WO2024201574A1 - 電解セルスタック装置及び電解セルスタック集合体 - Google Patents

電解セルスタック装置及び電解セルスタック集合体 Download PDF

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WO2024201574A1
WO2024201574A1 PCT/JP2023/011858 JP2023011858W WO2024201574A1 WO 2024201574 A1 WO2024201574 A1 WO 2024201574A1 JP 2023011858 W JP2023011858 W JP 2023011858W WO 2024201574 A1 WO2024201574 A1 WO 2024201574A1
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cell
cell stack
upstream
downstream
electrolysis
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French (fr)
Japanese (ja)
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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 JP2025509216A priority patent/JPWO2024201574A1/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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • 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
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • 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
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/02—Diaphragms; Spacing elements characterised by shape or form
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
    • C25B13/07—Diaphragms; Spacing elements characterised by the material based on inorganic materials based on ceramics
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells

Definitions

  • the present invention relates to an electrolysis cell stack device and an electrolysis cell stack assembly.
  • electrolytic cell stack devices that include multiple electrolytic cells stacked in a specific direction.
  • Patent document 1 discloses a method for distributing raw gas from a single raw gas flow path to each of all electrolysis cells.
  • the objective of the present invention is to provide an electrolysis cell stack device and an electrolysis cell stack assembly that can suppress the temperature distribution in each electrolysis cell.
  • the electrolytic cell stack device is an electrolytic cell stack device in which a plurality of electrolytic cells, including an upstream cell and a downstream cell, are stacked.
  • a plurality of electrolytic cells including an upstream cell and a downstream cell, are stacked.
  • at least a portion of the raw material gas that has passed through the upstream cell passes through the downstream cell.
  • the electrolytic cell stack device is related to the first aspect described above, and all of the electrolytic cells adjacent in the stacking direction are in an upstream-downstream relationship, and all of the raw material gas that has passed through the upstream cell passes through the downstream cell.
  • An electrolysis cell stack device is related to the first or second aspect, wherein each of the upstream cell and the downstream cell has a hydrogen electrode, an oxygen electrode, and an electrolyte, and the raw material gas contains H2O .
  • the electrolysis cell stack device according to the fourth aspect of the present invention relates to any one of the first to third aspects, and the thickness of the electrolyte in the upstream cell is thicker than the thickness of the electrolyte in the downstream cell.
  • the electrolysis cell stack device relates to any one of the first to fourth aspects, and the hydrogen electrode of the upstream cell includes a conductive oxide-based material that functions as an electrode catalyst, and the hydrogen electrode of the downstream cell includes a conductive metal-based material that functions as an electrode catalyst.
  • the electrolysis cell stack device relates to any one of the first to fifth aspects, and the area of the hydrogen electrode of the upstream cell when viewed in a plan view is smaller than the area of the hydrogen electrode of the downstream cell when viewed in a plan view.
  • the electrolysis cell stack assembly comprises a first electrolysis cell stack device in which a plurality of upstream cells are stacked, and a second electrolysis cell stack device in which a plurality of downstream cells are stacked. At least a portion of the raw gas that has passed through the first electrolysis cell stack device passes through the second electrolysis cell stack device.
  • the electrolysis cell stack assembly according to the eighth aspect of the present invention is related to the first aspect above, and all of the raw material gas that has passed through the first electrolysis cell stack device passes through the second electrolysis cell stack device.
  • An electrolysis cell stack assembly is related to the seventh aspect, wherein each of the upstream cell and the downstream cell has a hydrogen electrode, an oxygen electrode, and an electrolyte, and the raw material gas contains H2O .
  • the electrolysis cell stack assembly according to the tenth aspect of the present invention relates to any one of the seventh to ninth aspects, and the thickness of the electrolyte in the upstream cell is thicker than the thickness of the electrolyte in the downstream cell.
