Electrochemical cell, electrochemical cell device, module, and module housing device

Abstract

An electrochemical cell includes a first electrode layer, a second electrode layer, a solid electrolyte layer, and an intermediate layer. The solid electrolyte layer is located between the first electrode layer and the second electrode layer. The intermediate layer is located between the solid electrolyte layer and the first electrode layer and contains Ce. In addition, the electrochemical cell contains Al at the boundary between the solid electrolyte layer and the intermediate layer.

Description

Technical Field

[0001] The present disclosure relates to an electrochemical cell, an electrochemical cell device, a module, and a module receiving device. Background Art

[0002] In recent years, various fuel cell stack devices including a plurality of fuel cells have been proposed as next-generation energy sources. A fuel cell is a type of cell that can generate electricity using a fuel gas such as a hydrogen-containing gas and an oxygen-containing gas such as air.

[0003] Prior Art Literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2017-147030 Summary of the invention

[0006] An electrochemical cell according to one embodiment includes a first electrode layer, a second electrode layer, a solid electrolyte layer, and an intermediate layer. The solid electrolyte layer is located between the first electrode layer and the second electrode layer. The intermediate layer is located between the solid electrolyte layer and the first electrode layer and contains Ce. The electrochemical cell contains Al at a boundary between the solid electrolyte layer and the intermediate layer.

[0007] Furthermore, the electrochemical cell device of the present disclosure includes a cell stack including the electrochemical cell described above.

[0008] Furthermore, a module of the present disclosure includes: the electrochemical cell device described above; and a storage container for storing the electrochemical cell device.

[0009] Furthermore, the module housing device of the present disclosure includes: the module described above; an auxiliary machine for operating the module; and an outer casing for housing the module and the auxiliary machine. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1A This is a cross-sectional view showing an example of the electrochemical cell according to the first embodiment.

[0011] Figure 1B This is a side view of an example of the electrochemical cell according to the first embodiment as viewed from the air electrode side.

[0012] Figure 1C This is a side view of an example of the electrochemical cell according to the first embodiment as viewed from the interconnector side.

[0013] Figure 2A It is a perspective view showing an example of the electrochemical cell device according to the first embodiment.

[0014] Figure 2B yes Figure 2A A cross-sectional view along line XX is shown.

[0015] Figure 2C It is a top view showing an example of the electrochemical cell device according to the first embodiment.

[0016] Figure 3 Yes Figure 1A An enlarged cross-sectional view of region R1 is shown.

[0017] Figure 4 It is an external perspective view showing an example of the module according to the first embodiment.

[0018] Figure 5 It is an exploded perspective view schematically showing an example of the module housing device according to the first embodiment.

[0019] Figure 6 It is a cross-sectional view showing an example of an electrochemical cell device according to the second embodiment.

[0020] Figure 7 It is a cross-sectional view showing an electrochemical cell according to a second embodiment.

[0021] Figure 8 Yes Figure 7 An enlarged cross-sectional view of region R2 is shown.

[0022] Fig. 9 It is a perspective view showing an example of an electrochemical cell according to a third embodiment.

[0023] Fig.10 yes Fig. 9 A partial cross-sectional view of an electrochemical cell is shown.

[0024] Fig.11 Yes Fig.10 An enlarged cross-sectional view of region R3 is shown.

[0025] Fig. 12A This is a cross-sectional view showing an example of an electrochemical cell according to a fourth embodiment.

[0026] Fig. 12B This is a cross-sectional view showing another example of the electrochemical cell according to the fourth embodiment.

[0027] Fig. 12C This is a cross-sectional view showing another example of the electrochemical cell according to the fourth embodiment.

[0028] Fig.13 Yes Fig. 12A An enlarged cross-sectional view of region R4 is shown. DETAILED DESCRIPTION

[0029] In the above-mentioned fuel cell stack device, there is still room for improvement in terms of improving power generation performance.

[0030] Therefore, it is desired to provide an electrochemical cell, an electrochemical cell device, a module, and a module housing device that can improve performance.

[0031] Embodiments of the electrochemical cell, electrochemical cell device, module, and module storage device disclosed in the present application will be described in detail below with reference to the accompanying drawings. The present disclosure is not limited to the embodiments described below.

[0032] In addition, it should be noted that the drawings are schematic, and the relationship between the dimensions of each element, the ratio of each element, etc. may be different from the actual. Furthermore, the drawings may also contain different parts such as the relationship between the dimensions and the ratio.

