WO2025047928A1 - 電気化学セル装置、モジュールおよびモジュール収容装置 - Google Patents

電気化学セル装置、モジュールおよびモジュール収容装置 Download PDF

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Publication number
WO2025047928A1
WO2025047928A1 PCT/JP2024/031161 JP2024031161W WO2025047928A1 WO 2025047928 A1 WO2025047928 A1 WO 2025047928A1 JP 2024031161 W JP2024031161 W JP 2024031161W WO 2025047928 A1 WO2025047928 A1 WO 2025047928A1
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WIPO (PCT)
Prior art keywords
cell
cell stack
pull
out portion
module
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Pending
Application number
PCT/JP2024/031161
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English (en)
French (fr)
Japanese (ja)
Inventor
和也 今仲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyocera Corp
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Kyocera Corp
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Priority to JP2025543616A priority Critical patent/JPWO2025047928A1/ja
Publication of WO2025047928A1 publication Critical patent/WO2025047928A1/ja
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
    • H01M8/2475—Enclosures, casings or containers of fuel cell stacks
    • 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

  • next-generation energy sources which have fuel cell units, a type of cell that can generate electricity using fuel gases such as hydrogen-containing gas and oxygen-containing gases such as air.
  • the module of the present disclosure also includes the electrochemical cell device described above and a storage container for storing the electrochemical cell device.
  • the module housing device of the present disclosure also includes the module described above, ancillary equipment for operating the module, and an exterior case that houses the module and the auxiliaries.
  • FIG. 1A is a cross-sectional view illustrating an example of an electrochemical cell according to a first embodiment.
  • FIG. 1B is a side view of an example of the electrochemical cell according to the first embodiment, as viewed from the air electrode side.
  • FIG. 1C is a side view of an example of an electrochemical cell according to the first embodiment, as viewed from the interconnector side.
  • FIG. 2A is a perspective view showing an example of an electrochemical cell device according to the first embodiment.
  • FIG. 2B is a top view illustrating an example of the electrochemical cell device according to the first embodiment.
  • FIG. 2C is a cross-sectional view taken along line XX shown in FIG. 2A.
  • FIG. 3 is a cross-sectional view showing an example of a connection member included in the electrochemical cell according to the first embodiment.
  • FIG. 4 is a plan view of the connection member shown in FIG.
  • FIG. 5 is a cross-sectional view showing another example of the connection member of the electrochemical cell according to the first embodiment.
  • FIG. 6 is a plan view of the connection member shown in FIG.
  • FIG. 7 is a plan view showing another example of the connection member of the electrochemical cell according to the first embodiment.
  • FIG. 8 is an external perspective view illustrating an example of a module according to the embodiment.
  • FIG. 9 is an exploded perspective view illustrating an example of a module housing device according to an embodiment.
  • FIG. 10 is a perspective view illustrating an example of an electrochemical cell according to the second embodiment.
  • FIG. 10 is a perspective view illustrating an example of an electrochemical cell according to the second embodiment.
  • FIG. 11 is a perspective view showing an example of an electrochemical cell device according to the second embodiment.
  • FIG. 12 is a perspective view illustrating an example of an electrochemical cell according to the third embodiment.
  • FIG. 13 is a perspective view showing an example of an electrochemical cell device according to the third embodiment.
  • the electrochemical cell device may include a cell stack having a plurality of electrochemical cells.
  • An electrochemical cell device having a plurality of electrochemical cells will be simply referred to as a cell stack device.
  • FIG. 1A is a cross-sectional view showing an example of an electrochemical cell according to the first embodiment.
  • FIG. 1B is a side view of an example of an electrochemical cell according to the first embodiment, viewed from the air electrode side.
  • FIG. 1C is a side view of an example of an electrochemical cell according to the first embodiment, viewed from the interconnector side. Note that FIGS. 1A to 1C show enlarged views of a portion of each component of the electrochemical cell.
  • the electrochemical cell may also be simply referred to as a cell.
  • cell 1 is a hollow flat plate-like elongated plate.
