Conductive member, electrochemical cell device, module, and module housing device

Abstract

The conductive member is provided with a base material containing chromium, a first layer containing first particles of a conductive oxide, and a second layer containing second particles of a conductive oxide. The first layer is on the substrate. The second layer is on the first layer. The first layer has an open pore that opens at an interface with the second layer. The second particles include particles having a particle diameter smaller than the diameter of the open pores.

Description

Technical Field

[0001] The present disclosure relates to a conductive member, an electrochemical cell device, a component, and a component 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 electrochemical cell that can generate electric power 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: International Publication No. 2009 / 131180 Summary of the invention

[0006] Problems to be solved by the invention

[0007] A conductive member according to one embodiment of the present invention comprises: a substrate containing chromium; a first layer containing first particles of a conductive oxide; and a second layer containing second particles of a conductive oxide. The first layer is located on the substrate. The second layer is located on the first layer. The first layer has open pores that open at an interface with the second layer. The second particles include particles having a particle diameter smaller than a diameter of the open pores.

[0008] In addition, the electrochemical cell device of the present disclosure comprises the above-described conductive member and an electrochemical cell having a first electrode. The first electrode is bonded to a third layer located on the second layer. The third layer comprises third particles having an average particle size larger than that of the second particles.

[0009] Furthermore, the kit of the present disclosure includes the electrochemical cell device described above and a storage container for storing the electrochemical cell device.

[0010] Furthermore, the component housing device of the present disclosure includes: the above-described component; an auxiliary machine for operating the component; and an outer casing that houses the component and the auxiliary machine. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1A It is a cross-sectional view showing an example of the electrochemical cell according to the first embodiment.

[0012] 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.

[0013] 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.

[0014] Figure 2A It is a perspective view showing an example of the electrochemical cell device according to the first embodiment.

[0015] Figure 2B yes Figure 2A X-ray cross-sectional view shown.

[0016] Figure 2C It is a plan view showing an example of the electrochemical cell device according to the first embodiment.

[0017] Figure 3A This is a cross-sectional view showing an example of the electrochemical cell device according to the first embodiment.

[0018] Figure 3B It is along Figure 3A A cross-sectional view along line A-A is shown.

[0019] Figure 4A yes Figure 3B An enlarged view of area B is shown.

[0020] Figure 4B yes Figure 4A An enlarged view of area C is shown.

[0021] Figure 5 It is an external perspective view showing an example of the assembly of the first embodiment.

[0022] Figure 6 It is an exploded perspective view schematically showing an example of the component housing device according to the first embodiment.

[0023] Fig. 7A It is a cross-sectional view showing an example of the electrochemical cell device according to the second embodiment.

[0024] Figure 7B It is a cross-sectional view showing another example of the electrochemical cell device according to the second embodiment.

[0025] Fig. 8A It is along Fig. 7A An enlarged view of the cross section along line DD is shown.

[0026] Figure 8B It is along Fig. 7A An enlarged view of the cross section along line DD is shown.

[0027] Figure 8C It is an enlarged cross-sectional view showing another example of the conductive member according to the second embodiment.

[0028] Fig. 9 It is a cross-sectional view showing an example of the electrochemical cell device according to the third embodiment.

[0029] Fig.10 yes Fig. 9 An enlarged view of area E is shown.

[0030] Fig.11A It is a perspective view showing an example of an electrochemical cell according to a fourth embodiment.

[0031] Fig. 11B yes Fig.11A A partial cross-sectional view of an electrochemical cell is shown. DETAILED DESCRIPTION

[0032] In the above-described fuel cell stack device, there is room for improvement in the durability of the conductive member joined to the fuel cell unit.

[0033] Therefore, it is desired to provide a highly durable conductive member, an electrochemical cell device, a module, and a module housing device.

[0034] Hereinafter, embodiments of the conductive member, electrochemical cell device, assembly, and assembly housing device disclosed in the present application will be described in detail with reference to the accompanying drawings. It should be noted that the present disclosure is not limited to the embodiments described below.