[0033] [First embodiment]

[0034] <Structure of Electrochemical Cell>

[0035] First, refer to Figure 1A to Figure 1C The electrochemical cell involved in the first embodiment is described using an example of a solid oxide fuel cell. The electrochemical cell device may include a cell stack having a plurality of electrochemical cells. The electrochemical cell device having a plurality of electrochemical cells is referred to as a cell stack device.

[0036] Figure 1A This is a cross-sectional view showing an example of the electrochemical cell according to the first embodiment. Figure 1B This is a side view of an example of the electrochemical cell according to the first embodiment as viewed from the air electrode side. Figure 1C This is a side view of an example of the electrochemical cell according to the first embodiment as viewed from the interconnector side. Figure 1A to Figure 1C A portion of each structure of an electrochemical cell is shown in an enlarged manner. Hereinafter, an electrochemical cell may be simply referred to as a cell.

[0037] exist Figure 1A to Figure 1C In the example shown, the single cell 1 is a hollow flat plate type, and is in the shape of an elongated plate. Figure 1B As shown, the overall shape of the cell 1 when viewed from the side is, for example, a rectangle with a side length of 5 to 50 cm in the longitudinal direction L and a length of 1 to 10 cm in the width direction W perpendicular to the longitudinal direction L. The overall thickness of the cell 1 in the thickness direction T is, for example, 1 to 5 mm.

[0038] like Figure 1AAs shown, the cell 1 includes a conductive support substrate 2, an element portion 3, and an interconnector 4. The support substrate 2 is a column having a pair of opposing flat surfaces, namely, a first surface n1 and a second surface n2, and a pair of arc-shaped side surfaces m connecting the first surface n1 and the second surface n2.

[0039] The element portion 3 is located on the first surface n1 of the support substrate 2. The element portion 3 includes a fuel electrode 5, a solid electrolyte layer 6, an intermediate layer 7, and an air electrode 8.

[0040] In addition, if Figure 1B As shown in FIG. 1 , the air electrode 8 does not extend to the lower end of the cell 1. At the lower end of the cell 1, only the solid electrolyte layer 6 is exposed on the surface of the first surface n1. Figure 1C As shown in FIG. 1 , the interconnector 4 may also extend to the lower end of the cell 1. At the lower end of the cell 1, the interconnector 4 and the solid electrolyte layer 6 are exposed on the surface. Figure 1A As shown, the solid electrolyte layer 6 is exposed on the surface of the pair of arc-shaped side surfaces m of the unit cell 1. The interconnector 4 may not extend to the lower end of the unit cell 1.

[0041] Hereinafter, each member constituting the cell 1 will be described.

[0042] The support substrate 2 has a gas flow path 2 a inside thereof through which a gas flows. Figure 1A The example of the support substrate 2 shown 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 the fuel electrode 5. The support substrate 2 may also have conductivity. The conductive support substrate 2 collects the electricity generated in the element part 3 to the interconnector 4.

[0043] 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 (scandium), Y (yttrium), La (lanthanum), Nd (neodymium), Sm (samarium), Gd (gadolinium), Dy (dysprosium), and Yb (ytterbium).

[0044] The fuel electrode 5 can be made of a generally known material. The fuel electrode 5 can be made of a porous conductive ceramic, for example, ZrO containing calcium oxide, magnesium oxide, or a rare earth element oxide dissolved therein. 2 , and ceramics of Ni and / or NiO. The rare earth element oxide may contain, for example, a plurality of rare earth elements selected from Sc, Y, La, Nd, Sm, Gd, Dy and Yb. Sometimes, ZrO2 in which calcium oxide, magnesium oxide or rare earth element oxide is dissolved is used. 2It is called stabilized zirconia. Stabilized zirconia may also contain partially stabilized zirconia.

[0045] The solid electrolyte layer 6 is an electrolyte, and exchanges ions between the fuel electrode 5 and the air electrode 8. The solid electrolyte layer 6 has a gas barrier property, and thus the fuel gas and the oxygen-containing gas are unlikely to leak.

[0046] The material of the solid electrolyte layer 6 can be, for example, ZrO in which 3 mol % to 15 mol % of a rare earth element oxide is solid-dissolved. 2 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 in which Yb, Sc, or Gd is dissolved. 2 , and may also contain BaZrO in which Sc or Yb is dissolved 3 .