  • the electrolysis cell stack assembly according to an eleventh aspect of the present invention relates to any one of the seventh to tenth aspects above, and the hydrogen electrode of the upstream cell includes a conductive oxide-based material that functions as an electrode catalyst, and the hydrogen electrode of the downstream cell includes a conductive metal-based material that functions as an electrode catalyst.
  • the electrolysis cell stack assembly according to the twelfth aspect of the present invention relates to any one of the seventh to eleventh aspects, and the area of the hydrogen electrode of the upstream cell when viewed in a plan view is smaller than the area of the hydrogen electrode of the downstream cell when viewed in a plan view.
  • the present invention provides an electrolysis cell stack device and an electrolysis cell stack assembly that can suppress temperature distribution in each electrolysis cell.
  • FIG. 1 is a perspective view of an electrolysis cell stack device according to an embodiment.
  • 2 is a cross-sectional view taken along line AA in FIG. 1 .
  • FIG. 13 is a schematic diagram showing a route of a raw material gas flowing through an electrolysis cell stack device according to Modification 1.
  • FIG. 11 is a schematic diagram showing a route of a raw material gas flowing within an electrolysis cell stack assembly according to Modification 2.
  • FIG. 1 is a perspective view of an electrolysis cell stack device 10 according to an embodiment.
  • the shape of the electrolysis cell stack device 10 is rectangular when viewed in a plan view from the x-axis direction (stacking direction), but the planar shape of the electrolysis cell stack device 10 is not particularly limited and can be, for example, a square, a polygon with five or more sides, a circle, an ellipse, etc.
  • the electrolytic cell stack device 10 includes first to sixth electrolytic cells 11a to 11f, a first end plate 12a, and a second end plate 12b.
  • the first to sixth electrolytic cells 11a to 11f may be abbreviated as electrolytic cells 11.
  • the first to sixth electrolytic cells 11a to 11f are stacked in this order in the x-axis direction.
  • the x-axis direction is the stacking direction of the first to sixth electrolytic cells 11a to 11f.
  • the first electrolytic cell 11a is the electrolytic cell closest to the first end plate 12a among the six electrolytic cells 11.
  • the sixth electrolytic cell 11f is the electrolytic cell closest to the second end plate 12b among the six electrolytic cells 11 (i.e., the electrolytic cell farthest from the first end plate 12a).
  • the stacked first to sixth electrolytic cells 11a to 11f are sandwiched between the first and second end plates 12a, 12b.
  • the first to sixth electrolytic cells 11a to 11f include the "upstream cell” and "downstream cell” according to the present invention. Whether each electrolytic cell 11 corresponds to an upstream cell or a downstream cell is determined relatively based on the flow direction of the raw material gas described below. For example, in the flow direction of the raw material gas, the fourth electrolytic cell 11d is located downstream of the first to third electrolytic cells 11a to 11c and upstream of the fifth and sixth electrolytic cells 11e, 11f. Therefore, the fourth electrolytic cell 11d corresponds to a "downstream cell” with respect to the first to third electrolytic cells 11a to 11c, and corresponds to an "upstream cell” with respect to the fifth and sixth electrolytic cells 11e, 11f. However, the first electrolytic cell 11a located at the most upstream position is never a "downstream cell", and the sixth electrolytic cell 11f located at the most downstream position is never an "upstream cell".
  • all electrolytic cells 11 adjacent to each other in the stacking direction are in an upstream-downstream relationship.
  • the upstream cell and the downstream cell are always adjacent to each other in the stacking direction.
  • the electrolytic cell stack device 10 includes the first to sixth electrolytic cells 11a to 11f, but the number of electrolytic cells 11 is not particularly limited as long as it is two or more.
  • the electrolysis cell stack device 10 has a first outer surface R1 and a second outer surface R2.
  • the first outer surface R1 is provided on the opposite side of the second outer surface R2 in the x-axis direction.
  • the first outer surface R1 is the surface of the first end plate 12a.
  • a raw material gas inlet 13 and an air inlet 14 are formed on the first outer surface R1.
  • the second outer surface R2 is the surface of the second end plate 12b.
