WO2024225476A1 - 固体電解質層、電気化学セル、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

固体電解質層、電気化学セル、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
WO2024225476A1
WO2024225476A1 PCT/JP2024/016584 JP2024016584W WO2024225476A1 WO 2024225476 A1 WO2024225476 A1 WO 2024225476A1 JP 2024016584 W JP2024016584 W JP 2024016584W WO 2024225476 A1 WO2024225476 A1 WO 2024225476A1
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Prior art keywords
particles
solid electrolyte
electrolyte layer
electrochemical cell
cell
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English (en)
French (fr)
Japanese (ja)
Inventor
一成 宮▲崎▼
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Kyocera Corp
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Kyocera Corp
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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
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • 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

Definitions

  • the present disclosure relates to solid electrolyte layers, electrochemical cells, electrochemical cell devices, modules, and module housing devices.
  • a fuel cell is a type of electrochemical cell that can generate electricity using a fuel gas such as a hydrogen-containing gas and an oxygen-containing gas such as air.
  • the solid electrolyte layer according to one aspect of the embodiment has a plurality of electrolyte particles including an oxide.
  • the plurality of electrolyte particles include first particles and second particles.
  • the first particles have a particle size that is 1/10 or more of the average thickness of the solid electrolyte layer.
  • the second particles have a particle size smaller than that of the first particles.
  • the electrochemical cell of the present disclosure also includes the solid electrolyte layer described above.
  • the electrochemical cell device disclosed herein also has a cell stack including the electrochemical cell described above.
  • 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, auxiliary equipment for operating the module, and an exterior case that houses the module and auxiliary equipment.
  • 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 cross-sectional view taken along line XX shown in FIG. 2A.
  • FIG. 2C is a top view illustrating an example of the electrochemical cell device according to the first embodiment.
  • FIG. 3 is an enlarged cross-sectional view of a region R1 shown in FIG. 1A.
  • FIG. 4 is an external perspective view illustrating an example of a module according to the first embodiment.
  • FIG. 5 is an exploded perspective view illustrating an example of a module housing device according to the first embodiment.
  • FIG. 6A is a cross-sectional view showing an example of an electrochemical cell device according to the second embodiment.
  • FIG. 6B is a cross-sectional view illustrating an example of an electrochemical cell according to the second embodiment.
  • FIG. 7 is an enlarged cross-sectional view of region R2 shown in FIG. 6B.
  • FIG. 8 is a perspective view illustrating an example of an electrochemical cell according to the third embodiment.
  • FIG. 9 is a partial cross-sectional view showing an example of the electrochemical cell shown in FIG. FIG.
  • FIG. 10 is an enlarged cross-sectional view of a region R3 shown in FIG.
  • FIG. 11A is a cross-sectional view illustrating an example of an electrochemical cell according to a fourth embodiment.
  • FIG. 11B is a cross-sectional view showing another example of the electrochemical cell according to the fourth embodiment.
  • FIG. 11C is a cross-sectional view showing another example of the electrochemical cell according to the fourth embodiment.
  • FIG. 12 is an enlarged cross-sectional view of a region R4 shown in FIG. 11A.
  • 13 is a diagram showing the evaluation results of Samples No. 1 to 4.
  • 14 is a diagram showing the evaluation results of Samples Nos. 5 to 8.
  • the above-mentioned fuel cell stack device had room for improvement in terms of performance.
  • 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, for example, 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 and has a pair of opposing flat surfaces, a first flat surface n1 and a second flat surface n2, and a pair of arc-shaped side surfaces m that connect the first flat surface n1 and the second flat surface n2.
  • the element portion 3 is located on the first flat surface n1 of the support substrate 2.
  • the element portion 3 has a fuel electrode 5 as a first electrode, a solid electrolyte layer 6, an intermediate layer 7, and an air electrode 8 as a second electrode.
  • 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 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 surfaces 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 fuel 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 section 3 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 referred to as stabilized zirconia.