  • the shape of cell 1 as a whole viewed from the side may be, for example, a rectangle with a side length in the length direction L of 5 cm to 50 cm and a length in the width direction W perpendicular to the length direction L of 1 cm to 10 cm.
  • the thickness of the entire cell 1 in the thickness direction T may be, for example, 1 mm to 5 mm.
  • the cell 1 includes a conductive support substrate 2, an element section 3, and an interconnector 4.
  • the support substrate 2 is columnar, having a pair of opposing flat surfaces, n1 and n2, and a pair of arc-shaped side surfaces m that connect the surfaces n1 and n2.
  • the element section 3 is located on the surface n1 of the support substrate 2.
  • the element section 3 has a fuel electrode 5, a solid electrolyte layer 6, and an air electrode 8.
  • the interconnector 4 is located on the surface n2 of the cell 1.
  • the cell 1 may also have an intermediate layer 7 between the solid electrolyte layer 6 and the air electrode 8.
  • the air electrode 8 does not extend to the lower end of the cell 1.
  • the air electrode 8 does not extend to the lower end of the cell 1.
  • the solid electrolyte layer 6 is exposed on the surface of face n1.
  • the interconnector 4 may extend to the lower end of the cell 1.
  • the interconnector 4 and the solid electrolyte layer 6 are exposed on the surface.
  • the solid electrolyte layer 6 is exposed on the surface of a pair of arc-shaped side faces m of the cell 1.
  • the interconnector 4 does not have to extend to the lower end of the cell 1.
  • the support substrate 2 has gas flow paths 2a therein through which gas flows.
  • the example of the support substrate 2 shown in FIG. 1A has six gas flow paths 2a.
  • the support substrate 2 has gas permeability, and allows the gas flowing through the gas flow paths 2a to pass through to the fuel electrode 5.
  • the support substrate 2 may be conductive.
  • the conductive support substrate 2 collects electricity generated in the element portion to the interconnector 4.
  • the material of the support substrate 2 includes, for example, an iron group metal component and an inorganic oxide.
  • the iron group metal component may be, for example, Ni (nickel) and/or NiO.
  • the inorganic oxide may be, for example, a specific rare earth element oxide.
  • the rare earth element oxide may include, for example, one or more rare earth elements selected from Sc, Y, La, Nd, Sm, Gd, Dy, and Yb.
  • the material of the fuel electrode 5 may be a generally known material.
  • the fuel electrode 5 may be made of a porous conductive ceramic, such as a ceramic containing calcium oxide, magnesium oxide, or ZrO 2 in which a rare earth element oxide is dissolved, and Ni and/or NiO.
  • the rare earth element oxide may contain a plurality of rare earth elements selected from Sc, Y, La, Nd, Sm, Gd, Dy, and Yb. Calcium oxide, magnesium oxide, or ZrO 2 in which a rare earth element oxide is dissolved may be called stabilized zirconia.
  • the stabilized zirconia may include partially stabilized zirconia.
  • the solid electrolyte layer 6 is an electrolyte and transfers ions between the fuel electrode 5 and the air electrode 8. At the same time, the solid electrolyte layer 6 has gas barrier properties, making it difficult for leakage of fuel gas and oxygen-containing gas to occur.
  • the material of the solid electrolyte layer 6 may be, for example, ZrO 2 in which 3 mol % to 15 mol % of a rare earth element oxide is dissolved.
  • the rare earth element oxide may include, for example, one or more rare earth elements selected from Sc, Y, La, Nd, Sm, Gd, Dy, and Yb.
  • the solid electrolyte layer 6 may include, for example, ZrO 2 in which Yb, Sc, or Gd is dissolved, CeO 2 in which La, Nd, or Yb is dissolved, BaZrO 3 in which Sc or Yb is dissolved, or BaCeO 3 in which Sc or Yb is dissolved.
  • the air electrode 8 is gas permeable.
  • the open porosity of the air electrode 8 may be, for example, in the range of 20% to 50%, particularly 30% to 50%.
  • the open porosity of the air electrode 8 may also be referred to as the void ratio of the air electrode 8.
  • the material of the air electrode 8 may be, for example, a conductive ceramic such as a so-called ABO3 type perovskite oxide.