  • a raw material gas outlet 15 and an air outlet 16 are formed on the second outer surface R2.
  • Figure 2 is a cross-sectional view taken along line A-A in Figure 1.
  • each of the first to sixth electrolytic cells 11a to 11f has an element portion 20, a pair of interconnectors 30, and a frame 40.
  • the element unit 20 is a well-known element unit used in a flat-plate solid oxide electrolysis cell (SOEC).
  • SOEC solid oxide electrolysis cell
  • the element unit 20 has a hydrogen electrode 21, an electrolyte 22, and an oxygen electrode 23.
  • the electrolyte 22 is disposed between the hydrogen electrode 21 and the oxygen electrode 23.
  • a source gas containing H2O is supplied to the hydrogen electrode 21.
  • the hydrogen electrode 21 produces H 2 from the raw material gas in accordance with the electrochemical reaction of water electrolysis shown in the following formula (1).
  • Hydrogen electrode 21 H 2 O + 2e ⁇ ⁇ H 2 + O 2 ⁇ (1)
  • the hydrogen electrode 21 produces H 2 , CO, and O 2 ⁇ from the raw material gas in accordance with the co-electrochemical reactions shown in the following formulas (2), (3), and (4).
  • Hydrogen electrode 21 H 2 O + CO 2 + 4e ⁇ ⁇ CO + H 2 + 2O 2 ⁇ (2)
  • the hydrogen electrode 21 contains an electrode catalyst.
  • the hydrogen electrode 21 may contain an oxygen ion conductive material.
  • O 2 ⁇ is transferred to the oxygen electrode 23 from the hydrogen electrode 21 via the electrolyte 22.
  • the oxygen electrode 23 produces O 2 from O 2 ⁇ in accordance with the chemical reaction of the following formula (5).
  • the element unit 20 may be an element unit used in a known electrolytic cell. Therefore, the configuration of the element unit 20 may be modified as appropriate.
  • the element unit 20 may have a reaction prevention layer disposed between the electrolyte 22 and the oxygen electrode 23. A preferred configuration of the element unit 20 will be described later.
  • the pair of interconnectors 30 sandwich the element unit 20 between them.
  • a metal plate can be used as the interconnector 30.
  • the interconnector 30 has a plurality of first connection parts 31 and a plurality of second connection parts 32.
  • Each of the first connection parts 31 is formed on one main surface of the interconnector 30 and is electrically connected to the hydrogen electrode 21.
  • Each of the second connection parts 32 is formed on the other main surface of the interconnector 30 and is electrically connected to the oxygen electrode 23.
  • a pair of interconnectors 30 is shared by two adjacent electrolysis cells 11.
  • the frame 40 is made of an electrically insulating material.
  • the frame 40 surrounds the electrolytic cell 11.
  • the frame 40 provides a seal between the two interconnectors 30.
  • the electrolyte 22 of the element unit 20, the interconnector 30, and the frame 40 define a source gas flow path P1 on the hydrogen electrode 21 side of the element unit 20.
  • the electrolyte 22 of the element unit 20, the interconnector 30, and the frame 40 define an air flow path P2 on the oxygen electrode 23 side of the element unit 20.
  • the electrolysis cell stack device 10 has a raw material gas supply path S1, first to fifth connection paths T1 to T5, and a raw material gas discharge path S2.
  • the raw gas supply passage S1 is formed in the first end plate 12a and the interconnector 30 and frame 40 of the first electrolysis cell 11a.
  • the raw gas supply passage S1 is connected to the raw gas inlet 13 and the raw gas flow passage P1 of the first electrolysis cell 11a.
  • the first to fifth connection paths T1 to T5 are formed in the interconnector 30 and frame 40 of each of the first to sixth electrolysis cells 11a to 11f.
  • the first, third and fifth connection paths T1, T3, T5 are provided on the opposite side to the second, fourth and sixth connection paths T2, T4, T6.