  • the stabilized zirconia may also 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 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 Y, Yb, Sc, or Gd is dissolved, or may include BaZrO 3 in which Sc, Y, or Yb is dissolved. Details of the solid electrolyte layer 6 will be described later.
  • the intermediate layer 7 functions as a diffusion suppression layer.
  • the intermediate layer 7 makes it difficult for Sr (strontium) contained in the air electrode 8 (described later) to diffuse into the solid electrolyte layer 6, thereby making it difficult for an electrical resistance layer of SrZrO3 to be formed in the solid electrolyte layer 6.
  • the material of the intermediate layer 7 is not particularly limited as long as it generally prevents diffusion of elements between the air electrode 8 and the solid electrolyte layer 6.
  • 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
  • Gd gadolinium
  • Sm sinarium
  • the air electrode 8 is gas permeable.
  • the open porosity of the air electrode 8 may be, for example, 20% or more, and particularly in the range of 30% to 50%.
  • 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 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 (La, Sr) TiO3 -based oxide)
  • These materials are conductive and are not easily reduced or oxidized even when in 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 cross-sectional view taken along line XX shown in Figure 2A.
  • Figure 2C is a top view showing an example of the electrochemical cell device according to the first embodiment.
  • 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 body 15 and a gas tank 16.
  • the support body 15 and the gas tank 16, which are the support member 14, are made of, for example, metal.
  • 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 steam reforming the raw fuel.
  • fuel gas is produced by steam reforming, the fuel gas contains water vapor.
  • FIG. 2A has 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 support 15.
  • the gas tank 16 has two through holes on the top surface.
  • a support 15 is disposed in each through hole.
  • the internal space 22 is formed by one gas tank 16 and two supports 15.
  • the shape of the insertion hole 15a is, for example, an oval shape when viewed from above.
  • the length of the insertion hole 15a in the arrangement direction of the cells 1, i.e., the thickness direction T, is greater than the distance between the two end current collecting members 17 located at both ends of the cell stack 11.
  • the width of the insertion hole 15a is, for example, greater than the length of the cell 1 in the width direction W (see FIG. 1A).
  • the joint between the inner wall of the insertion hole 15a and the lower end of the cell 1 is filled with a fixing material 13 and solidified. This bonds and fixes the inner wall of the insertion hole 15a to the lower end of each of the multiple cells 1, and also bonds and fixes the lower ends of the cells 1 to each other.
  • the gas flow path 2a of each cell 1 communicates with the internal space 22 of the support member 14 at its lower end.
  • the fixing material 13 and the bonding material 21 may be made of a material with low electrical conductivity, such as glass.
  • Specific materials for the fixing material 13 and the bonding material 21 may include amorphous glass, and in particular, crystallized glass.
  • any of SiO 2 -CaO based, MgO-B 2 O 3 based, La 2 O 3 -B 2 O 3 -MgO based, La 2 O 3 -B 2 O 3 -ZnO based, SiO 2 -CaO-ZnO based materials may be used, and in particular, SiO 2 -MgO based materials may be used.
  • connection member 18 is interposed between adjacent cells 1 among the multiple cells 1.
  • the connection member 18 electrically connects the fuel electrode 5 of one adjacent cell 1 to the air electrode 8 of the other cell 1 in series. More specifically, the connection member 18 connects the interconnector 4 electrically connected to the fuel electrode 5 of one adjacent cell 1 to the air electrode 8 of the other cell 1.
  • an end current collecting member 17 is electrically connected to the cell 1 located on the outermost side in the arrangement direction of the multiple cells 1.
  • the end current collecting member 17 is connected to a conductive part 19 that protrudes to the outside of the cell stack 11.
  • the conductive part 19 collects electricity generated by power generation in the cell 1 and draws it out to the outside. Note that the end current collecting member 17 is not shown in FIG. 2A.
  • the cell stack device 10 may be a single battery in which two cell stacks 11A, 11B are connected in series.
