 . Further, the volume ratio of Ni in terms of metal was set to 75%, and the sintering temperature of the fuel electrode was set to 1200°C.
  • Example 33 A SOEC was produced in the same manner as in Example 1. However, in this Example 33, the weighing value during the preparation of Compound A was changed so that the final composition was CaAl 2 O 4 . Further, the volume ratio of Ni in terms of metal was set to 75%, and the sintering temperature of the fuel electrode was set to 1100°C.
  • Example 34 A SOEC was produced in the same manner as in Example 1. However, in this Example 34, calcium carbonate powder (manufactured by Kojundo Kagaku Kenkyusho) was used as compound A. Further, the volume ratio of Ni in terms of metal was set to 75%, and the sintering temperature of the fuel electrode was set to 1100°C.
  • Example 35 A SOEC was produced in the same manner as in Example 1. However, in this Example 35, La 2 O 3 powder (manufactured by Junsei Kagaku) was used as compound A. Further, the volume ratio of Ni in terms of metal was set to 75%, and the sintering temperature of the fuel electrode was set to 1100°C.
  • Each cell was operated at 800°C, and changes in operating voltage during electrolysis were measured.
  • As the measurement device a single cell evaluation device for solid oxide fuel cells, BEL-SOFC (manufactured by Microtrack Bell Co., Ltd.), was used.
  • the hydrogen feed rate was 10 ml/min
  • the argon feed rate was 70 ml/min
  • the water vapor feed rate was 10 ml/min
  • the carbon dioxide feed rate was 10 ml/min.
  • pure oxygen was supplied to the oxygen electrode side at a supply rate of 100 ml/min.
  • the electrolysis current density was 0.2 A/cm 2 and the electrolysis time was 5 to 50 hours.
  • Table 5 summarizes the composition of the fuel electrode containing Compound A assumed in each example and the evaluation results.
  • a solid oxide electrolysis cell having a fuel electrode, an oxygen electrode, and a solid electrolyte layer between the fuel electrode and the oxygen electrode, further comprising an intermediate layer between the solid electrolyte layer and the fuel electrode, the intermediate layer comprising cerium oxide;
  • the fuel electrode includes a metal or a metal oxide and a compound A, The ratio of the metal or the oxide of the metal to the entire fuel electrode is in the range of 40 vol% to 80 vol% in terms of metal volume ratio,
  • the metal includes at least one selected from the group consisting of nickel (Ni), copper (Cu), silver (Ag), tungsten (W), platinum (Pt), iron (Fe), and tin (Sn).
  • the compound A is a solid oxide electrolytic cell containing a mayenite-type compound and/or a perovskite-type compound containing an alkaline earth metal element.
  • (Aspect 2) The solid oxide according to aspect 1, wherein the mayenite-type compound is a 12CaO.7Al2O3 - based mayenite-type compound, a 12SrO.7Al2O3 - based mayenite-type compound, or a 12MgO.7Al2O3 - based mayenite-type compound. shaped electrolytic cell.
  • Compound A is The mayenite type compound; with another compound B, has The other compound B is lithium (Li), sodium (Na), potassium (K), barium (Ba), magnesium (Mg), strontium (Sr), titanium (Ti), yttrium (Y), cerium (Ce). ), lanthanum (La), and neodymium (Nd),
  • Compound A is The perovskite compound; Another compound C, has The other compound C includes an aluminum (Al) compound, 5.
  • a solid oxide electrolytic cell system The module according to aspect 9, a power supply device that supplies power to the module; a gas supply device that supplies water vapor and/or carbon dioxide to the module; a gas separation device that separates hydrogen and/or carbon monoxide generated from the module; a storage device that stores the hydrogen and/or carbon monoxide separated by the gas separation device; A solid oxide electrolytic cell system with
  • a solid oxide electrolysis cell having a fuel electrode, an oxygen electrode, and a solid electrolyte layer between the fuel electrode and the oxygen electrode, further comprising an intermediate layer between the solid electrolyte layer and the fuel electrode, the intermediate layer comprising cerium oxide;
  • the fuel electrode includes a metal or a metal oxide and a compound A, The ratio of the metal or the oxide of the metal to the entire fuel electrode is in the range of 40 vol% to 80 vol% in terms of metal volume ratio,
  • the metal includes at least one selected from the group consisting of nickel (Ni), copper (Cu), silver (Ag), tungsten (W), platinum (Pt), iron (Fe), and tin (Sn).
  • the compound A contains an oxide containing an alkaline earth metal element and/or a rare earth element other than Sc and Y, and the ratio of the alkaline earth metal element and/or rare earth element other than Sc and Y to the metal is molar.
  • Solid oxide type electrolytic cell with a ratio of 1.0% or more.
  • a solid oxide electrolytic cell system The module according to aspect 12, a power supply device that supplies power to the module; a gas supply device that supplies water vapor and/or carbon dioxide to the module; a gas separation device that separates hydrogen and/or carbon monoxide generated from the module; a storage device that stores the hydrogen and/or carbon monoxide separated by the gas separation device; A solid oxide electrolytic cell system with
  • First cell 110
  • Fuel electrode 120
  • Oxygen electrode 130
  • Solid electrolyte layer 150
  • External power supply 201
  • SOEC system 210
  • Power supply device 230
  • Gas supply device 240
  • Gas separation device 250
  • Storage device