[0047] The intermediate layer 7 has a function 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, and thus it is difficult to form SrZrO in the solid electrolyte layer 6. 3 resistance layer.

[0048] The intermediate layer 7 contains Ce (cerium). For example, the material of the intermediate layer 7 contains cerium oxide (CeO) in which a rare earth element other than Ce (cerium) is solid-dissolved. 2 ). As the related rare earth elements, Gd (gadolinium), Sm (samarium), etc. can be used.

[0049] The air electrode 8 has gas permeability. The open porosity of the air electrode 8 is, for example, 20% or more, particularly in the range of 30% to 50%.

[0050] The material of the air electrode 8 is not particularly limited as long as it is a material generally used in air electrodes. The material of the air electrode 8 can be, for example, so-called ABO 3 Conductive ceramics such as perovskite oxides.

[0051] 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. Examples of such a composite oxide include La x Sr 1-x Co y Fe 1-y O 3 ,La x Sr 1-x MnO 3 ,La x Sr 1-x FeO 3 ,La x Sr1-x CoO 3 etc. In addition, 0 < x < 1 and 0 < y < 1.

[0052] In addition, the interconnector 4 is dense and it is difficult to generate leakage of fuel gas flowing through the gas flow path 2a inside the support substrate 2 and oxygen-containing gas flowing outside the support substrate 2. The interconnector 4 may have a relative density of 93% or more, particularly 95% or more.

[0053] As the material of the interconnector 4, perovskite-type oxides of the lanthanum chromate series (LaCrO 3 series oxides), perovskite-type oxides of the lanthanum strontium titanate series (LaSrTiO 3 series oxides), etc. can be used. These materials have conductivity and are neither reduced nor oxidized even when in contact with fuel gases such as hydrogen-containing gases and oxygen-containing gases such as air.

[0054] <Structure of the Electrochemical Single Cell Device>

[0055] Next, with reference to Figure 2A to Figure 2C the electrochemical single cell device according to the present embodiment using the above single cell 1 will be described. Figure 2A FIG. is a perspective view showing an example of the electrochemical single cell device according to the first embodiment. Figure 2B is Figure 2A a cross-sectional view taken along the line X-X shown in FIG. Figure 2C FIG. is a top view showing an example of the electrochemical single cell device according to the first embodiment.

[0056] As Figure 2A shown, the single cell stack device 10 includes: a single cell stack 11 having a plurality of single cells 1 arranged (stacked) in the thickness direction T ( Figure 1A reference) of the single cell 1; and a fixing member 12.

[0057] The fixing member 12 has a fixing piece 13 and a supporting member 14. The supporting member 14 supports the single cell 1. The fixing piece 13 fixes the single cell 1 to the supporting member 14. In addition, the supporting member 14 has a support body 15 and a gas tank 16. The support body 15 and the gas tank 16 of the supporting member 14 are, for example, made of metal.

[0058] As Figure 2B shown, the support body 15 has insertion holes 15a into which the lower ends of the plurality of single cells 1 are inserted. The lower ends of the plurality of single cells 1 and the inner walls of the insertion holes 15a are joined by the fixing piece 13.

[0059] The gas tank 16 has an opening for supplying reaction gas to the plurality of cells 1 through the insertion hole 15a and a groove 16a around the opening. The end of the outer periphery of the support body 15 is joined to the gas tank 16 by a joint 21 filled in the groove 16a of the gas tank 16.

[0060] exist Figure 2A In the example shown, fuel gas is stored in an internal space 22 formed by a support body 15 as a support member 14 and a gas tank 16. A gas flow pipe 20 is connected to the gas tank 16. The fuel gas is supplied to the gas tank 16 through the gas flow pipe 20, and is supplied from the gas tank 16 to a gas flow path 2a (see FIG. 2 ) inside the single cell 1. Figure 1A The fuel gas supplied to the gas tank 16 is reformed in the reformer 102 (see Figure 4 )generate.

[0061] The hydrogen-rich fuel gas can be produced by steam reforming the raw fuel, etc. When the fuel gas is produced by steam reforming, the fuel gas contains water vapor.

[0062] exist Figure 2A In the example shown, there are two rows of single cell stacks 11, two supports 15, and a gas tank 16. The two rows of single cell stacks 11 each have a plurality of single cells 1. Each single cell stack 11 is fixed to each support 15. The gas tank 16 has two through holes on the upper surface. Each support 15 is arranged in each through hole. The internal space 22 is formed by one gas tank 16 and two supports 15.