  • the conductive portion 19 of the cell stack device 10 is divided into a positive terminal 19A, a negative terminal 19B, and a connection terminal 19C.
  • the positive terminal 19A is the positive electrode when the power generated by the cell stack 11 is output to the outside, and is electrically connected to the positive end current collector 17 of the cell stack 11A.
  • the negative terminal 19B is the negative electrode when the power generated by the cell stack 11 is output to the outside, and is electrically connected to the negative end current collector 17 of the cell stack 11B.
  • connection terminal 19C electrically connects the end current collecting member 17 on the negative electrode side of the cell stack 11A to the end current collecting member 17 on the positive electrode side of the cell stack 11B.
  • Fig. 3 is an enlarged cross-sectional view of a region R1 shown in Fig. 1A.
  • the solid electrolyte layer 6 has a first surface 6a and a second surface 6b located at both ends in the thickness direction T.
  • the first surface 6a is in contact with the fuel electrode 5.
  • the second surface 6b is in contact with the intermediate layer 7.
  • the solid electrolyte layer 6 has a plurality of electrolyte particles 61.
  • Each of the plurality of electrolyte particles 61 contains an oxide. Adjacent electrolyte particles 61 are separated by grain boundaries 60.
  • the electrolyte particles 61 include a first particle 61a and a second particle 61b.
  • the first particle 61a is an electrolyte particle 61 having a particle size of 1/10 or more of the average thickness of the solid electrolyte layer 6.
  • the second particle 61b is an electrolyte particle 61 having a particle size of less than 1/10 of the average thickness of the solid electrolyte layer 6. That is, when the average thickness of the solid electrolyte layer 6 is t, the first particle 61a has a particle size of (1/10)t or more, and the second particle 61b has a particle size of less than (1/10)t.
  • the second particle 61b is an electrolyte particle 61 having a smaller particle size than the first particle 61a.
  • the particle size of the electrolyte particle 61 is a circle equivalent diameter obtained by observing a cross section of the solid electrolyte layer 6.
  • the average particle size of the second particle 61b may be 1/5 or less of the average particle size of the first particle 61a.
  • the solid electrolyte layer 6 has a plurality of electrolyte particles 61 including first particles 61a and second particles 61b, which makes it difficult for gaps to form between adjacent electrolyte particles 61. This improves the bending strength of the solid electrolyte layer 6, for example, compared to a case in which the plurality of electrolyte particles 61 do not include second particles 61b. Furthermore, a cell 1 having such a solid electrolyte layer 6 has improved performance, for example.
  • the second particle 61b may include a second particle 61b that is in contact with two or more first particles 61a and surrounded by the two or more first particles 61a. This, for example, makes it easier to relieve stress generated inside the solid electrolyte layer 6, and further improves the bending strength of the solid electrolyte layer 6. Furthermore, according to the cell 1 having such a solid electrolyte layer 6, for example, the performance is further improved.
  • the second particle 61b that is in contact with two or more first particles 61a and surrounded by the two or more first particles 61a is simply referred to as the second particle 61b surrounded by two or more first particles 61a.
  • the second particle 61b may be in contact with the first particle 61a via a grain boundary phase.
  • the grain boundary phase may have a thickness equal to or less than the grain size of the second particle 61b.
  • the second particles 61b surrounded by two or more first particles 61a may be two or less second particles 61b that are in contact with each other. This makes it difficult for the movement of ions in the thickness direction T inside the solid electrolyte layer 6 to be impeded, improving ion conductivity, for example. Furthermore, a cell 1 having such a solid electrolyte layer 6 improves power generation performance, for example.
  • one or more first particles 61a may be located between the first surface 6a and the second particle 61b. Also, one or more first particles 61a may be located between the second surface 6b and the second particle 61b. In other words, the solid electrolyte layer 6 may have one or more first particles 61a between the first surface 6a and the second surface 6b and the second particle 61b. Or, the second particle 61b may not face the first surface 6a and the second surface 6b. In this way, the solid electrolyte layer 6 has second particles 61b located away from the first surface 6a and the second surface 6b.