[0035] 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 include portions where the relationship between the dimensions, the ratio, etc. are different.

[0036] [First embodiment]

[0037] <Structure of electrochemical cell>

[0038] First, refer to Figure 1A to Figure 1C As the electrochemical cell of the first embodiment, a solid oxide fuel cell unit is used as an example for explanation. The electrochemical cell device may also include a cell stack including a plurality of electrochemical cells. The electrochemical cell device including a plurality of electrochemical cells is simply referred to as a cell stack device.

[0039] Figure 1A It 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 of the first embodiment as viewed from the interconnector side. Figure 1A to Figure 1C A portion of each component of an electrochemical cell is shown in an enlarged manner. Hereinafter, an electrochemical cell may also be simply referred to as a battery.

[0040] exist Figure 1A to Figure 1CIn the example shown, the battery 1 is a hollow flat plate type and has an elongated plate shape. Figure 1B As shown, the overall shape of the battery 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 battery 1 in the thickness direction T is, for example, 1 to 5 mm.

[0041] like Figure 1A As shown, the battery 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 first surfaces n1, a second surface n2, and a pair of arc-shaped side surfaces m connecting the first surface n1 and the second surface n2.

[0042] The element part 3 is located on the first surface n1 of the support substrate 2. The element part 3 includes a fuel electrode 5, a solid electrolyte layer 6, and an air electrode 8. Figure 1A In the example shown, the interconnector 4 is located on the second surface n2 of the battery 1. It should be noted that the battery 1 may also include an intermediate layer 7 between the solid electrolyte layer 6 and the air electrode 8.

[0043] In addition, if Figure 1B As shown in FIG. 1 , the air electrode 8 does not extend to the lower end of the battery 1. At the lower end of the battery 1, only the solid electrolyte layer 6 is exposed on the surface of the first surface n1. Figure 1C As shown, the interconnector 4 may also extend to the lower end of the battery 1. At the lower end of the battery 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 surfaces of the pair of arc-shaped side surfaces m of the battery 1. The interconnector 4 may not extend to the lower end of the battery 1.

[0044] Hereinafter, each component constituting the battery 1 will be described.

[0045] 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 gas flowing in the gas flow paths 2a to pass through to the fuel electrode 5. The support substrate 2 may have electrical conductivity. The conductive support substrate 2 collects the power generated in the element part to the interconnector 4.

[0046] 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.

[0047] The material of the fuel electrode 5 can use a generally known material. The fuel electrode 5 can also be a porous conductive ceramic containing a material having electronic conductivity and a material having ion conductivity. As conductive ceramics, for example, ZrO2 in which calcium oxide, magnesium oxide or rare earth element oxide is solid-dissolved and ceramics containing Ni and / or NiO can be used. The rare earth element oxide can, for example, contain a plurality of rare earth elements selected from Sc, Y, La, Nd, Sm, Gd, Dy and Yb. ZrO2 in which calcium oxide, magnesium oxide or rare earth element oxide is solid-dissolved is sometimes referred to as stabilized zirconia. Stabilized zirconia can also contain partially stabilized zirconia.

[0048] 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 also has a gas barrier property, and thus the fuel gas and the oxygen-containing gas are unlikely to leak.

[0049] The material of the solid electrolyte layer 6 may be, for example, ZrO2 in which 3 mol% to 15 mol% of rare earth element oxide is solid-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, ZrO2 in which Yb, Sc, or Gd is solid-dissolved, CeO2 in which La, Nd, or Yb is solid-dissolved, BaZrO3 in which Sc or Yb is solid-dissolved, or BaCeO3 in which Sc or Yb is solid-dissolved.

[0050] The air electrode 8 has air permeability. The open porosity of the air electrode 8 may be, for example, 20% to 50%, particularly 30% to 50%. The open porosity of the air electrode 8 is sometimes referred to as the void ratio of the air electrode 8 .