  • the material of the air electrode 8 may be, for example, a composite oxide in which Sr (strontium) and La (lanthanum) coexist at the A site.
  • composite oxides include LaxSr1 - xCoyFe1 - yO3 , LaxSr1 -xMnO3 , LaxSr1 - xFeO3 , and LaxSr1 - xCoO3 , where x is 0 ⁇ x ⁇ 1 and y is 0 ⁇ y ⁇ 1 .
  • the intermediate layer 7 functions as a diffusion suppression layer.
  • Sr frontium
  • SrZrO3 resistance layer of SrZrO3 is formed in the solid electrolyte layer 6.
  • the intermediate layer 7 makes it difficult for Sr to diffuse, thereby making it difficult for SrZrO3 to be formed.
  • the material of the intermediate layer 7 may contain, for example, cerium oxide (CeO 2 ) in which a rare earth element other than Ce (cerium) is dissolved.
  • CeO 2 cerium oxide
  • a rare earth element for example, Gd (gadolinium), Sm (samarium), etc. may be used.
  • the interconnector 4 is dense, which makes it difficult for the fuel gas flowing through the gas flow passage 2a located inside the support substrate 2 and the oxygen-containing gas flowing outside the support substrate 2 to leak.
  • the interconnector 4 may have a relative density of 93% or more, particularly 95% or more.
  • Lanthanum chromite-based perovskite oxide LaCrO3 -based oxide
  • lanthanum strontium titanium-based perovskite oxide LaSrTiO3 - based oxide
  • These materials are conductive and are not easily reduced or oxidized even when they come into contact with a fuel gas such as a hydrogen-containing gas and an oxygen-containing gas such as air.
  • FIG. 2A is a perspective view showing an example of the electrochemical cell device according to the first embodiment.
  • Figure 2B is a top view showing an example of the electrochemical cell device according to the first embodiment.
  • Figure 2C is a cross-sectional view taken along line XX shown in Figure 2A.
  • the cell stack device 10 includes a cell stack 11 having a plurality of cells 1 arranged (stacked) in the thickness direction T of the cells 1 (see FIG. 1A), and a fixing member 12.
  • the fixing member 12 has a fixing material 13 and a support member 14.
  • the support member 14 supports the cell 1.
  • the fixing material 13 fixes the cell 1 to the support member 14.
  • the support member 14 also has a support 15 and a gas tank 16.
  • the support member 14, which is made of metal, has electrical conductivity.
  • the support 15 has insertion holes 15a into which the lower ends of the multiple cells 1 are inserted.
  • the lower ends of the multiple cells 1 and the inner wall of the insertion holes 15a are joined with a fixing material 13.
  • the gas tank 16 has an opening for supplying reactive gas to the multiple cells 1 through the insertion holes 15a, and a groove 16a located around the opening.
  • the outer peripheral edge of the support 15 is joined to the gas tank 16 by a bonding material 21 filled in the groove 16a of the gas tank 16.
  • fuel gas is stored in an internal space 22 (see FIG. 2B) formed by the support body 15, which is the support member 14, and the gas tank 16.
  • a gas circulation pipe 20 is connected to the gas tank 16.
  • the fuel gas is supplied to the gas tank 16 through this gas circulation pipe 20, and is supplied from the gas tank 16 to a gas flow path 2a (see FIG. 1A) inside the cell 1.
  • the fuel gas supplied to the gas tank 16 is generated in a reformer 102 (see FIG. 4), which will be described later.
  • Hydrogen-rich fuel gas can be produced by, for example, steam reforming the raw fuel.
  • fuel gas is produced by steam reforming, the fuel gas contains water vapor.
  • FIG. 2A includes two rows of cell stacks 11, two supports 15, and a gas tank 16.
  • Each of the two rows of cell stacks 11 has a plurality of cells 1.
  • Each cell stack 11 is fixed to each of the supports 15.
  • the gas tank 16 has two through holes on the top surface.
  • Each of the supports 15 is disposed in each of the through holes.
  • the internal space 22 is formed by one gas tank 16 and two supports 15.
  • an end current collecting member 17 is electrically connected to the cell 1 located at the outermost position in the arrangement direction of the multiple cells 1.