[0063] The shape of the insertion hole 15a is, for example, an oblong 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 width direction W of the cell 1 (see Figure 1A ) length.

[0064] like Figure 2B As shown in the figure, the fixing material 13 is filled in the joint between the inner wall of the insertion hole 15a and the lower end of the single cell 1 and cured. Thus, the inner wall of the insertion hole 15a and the lower ends of the plurality of single cells 1 are joined and fixed, respectively, and the lower ends of the single cells 1 are joined and fixed to each other. The gas flow path 2a of each single cell 1 communicates with the internal space 22 of the support member 14 at the lower end.

[0065] A material with low conductivity such as glass can be used for the fixing member 13 and the bonding member 21. As specific materials of the fixing member 13 and the bonding member 21, amorphous glass and the like can be used, and in particular, crystallized glass and the like can be used.

[0066] As the crystallized glass, for example, SiO2 -CaO series, MgO-B 2 O 3 Department, La 2 O 3 -B 2 O 3 -MgO series, La 2 O 3 -B 2 O 3 -ZnO series, SiO 2 -CaO-ZnO and other materials, especially SiO 2 -MgO-based materials.

[0067] In addition, if Figure 2B As shown, the connecting member 18 is interposed between adjacent cells 1 among the plurality of cells 1. The connecting member 18 electrically connects the fuel electrode 5 of one adjacent cell 1 and the air electrode 8 of another cell 1 in series. More specifically, the connecting member 18 connects the interconnector 4 electrically connected to the fuel electrode 5 of one adjacent cell 1 and the air electrode 8 of another cell 1.

[0068] In addition, if Figure 2B As shown in FIG. 1 , the outermost cell 1 in the arrangement direction of the plurality of cells 1 is electrically connected to an end current collecting member 17. The end current collecting member 17 is connected to a conductive portion 19 protruding to the outside of the cell stack 11. The conductive portion 19 collects the electricity generated by the cell 1 and leads it to the outside. Figure 2A In the figure, the end current collecting member 17 is omitted.

[0069] In addition, if Figure 2C As shown, the cell stack device 10 may be a battery in which two cell stacks 11A and 11B are connected in series. In this case, 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.

[0070] The positive terminal 19A is a positive electrode for outputting the electric power generated by the cell stack 11 to the outside, and is electrically connected to the end current collecting member 17 on the positive electrode side of the cell stack 11A. The negative terminal 19B is a negative electrode for outputting the electric power generated by the cell stack 11 to the outside, and is electrically connected to the end current collecting member 17 on the negative electrode side of the cell stack 11B.

[0071] The connection terminal 19C electrically connects the end current collecting member 17 on the negative electrode side in the cell stack 11A and the end current collecting member 17 on the positive electrode side in the cell stack 11B.

[0072] <Details of the components section>

[0073] Next, refer to Figure 3 The element unit 3 included in the electrochemical cell according to the first embodiment will be described in detail. Figure 3 Yes Figure 1A An enlarged cross-sectional view of region R1 is shown.

[0074] like Figure 3 As shown in FIG. 1 , the cell 1 contains Al at the boundary 41 between the solid electrolyte layer 6 and the intermediate layer 7. The boundary 41 includes the boundary 40 between the solid electrolyte layer 6 and the intermediate layer 7, and is a region where the distance from the boundary 40 to the boundary 40 in the thickness direction is 100 nm or less. In the boundary 40, the detected amount (atomic %) of Zr and the detected amount (atomic %) of Ce in elemental analysis are equal. For example, the boundary 41 may contain Al. 2 O 3 .

[0075] By containing Al in the boundary portion 41 between the solid electrolyte layer 6 and the intermediate layer 7, for example, during the manufacture of the element portion 3 or at high temperatures, the Zr component contained in the solid electrolyte layer 6 and the Ce component contained in the intermediate layer 7 are difficult to diffuse into each other. Therefore, since it is difficult to generate a composition having insulating properties of Zr and Ce inside the solid electrolyte layer 6 and / or the intermediate layer 7, the power generation performance of the single cell 1 can be improved. The content of Al contained in the boundary portion 41 is sufficient to be above the detection limit. In addition, the composition of the boundary portion 41 can be measured in the cross section of the element portion 3 using, for example, a SEM (scanning electron microscope) or a TEM (transmission electron microscope), and an EDX (energy dispersive X-ray analyzer).