  • a solid electrolyte layer 6 for example, compared to a case where the second particles 61b located away from the first surface 6a and the second surface 6b are not present, the stress generated inside the solid electrolyte layer 6 is more likely to be alleviated. As a result, the bending strength of the solid electrolyte layer 6 is improved. Furthermore, a cell 1 having such a solid electrolyte layer 6 can, for example, improve performance.
  • the second particles 61b located away from the first surface 6a and the second surface 6b may account for 90% or more in number.
  • the solid electrolyte layer 6 has a large number of second particles 61b located away from the first surface 6a and the second surface 6b, which, for example, makes it easier to relieve stress generated inside the solid electrolyte layer 6 and improves the bending strength of the solid electrolyte layer 6.
  • a cell 1 having such a solid electrolyte layer 6 can, for example, improve performance.
  • the multiple electrolyte particles 61 in the solid electrolyte layer 6 may contain 20% or less of the second particles 61b by number. This makes it less likely that the movement of ions in the thickness direction T inside the solid electrolyte layer 6 is hindered compared to when the multiple electrolyte particles 61 contain more than 20% of the second particles 61b, improving ion conductivity. Furthermore, a cell 1 having such a solid electrolyte layer 6 can improve, for example, power generation performance.
  • the multiple electrolyte particles 61 in the solid electrolyte layer 6 may contain 1% or more of the second particles 61b in terms of number ratio. This makes it easier for the stress generated inside the solid electrolyte layer 6 to be alleviated compared to, for example, a case in which the multiple electrolyte particles 61 contain less than 1% of the second particles 61b, and improves the bending strength of the solid electrolyte layer 6. Furthermore, a cell 1 having such a solid electrolyte layer 6 can, for example, improve performance.
  • the solid electrolyte layer 6 may have a porosity of 1% or less. This, for example, makes it difficult for the movement of ions in the thickness direction T inside the solid electrolyte layer 6 to be hindered, improving ion conductivity. Furthermore, a cell 1 having such a solid electrolyte layer 6 can, for example, improve power generation performance.
  • the average thickness t of the solid electrolyte layer 6 can be calculated using a cross-sectional photograph of the solid electrolyte layer 6.
  • the arrangement and particle size of the electrolyte particles 61 in the solid electrolyte layer 6 can be calculated based on the results of analysis using an electron backscatter diffraction (EBSD) method on a cross section of the solid electrolyte layer 6 intersecting the first surface 6a and the second surface 6b.
  • EBSD electron backscatter diffraction
  • a cross-sectional photograph of the solid electrolyte layer 6 is taken with an SEM at a magnification of, for example, 5000 times, and the obtained cross-sectional photograph is subjected to image analysis to calculate the particle size of each of the electrolyte particles 61 located in a region having 200 or more electrolyte particles 61 between the first surface 6a and the second surface 6b.
  • the particle size of the electrolyte particles 61 is calculated by, for example, measuring the area of the electrolyte particles 61 using image analysis software and converting the area into a circle equivalent diameter.
  • Fig. 4 is an external perspective view showing an example of a module according to a first embodiment.
  • Fig. 4 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 module 100 includes a storage container 101 and a cell stack device 10 stored in the storage container.
  • a reformer 102 is disposed above the cell stack device 10.
  • the reformer 102 reforms raw fuel such as natural gas or kerosene to generate fuel gas, which is then supplied to the cell 1.
  • the raw fuel is supplied to the reformer 102 through a raw fuel supply pipe 103.
  • the reformer 102 may also include a vaporizer 102a that vaporizes water, and a reformer 102b.
  • the reformer 102b includes a reforming catalyst (not shown) and reforms the raw fuel into fuel gas.
  • Such a reformer 102 can perform steam reforming, which is a highly efficient reforming reaction.
  • the fuel gas generated in the reformer 102 is then supplied to the gas flow path 2a (see Figure 1A) of the cell 1 through the gas flow pipe 20, the gas tank 16, and the support member 14.