[0051] The material of the air electrode 8 is not particularly limited as long as it is a material generally used for air electrodes. The material of the air electrode 8 may be, for example, a conductive ceramic such as a so-called ABO3 type perovskite oxide.

[0052] 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 O3, La x Sr 1－x MnO3、La x Sr 1－x FeO3、La x Sr 1－ xCoO3, etc. It should be noted that x is 0<x<1, and y is 0<y<1.

[0053] In addition, when the element portion 3 has the intermediate layer 7, the intermediate layer 7 has a function as a diffusion suppression layer. When Sr (strontium) contained in the air electrode 8 diffuses into the solid electrolyte layer 6, a 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 form.

[0054] The material of the intermediate layer 7 is not particularly limited as long as it is a material that generally makes it difficult for elements to diffuse between the air electrode 8 and the solid electrolyte layer 6. The material of the intermediate layer 7 may include, for example, cerium oxide (CeO2) in which a rare earth element other than Ce (cerium) is solid-dissolved. As the rare earth element, for example, Gd (gadolinium), Sm (samarium), etc. may be used.

[0055] In addition, the interconnector 4 is dense and hardly leaks the fuel gas flowing in the gas flow path 2a located inside the support substrate 2 and the 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.

[0056] The interconnector 4 may be made of lanthanum chromate-based perovskite oxides (LaCrO3-based oxides), lanthanum strontium titanium-based perovskite oxides (LaSrTiO3-based oxides), etc. These materials are conductive and are difficult to be reduced or oxidized even when in contact with fuel gases such as hydrogen-containing gas and oxygen-containing gases such as air.

[0057] <Structure of electrochemical battery device>

[0058] Next, refer to Figure 2A to Figure 2C , an electrochemical battery device according to the present embodiment using the above-mentioned battery 1 will be described. Figure 2A It is a perspective view showing an example of the electrochemical cell device according to the first embodiment. Figure 2B yes Figure 2A The sectional view taken along line X-X is shown. Figure 2C It is a plan view showing an example of the electrochemical cell device according to the first embodiment.

[0059] like Figure 2A As shown, the battery stack device 10 has a thickness direction T of the battery 1 (see Figure 1A ) A battery stack 11 of a plurality of batteries 1 arranged (stacked) and a fixing member 12.

[0060] The fixing member 12 includes a fixing material 13 and a supporting member 14. The supporting member 14 supports the battery 1. The fixing material 13 fixes the battery 1 to the supporting member 14. In addition, the supporting member 14 includes a supporting body 15 and a gas tank 16. The supporting body 15 and the gas tank 16 as the supporting member 14 are made of metal and have conductivity.

[0061] like Figure 2B As shown, the support body 15 has an insertion hole 15a into which the lower end portions of the plurality of batteries 1 are inserted. The lower end portions of the plurality of batteries 1 are joined to the inner wall of the insertion hole 15a by a fixing material 13.

[0062] 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 outer peripheral end of the support 15 is joined to the gas tank 16 by a joining material 21 filling the groove 16a of the gas tank 16.

[0063] 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 the fuel gas is supplied from the gas tank 16 to a gas flow path 2a (see FIG. 2 ) inside the battery 1. Figure 1A ) is supplied. The fuel gas supplied to the gas tank 16 is supplied by the reformer 102 (see Figure 5 )generate.

[0064] The hydrogen-rich fuel gas can be produced by steam reforming a raw fuel, etc. When the fuel gas is produced by steam reforming, the fuel gas contains water vapor.

[0065] Figure 2A The example shown has two rows of battery stacks 11, two supports 15, and a gas tank 16. The two rows of battery stacks 11 each have a plurality of batteries 1. Each battery 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.

[0066] 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 battery 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 battery stack 11. The width of the insertion hole 15a is, for example, greater than the width direction W of the battery 1 (see Figure 1A ) length.