  • the y-axis direction is the planar direction along the surface of the electrolyte 22 in each element portion 20, and roughly coincides with the flow direction of the raw material gas in a side view.
  • the first to fifth connection paths T1 to T5 alternately connect the raw gas flow paths P1 of the first to sixth electrolysis cells 11a to 11f.
  • the first connection path T1 communicates with the raw gas flow path P1 of the first electrolysis cell 11a and the raw gas flow path P1 of the second electrolysis cell 11b.
  • the second connection path T2 communicates with the raw gas flow path P1 of the second electrolysis cell 11b and the raw gas flow path P1 of the third electrolysis cell 11c.
  • the third and fifth connection paths T3, T5 are configured similarly to the first connection path T1
  • the fourth and sixth connection paths T4, T6 are configured similarly to the second connection path T2.
  • the raw material gas exhaust passage S2 is formed in the second end plate 12b and the interconnector 30 and frame 40 of the sixth electrolysis cell 11f.
  • the raw material gas exhaust passage S2 is connected to the raw material gas flow passage P1 and the raw material gas outlet 15 of the sixth electrolysis cell 11f.
  • the electrolytic cell stack device 10 a single flow path for the raw gas is formed by the supply path S1, the first to fifth connection paths T1 to T5, the raw gas discharge path S2, and the raw gas flow path P1 of each electrolytic cell 11. Therefore, the raw gas passes through the multiple electrolytic cells 11 sequentially from the downstream side to the upstream side. Specifically, it is as follows. All of the raw gas supplied from the raw gas supply path S1 passes through the raw gas flow path P1 of the first electrolytic cell 11a.
  • All of the raw gas that has passed through the raw gas flow path P1 of the first electrolytic cell 11a is supplied to the raw gas flow path P1 of the second electrolytic cell 11b through the first connection path T1, and passes through the raw gas flow path P1 of the second electrolytic cell 11b. After that, all of the raw gas that passed through the raw gas flow path P1 of the second electrolysis cell 11b passes sequentially through the raw gas flow paths P1 of the third to sixth electrolysis cells 11c to 11f, and is then discharged to the outside through the raw gas discharge path S2.
  • all of the multiple electrolysis cells 11 adjacent to each other in the stacking direction (x-axis direction) are in an upstream-downstream relationship, and all of the raw material gas that passes through the upstream cell passes through the downstream cell, so that it is possible to suppress the occurrence of temperature distribution in each of the upstream and downstream cells.
  • the rate of increase in the concentration of the product relative to the feed gas can be suppressed compared to the case where the feed gas is distributed to each of all the electrolytic cells 11. Therefore, the difference in the concentration of the feed material in the feed gas flow path P1 of the first electrolytic cell 11a can be reduced, and the occurrence of an equilibrium potential difference between the upstream and downstream parts of the hydrogen electrode 21 of the first electrolytic cell 11a can be suppressed.
  • the electrochemical reaction at the hydrogen electrode 21 of the first electrolytic cell 11a can be made uniform in the y-axis direction (plane direction), and the occurrence of a temperature distribution in the first electrolytic cell 11a can be suppressed.
  • This effect can be obtained in any of the second to sixth electrolytic cells 11b to 11f, which correspond to downstream cells with respect to the first electrolytic cell 11a.
  • the raw gas is to be distributed to each of the upstream and downstream cells, it is difficult to distribute the raw gas evenly to both the electrolytic cells close to the raw gas inlet 13 and the electrolytic cells far from the raw gas inlet 13.
  • the raw gas that has passed through the upstream cell passes through the downstream cell, so that the raw gas can be supplied evenly to each of the upstream cell and the downstream cell.
  • the above describes how the raw gas flows in the electrolysis cell stack device 10.
  • the flow of air from the air inlet 14 to the air outlet 16 through the air flow path P2 of each of the first to sixth electrolysis cells 11a to 11f is not particularly limited.
  • the air may be supplied and exhausted through a route with the same configuration as the raw gas, or may be supplied and exhausted through a route with a different configuration than the raw gas.