  • 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 module 100 can be configured to house a cell stack device 10 having cells 1 whose performance is improved, thereby making it possible to make the module 100 have improved performance.
  • Fig. 5 is an exploded perspective view that illustrates an example of a module housing device according to the first embodiment.
  • the module housing device 110 according to this embodiment includes an outer case 111, the module 100 illustrated in Fig. 4, and auxiliary equipment (not illustrated).
  • the auxiliary equipment operates the module 100.
  • the module 100 and the auxiliary equipment are housed in the outer case 111. Note that some components are omitted in Fig. 5.
  • the exterior case 111 of the module accommodating device 110 shown in Figure 5 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 5, 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.
  • the module housing device 110 by providing the module 100 with improved performance in the module housing chamber 115, the module housing device 110 can be made to have improved performance.
  • a hollow flat support substrate is used, but the present invention can also be applied to a cell stack device that uses a cylindrical support substrate.
  • FIG. 6A Second Embodiment Next, an electrochemical cell and an electrochemical cell device according to a second embodiment will be described with reference to FIGS. 6A to 7.
  • FIG. 6A Second Embodiment
  • a so-called “vertical stripe type” in which only one element part including a fuel electrode, a solid electrolyte layer, and an air electrode is provided on the surface of a support substrate is exemplified, but the present invention can also be applied to a horizontal stripe type electrochemical cell device in which so-called “horizontal stripe type” electrochemical cells are arranged in which element parts are provided at multiple locations spaced apart from each other on the surface of a support substrate and adjacent element parts are electrically connected.
  • FIG. 6A is a cross-sectional view showing an example of an electrochemical cell device according to the second embodiment.
  • FIG. 6B is a transverse cross-sectional view showing an example of an electrochemical cell according to the second embodiment.
  • FIG. 7 is an enlarged cross-sectional view of region R2 shown in FIG. 6B.
  • multiple cells 1A extend in the length direction L from a pipe 22a that circulates fuel gas.
  • the cells 1A have multiple element parts 3 on a support substrate 2. Inside the support substrate 2, a gas flow path 2a is provided through which the fuel gas flows from the pipe 22a.
  • the cells 1A are also electrically connected to each other via connection members 31.
  • the connection members 31 are located between the element portions 3 of the cells 1A, and connect the adjacent cells 1A.
  • the cell 1A includes a support substrate 2, a pair of element portions 3, and a sealing portion 30.
  • the support substrate 2 is columnar and has a pair of opposing flat surfaces, a first flat surface n1 and a second flat surface n2, and a pair of arc-shaped side surfaces m connecting the first flat surface n1 and the second flat surface n2.
  • the pair of element portions 3 are positioned so as to face each other on the first flat surface n1 and the second flat surface n2 of the support substrate 2.
  • the sealing portion 30 is positioned so as to cover the side surface m of the support substrate 2.
  • the solid electrolyte layer 6 has a first surface 6a and a second surface 6b located at both ends in the thickness direction T.
  • the first surface 6a is in contact with the fuel electrode 5.
  • the second surface 6b is in contact with the intermediate layer 7.
  • the solid electrolyte layer 6 has a plurality of electrolyte particles 61 separated by grain boundaries 60. Each of the plurality of electrolyte particles 61 contains an oxide.
  • the multiple electrolyte particles 61 include first particles 61a and second particles 61b.
  • the first particles 61a are electrolyte particles 61 having a particle size of 1/10 or more of the average thickness of the solid electrolyte layer 6.
  • the second particles 61b are electrolyte particles 61 having a smaller particle size than the first particles 61a.
  • the first particles 61a have a particle size of (1/10)t or more
  • the second particles 61b have a particle size of less than (1/10)t.
  • the solid electrolyte layer 6 has a plurality of electrolyte particles 61 including first particles 61a and second particles 61b, which makes it difficult for gaps to form between adjacent electrolyte particles 61. This improves the bending strength of the solid electrolyte layer 6, for example, compared to a case in which the plurality of electrolyte particles 61 do not include second particles 61b. Furthermore, a cell 1A having such a solid electrolyte layer 6 has improved performance, for example.