  • the end current collecting member 17 is connected to a connection member 19 that protrudes to the outside of the cell stack 11.
  • the connection member 19 collects electricity generated by the power generation of the cell 1 and draws it out to the outside. Note that the end current collecting member 17 is not shown in FIG. 2A.
  • Fig. 8 is an external perspective view showing an example of a module according to an embodiment.
  • Fig. 8 shows a state in which the front and rear surfaces, which are part of the storage container 101, have been removed and the cell stack device 10 of the fuel cell stored therein has been removed to the rear.
  • the temperature inside the module 100 during normal power generation is approximately 500°C to 1000°C due to the combustion of gas and power generation by the cell 1.
  • the exterior case 111 of the module accommodating device 110 shown in Figure 9 has support posts 112 and an exterior plate 113.
  • a partition plate 114 divides the interior of the exterior case 111 into upper and lower sections.
  • the space above the partition plate 114 in the exterior case 111 is a module accommodating chamber 115 that accommodates the module 100, and the space below the partition plate 114 in the exterior case 111 is an auxiliary equipment accommodating chamber 116 that accommodates the auxiliary equipment that operates the module 100. Note that in Figure 9, the auxiliary equipment accommodated in the auxiliary equipment accommodating chamber 116 is omitted.
  • the partition plate 114 also has an air flow port 117 for allowing air from the auxiliary equipment housing chamber 116 to flow toward the module housing chamber 115.
  • the exterior plate 113 that constitutes the module housing chamber 115 has an exhaust port 118 for exhausting air from within the module housing chamber 115.
  • FIG. 11 is a perspective view showing an example of an electrochemical cell device according to the second embodiment.
  • the cell stack device 10A shown in FIG. 11 is an electrochemical cell device in which flat electrochemical cells having an element portion 3 and conductive members 18 sandwiching the element portion 3 are stacked.
  • the cell stack device 10A has members 171 and 172, which are end current collecting members 17, located at both ends.
  • the first pull-out portion 19A1 and the second pull-out portion 19A2 are relatively high compared to the first pull-out portion 19A1, which has a higher temperature than the second pull-out portion 19A2. Furthermore, because the area of the second connection surface 19f2 is larger than the area of the first connection surface 19f1, the difference in the amount of current flow between the second pull-out portion 19A2 and the first pull-out portion 19A1 is reduced, and problems such as current imbalance are reduced. Therefore, according to this embodiment, the durability of the cell stack device 10A is increased.
  • Fig. 12 is a perspective view showing an example of an electrochemical cell according to the third embodiment.
  • the cell 1B shown in Fig. 12 has the same configuration as the cell 1A described above, except for the arrangement of the second gas flow path 182 of the conductive member 18.
  • the conductive member 18 has a first gas flow path 181 through which hydrogen-containing gas, which is a reducing gas, flows from one end to the other end in the first direction D1.
  • the conductive member 18 also has a second gas flow path 182 through which oxygen-containing gas flows from one end to the other end in the direction along the first direction D1.
  • the conductive member 18 is sealed with a sealing member or the like (not shown). In this way, in an electrochemical cell device having a cell 1B through which hydrogen-containing gas and oxygen-containing gas flow in the direction along the first direction D1, for example, the temperature near the outlet of the first gas flow path 181 through which the hydrogen-containing gas flows becomes higher than the temperature near the inlet of the first gas flow path 181.
  • FIG. 13 is a perspective view showing an example of an electrochemical cell device according to the third embodiment.
  • the cell stack device 10B shown in FIG. 13 is an electrochemical cell device in which flat electrochemical cells having an element portion 3 and conductive members 18 sandwiching the element portion 3 are stacked.
  • the cell stack device 10B has members 171 and 172, which are end current collecting members 17, located at both ends.
  • the first drawer portion 19A1 may be located near the exhaust port of the first gas flow path 181 of the member 171, and the second drawer portion 19A2 may be located near the inlet port of the first gas flow path 181 of the member 171.
  • the first drawer portion 19A1 may also serve as the first connection surface 19f1 located on the member 171.