[0076] For example, a sample of the present embodiment containing Al at the boundary 41 and another sample not containing Al at the boundary 41 are prepared, and a line analysis of the elements is performed with the boundary 41 clamped by TEM and EDX. In the sample of the present embodiment, at the boundary 41, Al is detected at a maximum of 4 atomic %, and the thickness of the portion containing 10 atomic % or more of Ce and Zr is approximately 100 nm. On the other hand, in the other samples, the thickness of the portion containing 10 atomic % or more of Al, Ce, and Zr is not detected at the boundary 41 is approximately 300 nm. The portion containing 10 atomic % or more of Ce and Zr can be regarded as an insulating composition having Zr and Ce.

[0077] Boundary portion 41 may contain Al uniformly throughout the entire boundary portion 41 , or may have a portion where Al is not provided. In addition, solid electrolyte layer 6 and / or intermediate layer 7 other than boundary portion 41 may contain Al.

[0078] The boundary portion 41 may include a solid solution portion 42 containing Al. The solid solution portion 42 may include, for example, Al 2 O3 and ZrO 2 Solid solution of Al 2 O 3 and CeO 2 The solid solution portion 42 may have Al 2 O 3 、ZrO 2 and CeO 2 of solid solution.

[0079] In this way, for example, Al can be sandwiched between the material of the solid electrolyte layer 6 and the material of the intermediate layer 7. 2 O 3 The Al component is sintered to form a structure containing Al in the boundary portion 41 between the solid electrolyte layer 6 and the intermediate layer 7. The method for making the boundary portion 41 and the solid solution portion 42 is not limited, and they can be made by any method.

[0080] <Module>

[0081] Next, use Figure 4 A module according to an embodiment of the present disclosure using the above-described electrochemical cell device will be described. Figure 4 1 is a perspective view showing the appearance of a module according to the first embodiment. Figure 4 , a state is shown in which the front and rear surfaces, which are part of the storage container 101, are removed and the single cell stack device 10 of the fuel cell accommodated inside is taken out to the rear.

[0082] like Figure 4 As shown, the module 100 includes a storage container 101 and a cell stack device 10 stored in the storage container. In addition, a reformer 102 is arranged above the cell stack device 10 .

[0083] The related reformer 102 reforms the raw fuel such as natural gas and kerosene to generate fuel gas and supplies it to the single cell 1. The raw fuel is supplied to the reformer 102 through the raw fuel supply pipe 103. In addition, the reformer 102 can include: a gasification section 102a for gasifying water; and a reforming section 102b. The reforming section 102b includes a reforming catalyst (not shown) to reform the raw fuel into fuel gas. Such a reformer 102 can perform steam reforming as a highly efficient reforming reaction.

[0084] Then, the fuel gas generated in the reformer 102 is supplied to the gas flow path 2a (refer to Figure 1A ).

[0085] In the module 100 having the above-described structure, the temperature inside the module 100 during power generation usually reaches about 500° C. to 1000° C. as the gas is combusted and the unit cells 1 generate power.

[0086] In such a module 100 , as described above, by accommodating the cell stack device 10 with improved power generation performance, it is possible to provide a module 100 with improved power generation performance.

[0087] <Module Storage Device>

[0088] Figure 5 1 is an exploded perspective view showing an example of a module storage device according to the first embodiment. The module storage device 110 according to this embodiment includes: an outer casing 111; Figure 4 The module 100 shown in the figure and the auxiliary machine not shown in the figure. The auxiliary machine operates the module 100. The module 100 and the auxiliary machine are accommodated in the outer casing 111. Figure 5 In the figure, a part of the structure is omitted.

[0089] Figure 5 The outer casing 111 of the module storage device 110 shown in the figure has a support 112 and an outer plate 113. The partition plate 114 divides the outer casing 111 into upper and lower areas. The space above the partition plate 114 in the outer casing 111 is a module storage chamber 115 for storing the module 100, and the space below the partition plate 114 in the outer casing 111 is an auxiliary machine storage chamber 116 for storing auxiliary machines of the operating module 100. Figure 5 In the figure, the auxiliary machines accommodated in the auxiliary machine accommodation chamber 116 are omitted.