  • the thickness of the electrolyte 22 in the upstream cell is thicker than the thickness of the electrolyte 22 in the downstream cell, so that the internal resistance of the electrolyte 22 in the upstream cell is greater than the internal resistance of the electrolyte 22 in the downstream cell, and therefore the amount of heat generated in the upstream cell can be made greater than that in the downstream cell.
  • the temperature of the upstream cell will be lower than the temperature of the downstream cell, as explained below.
  • the upstream cell and downstream cell are electrically connected in series, the current values flowing through each cell are equal, and the Joule heat generated in each cell is also equal.
  • the equilibrium potential of the upstream cell is lower than that of the downstream cell, so the upstream cell requires a lot of heat to reach the thermal neutral voltage where the Joule heat and the heat of reaction are balanced. Therefore, the upstream cell operates on the heat absorption side compared to the downstream cell, and the temperature of the upstream cell will be lower than that of the downstream cell.
  • the temperature difference between the upstream cell and the downstream cell can be suppressed by thickening the electrolyte 22 in the upstream cell to increase the amount of heat generated.
  • the difference in the amount of expansion and contraction between the upstream cell and the downstream cell can be reduced, which prevents uneven stress from occurring inside the electrolysis cell stack device 10 and damage to the electrolysis cell made of ceramic material.
  • the relationship in which the thickness of the electrolyte 22 in the upstream cell is thicker than that in the downstream cell is true for all of the first to sixth electrolysis cells 11a to 11f. In other words, it is preferable that the thickness of the electrolyte in the first to sixth electrolysis cells 11a to 11f is gradually reduced in this order.
  • the thickness of the electrolyte 22 in the upstream cell is thicker than that in the downstream cell only needs to be true for at least two of the first to sixth electrolytic cells 11a to 11f.
  • the thicknesses of the electrolyte 22 in the first to third electrolytic cells 11a to 11c (upstream cells) may be the same and thicker than the thickness of the electrolyte 22 in the fourth to sixth electrolytic cells 11d to 11f (downstream cells). Even in this case, the difference in the amount of expansion and contraction between the first to third electrolytic cells 11a to 11c and the fourth to sixth electrolytic cells 11d to 11f can be reduced.
  • the thickness of the electrolyte 22 is not particularly limited and can be, for example, 1 ⁇ m or more and 100 ⁇ m or less.
  • the thickness of the electrolyte 22 is obtained by taking the arithmetic average of the thicknesses at five randomly selected points on a cross-sectional SEM (electron microscope) image of the electrolyte 22 along the x-axis direction.
  • the hydrogen electrode 21 of the upstream cell contains a conductive oxide-based material that functions as an electrode catalyst
  • the hydrogen electrode 21 of the downstream cell contains a conductive metal-based material that functions as an electrode catalyst
  • SrTiO3 - based material As the oxide-based material, SrTiO3 - based material, (La, Sr)CrO3 - based material, (La, Sr)(Al, Mn) O3 -based material, (Ce, Mn, Fe) O2 , Sr2FeNbO6 , (Sr, Fe) MoO6 , Sr2TiNbO6 , (La, Sr) VO3 , and a mixed material of two or more of these can be used.
  • SrTiO3 - based material and (La, Sr) CrO3- based material are particularly preferable as the oxide-based material.
  • SrTiO3 -based materials, (La,Sr) CrO3- based materials, and (La,Sr)(Al,Mn) O3 -based materials may further contain other elements in one or both of the A site and the B site.
  • SrTiO3 -based materials include (Sr,Pr)(Ti,Fe) O3 , (Sr,La) TiO3 , (Sr,La)(Ti,Cu) O3 , (Sr,La)(Ti,Ni) O3 , (Sr,La)(Fe,Ni) O3 , (Sr,La)(Ni,Ti) O3 , (Sr,Y) TiO3 , (Sr,La)(Ti,Mn) O3 , and Sr(Ti,Nb) O3 .