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Abstract

L'invention concerne une cellule d'électrolyse à oxyde solide (SOEC) comprenant une électrode à combustible, une électrode à oxygène et une couche d'électrolyte solide entre l'électrode à combustible et l'électrode à oxygène, la SOEC comprenant en outre une couche intermédiaire entre la couche d'électrolyte solide et l'électrode à combustible. La couche intermédiaire comprend de l'oxyde de cérium et l'électrode à combustible comprend un métal ou un oxyde métallique et un composé A. La proportion du métal ou de l'oxyde métallique par rapport à la totalité de l'électrode à combustible en tant que rapport volumique en termes de métal est située dans la plage de 40 à 80 % en volume et le métal comprend au moins un métal choisi dans le groupe constitué par le nickel (Ni), le cuivre (Cu), l'argent (Ag), le tungstène (W), le platine (Pt), le fer (Fe) et l'étain (Sn). Le composé A comprend un composé de type mayénite et/ou un composé de type pérovskite contenant un élément de métal alcalino-terreux.
PCT/JP2023/025575 2022-07-14 2023-07-11 Cellule d'électrolyse à oxyde solide et système de cellule d'électrolyse à oxyde solide WO2024014454A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016115592A (ja) * 2014-12-16 2016-06-23 日本特殊陶業株式会社 固体酸化物形電気化学セル、固体酸化物形燃料電池、高温水蒸気電気分解装置
JP2017071831A (ja) * 2015-10-07 2017-04-13 株式会社日本触媒 水蒸気電解用セル
JP2017071830A (ja) * 2015-10-07 2017-04-13 株式会社日本触媒 水蒸気電解用セルおよびその製造方法
JP2018172763A (ja) * 2017-03-31 2018-11-08 株式会社日本触媒 水蒸気電解セル
JP2021025103A (ja) * 2019-08-06 2021-02-22 三井金属鉱業株式会社 固体電解質接合体
WO2021151692A1 (fr) * 2020-01-27 2021-08-05 Ceres Intellectual Property Company Limited Couche intermédiaire pour pile à oxyde solide
CN114561656A (zh) * 2022-04-06 2022-05-31 北京理工大学 一种中低温金属支撑固体氧化物电解池

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016115592A (ja) * 2014-12-16 2016-06-23 日本特殊陶業株式会社 固体酸化物形電気化学セル、固体酸化物形燃料電池、高温水蒸気電気分解装置
JP2017071831A (ja) * 2015-10-07 2017-04-13 株式会社日本触媒 水蒸気電解用セル
JP2017071830A (ja) * 2015-10-07 2017-04-13 株式会社日本触媒 水蒸気電解用セルおよびその製造方法
JP2018172763A (ja) * 2017-03-31 2018-11-08 株式会社日本触媒 水蒸気電解セル
JP2021025103A (ja) * 2019-08-06 2021-02-22 三井金属鉱業株式会社 固体電解質接合体
WO2021151692A1 (fr) * 2020-01-27 2021-08-05 Ceres Intellectual Property Company Limited Couche intermédiaire pour pile à oxyde solide
CN114561656A (zh) * 2022-04-06 2022-05-31 北京理工大学 一种中低温金属支撑固体氧化物电解池

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