  • Fig. 8 is a perspective view showing an example of an electrochemical cell according to the third embodiment
  • Fig. 9 is a partial cross-sectional view showing the example of the electrochemical cell shown in Fig. 8.
  • cell 1B has an element section 3B in which a fuel electrode 5, a solid electrolyte layer 6, an intermediate layer 7, and an air electrode 8 are stacked, and conductive members 91, 92.
  • a fuel electrode 5 a solid electrolyte layer 6, an intermediate layer 7, and an air electrode 8 are stacked
  • conductive members 91, 92 are electrically connected by conductive members 91, 92, which are adjacent metal layers.
  • the conductive members 91, 92 electrically connect adjacent cells 1B to each other, and have a gas flow path that supplies gas to the fuel electrode 5 or the air electrode 8.
  • cell 1B has a sealing material that hermetically seals the fuel gas flow path and the oxygen-containing gas flow path of the flat cell stack.
  • the sealing material is a fixing member 96 for the cell, and has a bonding material 93 and support members 94, 95 that are frames.
  • the bonding material 93 may be glass or a metal material such as silver solder.
  • the support member 94 may be a so-called separator that separates the fuel gas flow path from the oxygen-containing gas flow path.
  • the material of the support members 94, 95 may be, for example, a conductive metal or an insulating ceramic. Either or both of the support members 94, 95 may be made of an insulating material. If the support member 94 is made of metal, the support member 94 may be integrated with the conductive member 92. If the support member 95 is made of metal, the support member 95 may be integrated with the conductive member 91.
  • One of the support members 94, 95 is insulating, electrically insulating the two conductive members 91, 92 that sandwich the flat cell from each other.
  • FIG. 10 is an enlarged cross-sectional view of region R3 shown in FIG. 9.
  • the solid electrolyte layer 6 has a first surface 6a and a second surface 6b located at both ends in the thickness direction T.
  • the first surface 6a is in contact with the fuel electrode 5.
  • the second surface 6b is in contact with the intermediate layer 7.
  • the solid electrolyte layer 6 has a plurality of electrolyte particles 61 separated by grain boundaries 60. Each of the plurality of electrolyte particles 61 contains an oxide.
  • the multiple electrolyte particles 61 include first particles 61a and second particles 61b.
  • the first particles 61a are electrolyte particles 61 having a particle size of 1/10 or more of the average thickness of the solid electrolyte layer 6.
  • the second particles 61b are electrolyte particles 61 having a smaller particle size than the first particles 61a.
  • the first particles 61a have a particle size of (1/10)t or more
  • the second particles 61b have a particle size of less than (1/10)t.
  • the multiple electrolyte particles 61 include the first particles 61a and the second particles 61b, so that, for example, gaps are less likely to occur between adjacent electrolyte particles 61.
  • the bending strength of the solid electrolyte layer 6 is improved, for example, compared to a case in which the multiple electrolyte particles 61 do not include the second particles 61b.
  • a cell 1B having such a solid electrolyte layer 6 can, for example, improve performance.
  • Fig. 11A is a cross-sectional view showing an example of an electrochemical cell according to the fourth embodiment.
  • Fig. 11B and Fig. 11C are cross-sectional views showing another example of an electrochemical cell according to the fourth embodiment.
  • Fig. 12 is an enlarged view of a region R4 shown in Fig. 11A.
  • Fig. 12 can also be applied to the examples of Fig. 11B and Fig. 11C.
  • the cell 1C has an element section 3C in which a fuel electrode 5, a solid electrolyte layer 6, an intermediate layer 7, and an air electrode 8 are laminated, and a support substrate 2.
  • the support substrate 2 has a through hole or a fine hole at a portion in contact with the element section 3C, and has a member 120 located outside the gas flow path 2a.