  • Examples of (La, Sr) CrO3 -based materials include (La, Sr)(Cr, Mn) O3 -based materials and (La
  • the above-mentioned metallic materials can be nickel (Ni), cobalt (Co), iron (Fe), or a mixture of two or more of these.
  • the oxide-based materials have higher resistance to impurities (e.g., sulfur) that are mixed into the raw material gas than the metal-based materials, so that the electrode activity is less likely to decrease even if the material is poisoned by impurities.
  • impurities e.g., sulfur
  • the metal-based materials have higher electronic conductivity and electrode activity than the oxide-based materials, so they can promote electrochemical reactions.
  • the hydrogen electrode 21 of the upstream cell contain an oxide-based material as an electrode catalyst
  • the hydrogen electrode 21 of the downstream cell contain a metal-based material as an electrode catalyst
  • the metal-based material contained in the hydrogen electrode 21 of the downstream cell is Ni.
  • Ni has a property of being easily oxidized, since H2 is generated in the upstream cell, it is not necessary to add H2 to the source gas in advance to suppress the oxidation of Ni, or the amount of H2 added to the source gas can be reduced.
  • the hydrogen electrodes 21 of the upstream cell and the downstream cell may contain an oxygen ion conductive material.
  • the oxygen ion conductive material that can be used include YSZ, CSZ, ScSZ, gadolinium doped ceria (GDC), samarium doped ceria (SDC), lanthanum doped ceria (LDC), lanthanum gallate (LSGM), and mixed materials of two or more of these.
  • the oxygen ion conductive material contained in the upstream cell may be the same as or different from the oxygen ion conductive material contained in the downstream cell.
  • the hydrogen electrode 21 of the upstream cell can be formed by firing a molded body containing the above-mentioned oxide-based material and, optionally, an oxygen ion conductive material.
  • the hydrogen electrode 21 of the downstream cell can be formed by firing a molded body containing the above-mentioned metal-based material and, optionally, an oxygen ion conductive material.
  • the first to sixth electrolytic cells 11a to 11f each have at least one upstream cell having a hydrogen electrode 21 containing the oxide-based material and at least one downstream cell having a hydrogen electrode 21 containing the metal-based material.
  • the hydrogen electrodes 21 of the first to third electrolytic cells 11a to 11c may contain the oxide-based material
  • the hydrogen electrodes 21 of the fourth to sixth electrolytic cells 11d to 11f may contain the metal-based material.
  • the area of the hydrogen electrode 21 of the upstream cell when viewed in plan from the x-axis direction is smaller than the area of the hydrogen electrode 21 of the downstream cell when viewed in plan from the x-axis direction. This makes the current density at the hydrogen electrode 21 of the upstream cell larger than the current density at the hydrogen electrode 21 of the downstream cell, so that the amount of heat generated by the upstream cell can be made larger than that of the downstream cell.
  • the temperature of the upstream cell will be lower than the temperature of the downstream cell. Therefore, as described above, by reducing the area of the hydrogen electrode 21 of the upstream cell and increasing the amount of heat generated, the temperature difference between the upstream cell and the downstream cell can be suppressed. As a result, the difference in the amount of expansion and contraction between the upstream cell and the downstream cell can be reduced, and uneven stress generation inside the electrolysis cell stack device 10 can be suppressed.
  • the relationship in which the area of the hydrogen electrode 21 of the upstream cell is smaller than that of the downstream cell is satisfied for all of the first to sixth electrolysis cells 11a to 11f.
  • the areas of the hydrogen electrodes 21 of the first to sixth electrolysis cells 11a to 11f increase stepwise in this order.
  • the relationship that the area of the hydrogen electrode 21 of the upstream cell is smaller than that of the downstream cell only needs to be true for at least two of the first to sixth electrolytic cells 11a to 11f.
  • the areas of the hydrogen electrodes 21 of the first to third electrolytic cells 11a to 11c (upstream cells) may be the same as each other and smaller than the area of the hydrogen electrodes 21 of the fourth to sixth electrolytic cells 11d to 11f (downstream cells). Even in this case, the difference in the amount of expansion and contraction between the first to third electrolytic cells 11a to 11c and the fourth to sixth electrolytic cells 11d to 11f can be reduced.