  • the second drawer portion 19A2 may also serve as the second connection surface 19f2 located on the member 171.
  • the area of the second connection surface 19f2 may be larger than the area of the first connection surface 19f1.
  • the first pull-out portion 19A1 and the second pull-out portion 19A2 are relatively high compared to the first pull-out portion 19A1, which has a higher temperature than the second pull-out portion 19A2. Because the area of the second connection surface 19f2 is larger than the area of the first connection surface 19f1, the difference in the amount of current flow between the second pull-out portion 19A2 and the first pull-out portion 19A1 is reduced, and problems such as current imbalance are reduced. Therefore, according to this embodiment, the durability of the cell stack device 10B is increased.
  • FIG. 12 illustrates a case in which the hydrogen-containing gas and the oxygen-containing gas flow in opposite directions along the first direction D1, the hydrogen-containing gas and the oxygen-containing gas may also flow in the same direction along the first direction D1.
  • first drawer portion 19A1 and the second drawer portion 19A2 are located on the member 171 side, but the first drawer portion 19A1 and the second drawer portion 19A2 can also be located on the member 172 side in the same way as on the member 171 side.
  • a fuel cell, a fuel cell stack device, a fuel cell module, and a fuel cell device are shown as examples of an “electrochemical cell”, “electrochemical cell device”, “module”, and “module housing device”, but other examples may be an electrolytic cell, an electrolytic cell stack device, an electrolytic module, and an electrolytic device, respectively.
  • the electrolytic cell has a first electrode layer and a second electrode layer, and decomposes water vapor into hydrogen and oxygen, or carbon dioxide into carbon monoxide and oxygen, when supplied with electric power.
  • an oxide ion conductor or a hydrogen ion conductor is shown as an example of the electrolyte material of the electrochemical cell, but a hydroxide ion conductor may also be used.
  • Such an electrolytic cell, an electrolytic cell stack device, an electrolytic module, and an electrolytic device have high durability.
  • an electrochemical cell device includes a cell stack including a first cell and having a high potential portion and a low potential portion having a lower potential than the high potential portion; a connection member electrically connected to the high potential portion or the low potential portion of the cell stack, The connection member has a first lead-out portion located in a high temperature portion of the cell stack, and a second lead-out portion located in a low temperature portion of the cell stack that has a lower temperature than the high temperature portion.
  • the cross-sectional area of the connection member may be larger in the first pull-out portion than in the second pull-out portion.
  • the first draw-out portion has a first connection surface to be connected to an external device
  • the second drawer portion has a second connection surface connected to the external device
  • the second connection surface may have a larger area than the first connection surface
  • the first outlet portion may be located near an inlet of the first gas flow path through which the reducing gas is introduced into the interior of the cell stack, or near an outlet of the second gas flow path through which the oxidizing gas is discharged from the interior of the cell stack.
  • the module (6) comprises an electrochemical cell device according to any one of (1) to (5) above; and a container for housing the electrochemical cell device.
  • the module housing device (7) includes the module (6) and Auxiliary equipment for operating the module; and an exterior case that houses the module and the auxiliary equipment.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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PCT/JP2024/031161 2023-08-31 2024-08-30 電気化学セル装置、モジュールおよびモジュール収容装置 Pending WO2025047928A1 (ja)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007280678A (ja) * 2006-04-04 2007-10-25 Toyota Motor Corp 燃料電池
JP2019145225A (ja) * 2018-02-16 2019-08-29 パナソニックＩｐマネジメント株式会社 燃料電池システムと、それに用いられるスタックのエージング方法
WO2020175540A1 (ja) * 2019-02-27 2020-09-03 京セラ株式会社 セルスタック装置、モジュールおよびモジュール収容装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007280678A (ja) * 2006-04-04 2007-10-25 Toyota Motor Corp 燃料電池
JP2019145225A (ja) * 2018-02-16 2019-08-29 パナソニックＩｐマネジメント株式会社 燃料電池システムと、それに用いられるスタックのエージング方法
WO2020175540A1 (ja) * 2019-02-27 2020-09-03 京セラ株式会社 セルスタック装置、モジュールおよびモジュール収容装置

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