[0090] The partition plate 114 has an air flow port 117 for allowing air in the auxiliary machine accommodation chamber 116 to flow to the module accommodation chamber 115. The exterior plate 113 constituting the module accommodation chamber 115 has an exhaust port 118 for exhausting air in the module accommodation chamber 115.

[0091] In such a module housing device 110 , as described above, by providing the module 100 with improved power generation performance in the module housing chamber 115 , it is possible to provide the module housing device 110 with improved power generation performance.

[0092] Furthermore, in the above-described embodiment, an example is given of a case where a hollow flat-plate-type support substrate is used, but the present invention can also be applied to a cell stack device using a cylindrical-type support substrate.

[0093] [Second embodiment]

[0094] Next, refer to Figure 6 to Figure 8 An electrochemical cell and an electrochemical cell device according to a second embodiment will be described.

[0095] In the above-mentioned embodiment, a so-called "vertical stripe type" is exemplified in which only one element portion including a fuel electrode, a solid electrolyte layer and an air electrode is provided on the surface of a supporting substrate. However, it 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 portions are provided at a plurality of locations separated from each other on the surface of a supporting substrate and adjacent element portions are electrically connected.

[0096] Figure 6 It is a cross-sectional view showing an example of an electrochemical cell device according to the second embodiment. Figure 7 It is a cross-sectional view showing an electrochemical cell according to a second embodiment. Figure 8 yes Figure 7 An enlarged view of region R2 is shown.

[0097] like Figure 7 As shown, in the cell stack device 10A, a plurality of cells 1A extend from a pipe 22a through which fuel gas flows in a longitudinal direction L. The cell 1A has a plurality of element portions 3 on a support substrate 2. A gas flow path 2a is provided inside the support substrate 2 through which fuel gas flows from the pipe 22a.

[0098] Furthermore, the cells 1A are electrically connected to each other via a connection member 31. The connection member 31 is located between the element portions 3 included in each cell 1A, and connects the adjacent cells 1A.

[0099] In addition, if Figure 7 As shown, the cell 1A according to the second embodiment includes a support substrate 2, a pair of element portions 3, and a sealing portion 30. The support substrate 2 is a columnar structure having a pair of opposing flat surfaces, namely, a first surface n1 and a second surface n2, and a pair of arc-shaped side surfaces m connecting the first surface n1 and the second surface n2.

[0100] The pair of element portions 3 are provided on the first surface n1 and the second surface n2 of the support substrate 2 so as to face each other. In addition, the sealing portion 30 is provided so as to cover the side surface m of the support substrate 2 .

[0101] like Figure 8 As shown in FIG. 1 , Al is contained in the boundary 41 between the solid electrolyte layer 6 and the intermediate layer 7. The boundary 41 includes the boundary 40 between the solid electrolyte layer 6 and the intermediate layer 7, and is a region where the distance from the boundary 40 to the boundary 40 in the thickness direction is 100 nm or less. For example, the boundary 41 may contain Al. 2 O 3 Furthermore, the boundary portion 41 may have a solid solution portion 42 containing Al.

[0102] Thus, by containing Al in the boundary portion 41 between the solid electrolyte layer 6 and the intermediate layer 7, for example, during the manufacture of the element portion 3 or at high temperatures, the Zr component contained in the solid electrolyte layer 6 and the Ce component contained in the intermediate layer 7 are difficult to diffuse into each other. Therefore, since it is difficult to generate an insulating composition having Zr and Ce inside the solid electrolyte layer 6 and / or the intermediate layer 7, the power generation performance of the single cell 1A can be improved.

[0103] [Third embodiment]

[0104] Fig. 9 It is a perspective view showing an example of an electrochemical cell according to a third embodiment. Fig.10 yes Fig. 9 A partial cross-sectional view of an electrochemical cell is shown.

[0105] like Fig. 9 , Fig.10 As shown, the cell 1B has: an element portion 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. In an electrochemical cell device in which a plurality of flat-plate cells are stacked, for example, a plurality of cells 1B 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 for supplying gas to the fuel electrode 5 or the air electrode 8.

[0106] like Fig.10 As shown, the cell 1B has a seal that hermetically seals the flow path of the fuel gas and the flow path of the oxygen-containing gas of the flat cell stack. The seal is a fixing member 96 of the cell and has a bonding member 93 and supporting members 94 and 95 as a frame. The bonding member 93 can be glass or a metal material such as silver solder.