[0067] like Figure 2BAs shown, the fixing material 13 is filled and cured at the junction between the inner wall of the insertion hole 15a and the lower end of the battery 1. As a result, the inner wall of the insertion hole 15a is respectively joined and fixed to the lower ends of the plurality of batteries 1, and the lower ends of the batteries 1 are joined and fixed to each other. The gas flow path 2a of each battery 1 communicates with the internal space 22 of the support member 14 at the lower end.

[0068] A material with low conductivity such as glass can be used for the fixing material 13 and the bonding material 21. As specific materials for the fixing material 13 and the bonding material 21, amorphous glass and the like can be used, and in particular, crystallized glass and the like can also be used.

[0069] As the crystallized glass, for example, any of SiO2-CaO, MgO-B2O3, La2O3-B2O3-MgO, La2O3-B2O3-ZnO, SiO2-CaO-ZnO and other materials can be used, and in particular, SiO2-MgO materials can be used.

[0070] In addition, if Figure 2B As shown, the conductive member 18 is interposed between adjacent cells 1 among the plurality of cells 1. The conductive 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 interconnector 4 electrically connected to the fuel electrode 5 of one adjacent cell 1 is connected to the air electrode 8 of the other cell 1. It should be noted that the details of the connection between the adjacent cells 1 and the conductive member 18 will be described later.

[0071] In addition, if Figure 2B As shown, the end current collecting member 17 is electrically connected to the outermost battery 1 in the arrangement direction of the plurality of batteries 1. The end current collecting member 17 is connected to a conductive portion 19 protruding to the outside of the battery stack 11. The conductive portion 19 collects the power generated by the battery 1 and leads it to the outside. Figure 2A In the figure, the end current collecting member 17 is omitted.

[0072] In addition, if Figure 2C As shown, in the battery stack device 10, two battery stacks 11A and 11B are connected in series and function as one battery. Therefore, the conductive portion 19 of the battery stack device 10 is divided into a positive terminal 19A, a negative terminal 19B, and a connection terminal 19C.

[0073] The positive terminal 19A is the positive electrode when the power generated by the battery stack 11 is output to the outside, and is electrically connected to the end current collecting member 17 on the positive electrode side of the battery stack 11A. The negative terminal 19B is the negative electrode when the power generated by the battery stack 11 is output to the outside, and is electrically connected to the end current collecting member 17 on the negative electrode side of the battery stack 11B.

[0074] The connection terminal 19C electrically connects the end current collecting member 17 on the negative electrode side in the battery stack 11A and the end current collecting member 17 on the positive electrode side in the battery stack 11B.

[0075] <Details of electrochemical battery device>

[0076] Next, refer to Figure 3A to Figure 4B The electrochemical cell device of the first embodiment will be described in detail. Figure 3A This is a cross-sectional view showing an example of the electrochemical cell device according to the first embodiment.

[0077] like Figure 3A As shown, the battery stack device 10 has batteries 1 a and 1 b adjacent to each other in the thickness direction T and a conductive member 18 located between the battery 1 a and the battery 1 b.

[0078] The conductive member 18 has a connection portion 18a connected to the battery 1a of the adjacent battery 1 and a connection portion 18b connected to the battery 1b of the other battery 1. In addition, the conductive member 18 has a connecting portion 18c at both ends in the width direction W, connecting the connection portions 18a and 18b. Thus, the conductive member 18 can electrically connect the adjacent batteries 1 in the thickness direction T. It should be noted that Figure 3A In FIG. 1 , the shape of the battery 1 is simplified.

[0079] Figure 3B It is along Figure 3A The conductive member 18 extends in the length direction L of the battery 1. Figure 3B As shown, a plurality of connecting portions 18a and 18b of the conductive member 18 are provided staggered with each other along the longitudinal direction L of the battery 1. The conductive member 18 contacts the batteries 1a and 1b at the connecting portions 18a and 18b, respectively.

[0080] Figure 4A yes Figure 3B The enlarged view of area B is shown. Figure 4A As shown, the conductive member 18 has a substrate 40 , a first layer 41 , and a second layer 42 .