  • the support substrate 2 can circulate gas between the gas flow path 2a and the element section 3C.
  • the support substrate 2 may be composed of, for example, one or more metal plates.
  • the material of the metal plate may contain chromium.
  • the metal plate may have a conductive coating layer.
  • the support substrate 2 electrically connects adjacent cells 1C to each other.
  • the element section 3C may be formed directly on the support substrate 2, or may be bonded to the support substrate 2 by a bonding material.
  • the side of the fuel electrode 5 is covered with a solid electrolyte layer 6, which airtightly seals the gas flow path 2a through which the fuel gas flows.
  • the side of the fuel electrode 5 may be covered and sealed with a dense glass or ceramic sealing material 9.
  • the sealing material 9 that covers the side of the fuel electrode 5 may have electrical insulating properties.
  • gas flow path 2a of the support substrate 2 may be formed by a member 120 having projections and recesses as shown in FIG. 11C.
  • the solid electrolyte layer 6 has a first surface 6a and a second surface 6b located at both ends in the thickness direction T.
  • the first surface 6a is in contact with the fuel electrode 5.
  • the second surface 6b is in contact with the intermediate layer 7.
  • the solid electrolyte layer 6 has a plurality of electrolyte particles 61 separated by grain boundaries 60. Each of the plurality of electrolyte particles 61 contains an oxide.
  • the multiple electrolyte particles 61 include first particles 61a and second particles 61b.
  • the first particles 61a are electrolyte particles 61 having a particle size of 1/10 or more of the average thickness of the solid electrolyte layer 6.
  • the second particles 61b are electrolyte particles 61 having a smaller particle size than the first particles 61a.
  • the first particles 61a have a particle size of (1/10)t or more
  • the second particles 61b have a particle size of less than (1/10)t.
  • the solid electrolyte layer 6 has a plurality of electrolyte particles 61 including first particles 61a and second particles 61b, which makes it difficult for gaps to form between adjacent electrolyte particles 61. This improves the bending strength of the solid electrolyte layer 6, for example, compared to a case in which the plurality of electrolyte particles 61 do not include second particles 61b. Furthermore, a cell 1C having such a solid electrolyte layer 6 has improved performance, for example.
  • a solid oxide 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 a solid oxide electrolytic cell, an electrolytic cell stack device, an electrolytic module, and an electrolytic device, respectively.
  • the electrolytic cell has a first electrode and a second electrode, 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 can improve performance.
  • Samples No. 1 to 8 were created to mimic solid electrolyte layer 6, and their performance was evaluated.
  • Samples No. 1 to 8 were prepared using particulate electrolyte materials with different particle sizes.
  • electrolyte materials with different particle sizes two types of ZrO 2 materials (YSZ materials) in which Y 2 O 3 is dissolved at 8 mol % were prepared.
  • the two types of YSZ materials are material A with an average particle size of 2 ⁇ m and material B with an average particle size of 0.5 ⁇ m.
  • Two types of slurries were prepared using material A, material B, a solvent, and a dispersant. Slurry A was obtained by disintegrating material A together with a solvent and a dispersant in a ball mill for 10 hours.
  • Slurry B was obtained by disintegrating material B together with a solvent and a dispersant in a ball mill for 0.5 hours. The disintegration time was shortened for slurry B so that some of the particle aggregates remained.
  • the aggregated particles of material B are not easily absorbed by the particles of material A even when mixed with material A and fired, and tend to remain as second particles 61b in the solid electrolyte layer 6.
  • Slurry A and slurry B were mixed in the following ratios and dried to obtain mixed powders.
  • the mixing ratios of slurry A and slurry B, expressed as the mass ratio of material A to material B (A:B), were as follows for samples No. 1 and 5 (100:0), sample No. 2 and 6 (98:2), sample No. 3 and 7 (97:3), and sample No. 4 and 8 (95:5).
  • the mixed powder thus prepared was used to prepare test pieces (samples No. 1 to 4) for bending strength tests.