  • the entire source gas that has passed through the upstream cell passes through the downstream cell, but this is not limited thereto. Only a part of the source gas that has passed through the upstream cell may pass through the downstream cell.
  • FIG 3 is a schematic diagram showing the route of the raw material gas flowing through the electrolysis cell stack device 10a according to this modified example with arrows.
  • the raw material gas distributed to each of the first to third electrolysis cells 11a to 11c may be temporarily collected and then redistributed to each of the fourth to sixth electrolysis cells 11d to 11f.
  • each of the first to third electrolysis cells 11a to 11c corresponds to an upstream cell
  • each of the fourth to sixth electrolysis cells 11d to 11f corresponds to a downstream cell.
  • at least a portion of the raw material gas that has passed through the first electrolysis cell 11a passes through at least one of the fourth to sixth electrolysis cells 11d to 11f.
  • FIG. 4 is a schematic diagram showing the route of the raw material gas flowing in the electrolysis cell stack assembly 100 with arrows.
  • the electrolysis cell stack assembly 100 includes a first electrolysis cell stack device 110, a second electrolysis cell stack device 120, and a connection pipe 130.
  • the first electrolysis cell stack device 110 is disposed upstream of the second electrolysis cell stack device 120.
  • the first electrolysis cell stack device 110 has six stacked upstream cells 111.
  • the upstream cells 111 have the same configuration as the electrolysis cell 11 according to the above embodiment.
  • the second electrolysis cell stack device 120 has six stacked downstream cells 121.
  • the downstream cells 121 have the same configuration as the electrolysis cell 11 according to the above embodiment.
  • the first electrolysis cell stack device 110 and the second electrolysis cell stack device 120 are connected by the connection pipe 130.
  • the raw gas that has passed through the first electrolysis cell stack device 110 passes through the second electrolysis cell stack device 120. Specifically, the raw gas distributed to the six upstream cells 111 in the first electrolysis cell stack device 110 is temporarily collected in the connection pipe 130, and then redistributed to the six downstream cells 121 in the second electrolysis cell stack device 120.
  • the raw material gas that has passed through the first electrolysis cell stack device 110 passes through the second electrolysis cell stack device 120. Therefore, after reacting half of the raw material gas in each upstream cell 111 of the first electrolysis cell stack device 110, the remaining half of the raw material gas can be reacted in each downstream cell 121 of the second electrolysis cell stack device 120. Therefore, compared to the case where all of the raw material gas needs to be reacted in each cell of one electrolysis cell stack, the degree of change in the raw material gas composition in each upstream cell 111 and each downstream cell 121 can be reduced by half. As a result, it is possible to suppress the occurrence of temperature distribution in the upstream and downstream parts of the hydrogen electrodes 21 of each upstream cell 111 and each downstream cell 121.
  • FIG. 4 illustrates an example in which all of the raw gas that has passed through the first electrolysis cell stack device 110 passes through the second electrolysis cell stack device 120, but this is not limited to the above.
  • a portion (approximately half each) of the raw gas that has passed through the first electrolysis cell stack device 110 will pass through each of the two second electrolysis cell stack devices 120.
  • the preferred configuration of the element section 20 can be applied to the electrolysis cell stack assembly 100 as follows.
  • the thickness of the electrolyte 22 in each upstream cell 111 is preferably greater than the thickness of the electrolyte 22 in each downstream cell 121. This makes the internal resistance of the electrolyte 22 in each upstream cell 111 greater than the internal resistance of the electrolyte 22 in each downstream cell 121, thereby suppressing the temperature difference between the first electrolysis cell stack device 110 and the second electrolysis cell stack device 120.