[0107] The support member 94 may be a so-called spacer that divides the flow path of the fuel gas and the flow path of the oxygen-containing gas. The material of the support members 94 and 95 may be, for example, a conductive metal or an insulating ceramic. The support members 94 and 9 may be both or either of them insulating materials. When the support member 94 is metal, the support member 94 may be integrated with the conductive member 92. When the support member 95 is metal, the support member 95 may be integrated with the conductive member 91.

[0108] The joint member 93 and any one of the support members 94 and 95 is insulating, and electrically insulates the two conductive members 91 and 92 sandwiching the flat-type battery cell from each other.

[0109] Fig.11 Yes Fig.10 The enlarged cross-sectional view of the region R3 shown in FIG. Fig.11As shown, the cell 1B contains Al at the boundary 41 between the solid electrolyte layer 6 and the intermediate layer 7. The boundary 41 includes the boundary 40 between the solid electrolyte layer 6 and the intermediate layer 7, and is a region where the distance from the boundary 40 to the boundary 40 in the thickness direction is 100 nm or less. The boundary 41 may contain Al, for example. 2 O 3 Furthermore, the boundary portion 41 may have a solid solution portion 42 containing Al.

[0110] Thus, by containing Al in the boundary portion 41 between the solid electrolyte layer 6 and the intermediate layer 7, for example, during the manufacture of the element portion 3B or at high temperatures, the Zr component contained in the solid electrolyte layer 6 and the Ce component contained in the intermediate layer 7 are difficult to diffuse into each other. Therefore, since it is difficult to generate an insulating composition having Zr and Ce inside the solid electrolyte layer 6 and / or the intermediate layer 7, the power generation performance of the single cell 1B can be improved.

[0111] [Fourth embodiment]

[0112] Fig. 12A This is a cross-sectional view showing an example of an electrochemical cell according to a fourth embodiment. Fig. 12B , Fig. 12C This is a cross-sectional view showing another example of the electrochemical cell according to the fourth embodiment. Fig.13 yes Fig. 12A The enlarged view of the region R4 is shown. Fig.13 Also applicable to Fig. 12B , Fig. 12C .

[0113] like Figures 12A to 12C As shown, the single cell 1C has: an element portion 3C in which a fuel electrode 5, a solid electrolyte layer 6, an intermediate layer 7, and an air electrode 8 are stacked; and a supporting substrate 2. The supporting substrate 2 has a component 120, which has a through hole or a pore at a portion in contact with the element portion 3 and is located outside the gas flow path 2a. The supporting substrate 2 enables gas to flow between the gas flow path 2a and the element portion 3C. The supporting substrate 2 can be composed of one or more metal plates, for example. The material of the metal plate can contain chromium. The metal plate can have a conductive coating layer. The supporting substrate 2 electrically connects adjacent single cells 1C to each other. The element portion 3C can be directly formed on the supporting substrate 2, or it can be bonded to the supporting substrate 2 by a bonding member.

[0114] exist Fig. 12A In the example shown, the side surface of the fuel electrode 5 is covered with a solid electrolyte layer 6, and the gas flow path 2a through which the fuel gas flows is hermetically sealed. Fig. 12BAs shown, the side surface of the fuel electrode 5 may be covered and sealed by a dense glass or ceramic sealing member 9. The sealing member 9 covering the side surface of the fuel electrode 5 may have electrical insulation properties.

[0115] In addition, the gas flow path 2a of the support substrate 2 may be as follows Fig. 12C As shown, it is formed by a member 120 having projections and depressions.

[0116] Fig.13 Yes Fig. 12A The enlarged cross-sectional view of the region R4 is shown. Fig.13 As shown in FIG. 1 , the cell 1C contains Al at the boundary 41 between the solid electrolyte layer 6 and the intermediate layer 7. The boundary 41 includes the boundary 40 between the solid electrolyte layer 6 and the intermediate layer 7, and is a region where the distance from the boundary 40 to the boundary 40 in the thickness direction is 100 nm or less. The boundary 41 may contain Al, for example. 2 O 3 Furthermore, the boundary portion 41 may have a solid solution portion 42 containing Al.

[0117] Thus, by including Al in the boundary portion 41 between the solid electrolyte layer 6 and the intermediate layer 7, for example, during the manufacture of the element portion 3C or at high temperatures, the Zr component contained in the solid electrolyte layer 6 and the Ce component contained in the intermediate layer 7 are less likely to diffuse into each other. Therefore, since it is difficult to generate an insulating composition having Zr and Ce inside the solid electrolyte layer 6 and / or the intermediate layer 7, the power generation performance of the single cell 1C can be improved.