  • the mixed powder was uniaxially pressed to produce rectangular prism-shaped bodies.
  • the obtained bodies were sintered at 1500°C in air to produce sintered bodies with different contents of second particles 61b.
  • the resistance of the solid electrolyte layer 6 was evaluated by preparing single cells (samples No. 5 to 8) having a solid electrolyte layer 6 using the above-mentioned mixed powder, an anode 5, an intermediate layer 7, and an air electrode 8.
  • the laminated sheet was made by laminating a solid electrolyte sheet prepared using the above-mentioned mixed powder on an anode molded sheet, and was degreased and fired in air at 1500°C to obtain a laminated sintered body.
  • the solid electrolyte layer of the obtained laminated sintered body was coated with a slurry for the intermediate layer, degreased, and fired in air at 1350°C.
  • the formed intermediate layer was further coated with a slurry for the air electrode, degreased, and fired in air at 1150°C to obtain single cells having a solid electrolyte layer 6 with a different content of second particles 61b.
  • Fig. 13 is a diagram showing the evaluation results of Samples No. 1 to 4.
  • the content of the second particles 61b is the number ratio of the second particles 61b to the electrolyte particles 61 in each of Samples No. 1 to 4 in which the cross section was observed.
  • the bending strength is a four-point bending strength measured in accordance with JIS R 1601.
  • samples No. 2 to 4 which contained first particles 61a and second particles 61b, had higher bending strength than sample No. 1, which contained only first particles 61a. Furthermore, in samples No. 2 to 4, as the content of second particles 61b increased, the bending strength also increased accordingly.
  • Fig. 14 is a diagram showing the evaluation results of Samples No. 5 to 8.
  • the content of the second particles 61b is the number ratio of the second particles 61b to the electrolyte particles 61 in the solid electrolyte layer 6 of each of Samples No. 5 to 8 observed in cross section.
  • the resistance is an ohmic resistance measured by an AC impedance method.
  • the solid electrolyte layer is a solid electrolyte layer having a plurality of electrolyte particles including an oxide
  • the plurality of electrolyte particles include first particles having a particle size that is 1/10 or more of an average thickness of the solid electrolyte layer; and second particles having a smaller particle size than the first particles.
  • the solid electrolyte layer according to (1) above has a first surface and a second surface located at both ends in a thickness direction, In a cross section intersecting the first surface and the second surface, the second particle may include a second particle that is in contact with two or more of the first particles and is surrounded by the two or more first particles.
  • the two or more first particles may surround two or less of the surrounded second particles that are in contact with each other.
  • the electrochemical cell includes any one of the solid electrolyte layers (1) to (6) above.
  • the (8) electrochemical cell device has a cell stack including the electrochemical cell of (7) above.
  • the module (9) comprises the electrochemical cell device (8) described above, and a container for housing the electrochemical cell device.
  • the module housing device (10) includes the module (9) and Auxiliary equipment for operating the module; and an exterior case that houses the module and the auxiliary equipment.

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Publication number Priority date Publication date Assignee Title
JP2004355928A (ja) * 2003-05-28 2004-12-16 Kyocera Corp 電気化学素子及びその製法
JP2014026926A (ja) * 2012-07-30 2014-02-06 Kyocera Corp 固体酸化物形燃料電池セルおよびセルスタック装置ならびに燃料電池モジュール
JP2016534966A (ja) * 2013-08-01 2016-11-10 エルジー・ケム・リミテッド 無機酸化物粉末、およびその焼結体を含む電解質

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004355928A (ja) * 2003-05-28 2004-12-16 Kyocera Corp 電気化学素子及びその製法
JP2014026926A (ja) * 2012-07-30 2014-02-06 Kyocera Corp 固体酸化物形燃料電池セルおよびセルスタック装置ならびに燃料電池モジュール
JP2016534966A (ja) * 2013-08-01 2016-11-10 エルジー・ケム・リミテッド 無機酸化物粉末、およびその焼結体を含む電解質

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