  • the hydrogen electrode 21 of each upstream cell 111 contains a conductive oxide-based material that functions as an electrode catalyst
  • the hydrogen electrode 21 of each downstream cell 121 contains a conductive metal-based material that functions as an electrode catalyst. This makes it possible to simultaneously suppress the decrease in electrode activity in the first electrolysis cell stack device 110 and improve the electrode activity in the second electrolysis cell stack device 120.
  • the area of the hydrogen electrode 21 of each upstream cell 111 when viewed in a plane from the x-axis direction is preferably smaller than the area of the hydrogen electrode 21 of each downstream cell 121 when viewed in a plane from the x-axis direction. This makes the current density at the hydrogen electrode 21 of each upstream cell 111 greater than the current density at the hydrogen electrode 21 of each downstream cell 121, thereby suppressing the temperature difference between the first electrolysis cell stack device 110 and the second electrolysis cell stack device 120.
  • the element unit 20 is a well-known element unit used in a flat-plate solid oxide electrolysis cell, but is not limited to this.
  • the element unit 20 may be a well-known element unit used in a so-called metal-supported solid oxide electrolysis cell.
  • a metal-supported solid oxide electrolysis cell includes a metal support plate that supports the element unit 20.
  • the hydrogen electrode 21 of the element unit 20 is disposed on a first main surface of the metal support plate.
  • the metal support plate has a plurality of communication holes that connect the first main surface to the second main surface. Each communication hole supplies raw material gas to the hydrogen electrode 21 and exhausts product gas generated in the hydrogen electrode 21.
  • the element unit 20 may be a well-known element unit used in a so-called vertical stripe type solid oxide electrolysis cell.
  • a vertical stripe type solid oxide electrolysis cell includes an element unit arranged on one main surface of a support substrate and an interconnector arranged on the other main surface of the support substrate.
  • a vertical stripe type solid oxide electrolysis cell has a raw material gas flow path that penetrates the support substrate.
  • Electrolysis cell stack device 11 Electrolysis cell 12 End plate 13 Raw material gas inlet 14 Air inlet 15 Raw material gas outlet 16 Air outlet 20 Element portion 21 Hydrogen electrode 22 Electrolyte 23 Oxygen electrode 30 Interconnector 40 Frame S1 Raw material gas supply path S2 Raw material gas exhaust paths T1 to T5 First to fifth connection paths 100 Electrolysis cell stack assembly 110 First electrolysis cell stack device 111 Upstream cell 120 Second electrolysis cell stack device 121 Downstream cell

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  • Ceramic Engineering (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09129258A (ja) * 1995-11-02 1997-05-16 Mitsubishi Heavy Ind Ltd 円筒型電解セル
JPH11149934A (ja) * 1997-11-18 1999-06-02 Mitsubishi Heavy Ind Ltd 電解セル
JP2012532429A (ja) * 2009-07-06 2012-12-13 トプサー・フューエル・セル・アクチエゼルスカベット 燃料電池スタック又は電解質セルスタックにおける組み合わされたフローパターン
JP2015505344A (ja) * 2012-01-09 2015-02-19 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ 外熱式水素製造を備える高温水蒸気電解設備（ｈｔｓｅ）
JP7236588B1 (ja) * 2021-11-15 2023-03-09 日本碍子株式会社 電解セル、及びセルスタック装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09129258A (ja) * 1995-11-02 1997-05-16 Mitsubishi Heavy Ind Ltd 円筒型電解セル
JPH11149934A (ja) * 1997-11-18 1999-06-02 Mitsubishi Heavy Ind Ltd 電解セル
JP2012532429A (ja) * 2009-07-06 2012-12-13 トプサー・フューエル・セル・アクチエゼルスカベット 燃料電池スタック又は電解質セルスタックにおける組み合わされたフローパターン
JP2015505344A (ja) * 2012-01-09 2015-02-19 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ 外熱式水素製造を備える高温水蒸気電解設備（ｈｔｓｅ）
JP7236588B1 (ja) * 2021-11-15 2023-03-09 日本碍子株式会社 電解セル、及びセルスタック装置

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