[0118] [Other embodiments]

[0119] Next, electrochemical cell devices according to other embodiments will be described.

[0120] In the above-mentioned embodiments, 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", an "electrochemical cell device", a "module", and a "module housing device", but as other examples, an electrolysis cell, an electrolysis cell stack device, an electrolysis module, and an electrolysis device are shown. The electrolysis cell has a first electrode layer and a second electrode layer, and decomposes water vapor into hydrogen and oxygen, or decomposes carbon dioxide into carbon monoxide and oxygen by supplying electricity. In addition, in each of the above-mentioned embodiments, an oxide ion conductor or a hydrogen ion conductor is shown as an example of an electrolyte material for an electrochemical cell, but a hydroxide ion conductor may also be used. According to such an electrolysis cell, an electrolysis cell stack device, an electrolysis module, and an electrolysis device, the electrolysis performance can be improved.

[0121] As mentioned above, although this disclosure was described in detail, this disclosure is not limited to the above-mentioned embodiment, and various changes, improvements, etc. can be made within the scope which does not deviate from the summary of this disclosure.

[0122] In one embodiment, (1) an electrochemical cell comprises a first electrode layer, a second electrode layer, a solid electrolyte layer, and an intermediate layer. The solid electrolyte layer is located between the first electrode layer and the second electrode layer. The intermediate layer is located between the solid electrolyte layer and the first electrode layer and contains Ce. The electrochemical cell contains Al at a boundary between the solid electrolyte layer and the intermediate layer.

[0123] (2) In the electrochemical cell of (1) above, the solid electrolyte layer may contain Zr.

[0124] (3) In the electrochemical cell of (1) or (2) above, the boundary portion may have a solid solution portion including one or more metal elements contained in the solid electrolyte layer and one or more metal elements contained in the intermediate layer, and the solid solution portion may contain the Al.

[0125] (4) An electrochemical cell device includes a cell stack including any one of the electrochemical cells described in (1) to (3).

[0126] (5) A module comprising: the electrochemical cell device according to (4) above; and a storage container for storing the electrochemical cell device.

[0127] (6) A module housing device includes: the module according to (5) above; an auxiliary machine for operating the module; and an outer casing housing the module and the auxiliary machine.

[0128] The embodiments disclosed herein are illustrative in all respects and should not be considered restrictive. In fact, the above embodiments can be embodied in various forms. In addition, the above embodiments can be omitted, replaced, and changed in various forms without departing from the attached claims and their gist.

[0129] Explanation of symbols

[0130] 1. 1A~1C single battery

[0131] 2 Support base plate

[0132] 3 Components

[0133] 4 Interconnectors

[0134] 5 Fuel electrode

[0135] 6 Solid electrolyte layer

[0136] 7 Middle Layer

[0137] 8 Air electrode

[0138] 10 Single Cell Stack Device

[0139] 11 Single Cell Stack

[0140] 12 Fixed components

[0141] 13 Fixing parts

[0142] 14 Supporting member

[0143] 15 Support

[0144] 16 Gas Tanks

[0145] 17 End current collecting member

[0146] 18 Connecting components

[0147] 41 Boundary Department

[0148] 42 Solid solution part

[0149] 100 modules

[0150] 110 Module containment device.

Claims

1. An electrochemical cell comprising: A first electrode layer; A second electrode layer; a solid electrolyte layer located between the first electrode layer and the second electrode layer; and an intermediate layer located between the solid electrolyte layer and the first electrode layer and containing Ce, Al is contained in a boundary portion between the solid electrolyte layer and the intermediate layer.

2. The electrochemical cell according to claim 1, wherein: The solid electrolyte layer contains Zr.

3. The electrochemical cell according to claim 1 or 2, wherein: The boundary portion has a solid solution portion containing one or more metal elements contained in the solid electrolyte layer and one or more metal elements contained in the intermediate layer. The solid solution portion contains the Al. 4 . An electrochemical cell device comprising a cell stack, wherein the cell stack comprises the electrochemical cell according to claim 1 .

5. A module comprising: The electrochemical cell device of claim 4; and A storage container for storing the electrochemical cell device.

6. A module storage device, comprising: The module according to claim 5; Auxiliary machines for operating the modules; and An outer casing that accommodates the module and the auxiliary machine.

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