[0081] The substrate 40 has electrical conductivity and heat resistance. The substrate 40 contains chromium. The substrate 40 is, for example, stainless steel. The substrate 40 may contain, for example, a metal oxide.

[0082] In addition, the substrate 40 may have a laminated structure. Figure 4AIn the example shown, the substrate 40 has a first substrate portion 40a and a second substrate portion 40b. The second substrate portion 40b may have a higher content of, for example, chromium than the first substrate portion 40a. The second substrate portion 40b may contain, for example, chromium oxide (Cr2O3). In this way, the durability of the conductive member 18 is improved by the substrate 40 having the second substrate portion 40b. It should be noted that the substrate 40 may have the second substrate portion 40b in a manner covering the entire first substrate portion 40a, or may have the second substrate portion 40b partially. In addition, the substrate 40 may not have the second substrate portion 40b. The substrate 40 may have a further laminated structure.

[0083] The first layer 41 is located on the substrate 40. The first layer 41 is located between the substrate 40 and the second layer 42. The first layer 41 has a conductive oxide. The oxide may contain, for example, Mn (manganese) and Co (cobalt). In addition, the oxide may also contain elements other than Mn and Co, such as Zn (zinc) and Al (aluminum). The oxide may be a composite oxide having a spinel structure. As a composite oxide having this structure, for example, Zn (Co) such as ZnMnCoO4 can be used. x Mn 1－x )2O4 (0<x<1), Mn 1.5 Co 1.5 O4、MnCo2O 4、 CoMn2O4, etc. The first layer 41 may contain CeO2, for example.

[0084] The first layer 41 may include a plurality of first particles containing a conductive oxide. Alternatively, the first layer 41 may be a film covering the substrate 40. Alternatively, the first layer 41 may be a film covering the entire substrate 40. Alternatively, the first layer 41 may include components other than the conductive oxide.

[0085] The first layer 41 may be a sintered body or a powder compact. In addition, the first layer 41 may be crystalline or amorphous. In addition, the first layer 41 may contain a mixture of a crystalline phase and an amorphous phase.

[0086] The second layer 42 is located on the first layer 41. The second layer 42 has a first surface 181 and a second surface 182 that are opposite to each other via the substrate 40. In addition, the conductive member 18 has third surfaces 183 and 184 that connect the first surface 181 and the second surface 182.

[0087] The second layer 42 includes a plurality of second particles containing a conductive oxide. The material of the second layer 42 may be, for example, a conductive ceramic such as a so-called ABO3 type perovskite oxide.

[0088] The material of the second layer 42 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 O3, La x Sr 1－x MnO3、La x Sr 1－x FeO3、La x Sr 1－ x CoO3, etc. It should be noted that x is 0<x<1, and y is 0<y<1.

[0089] The second layer 42 can be located on the surface of the first layer 41 by a film forming method such as a DIP method, for example.

[0090] The conductive member 18 (connecting portion 18a) may further include a third layer 43. The third layer 43 is located on the second layer 42. Figure 4A In the example shown, the third layer 43 is located only on the first surface 181 of the second layer 42, but the third layer 43 may be located on the third surfaces 183 and 184, for example. The third layer 43 is located between the air electrode 8 of the battery 1a and the second layer 42, and joins the air electrode 8 of the battery 1a to the conductive member 18. The air electrode 8 is the first electrode joined to the conductive member 18.

[0091] The material of the third layer 43 may be, for example, a conductive ceramic such as a so-called ABO 3 type perovskite oxide.

[0092] The material of the third layer 43 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 O3, La x Sr 1－x MnO3、La x Sr 1－x FeO3、La x Sr 1－ x CoO3, etc. It should be noted that x is 0<x<1, and y is 0<y<1.

[0093] The third layer 43 may have air permeability. The porosity of the third layer 43 may be, for example, 50% or less. The porosity of the third layer 43 may be greater than the porosity of the second layer 42, for example.

[0094] Figure 4B yes Figure 4AThe enlarged view of area C is shown. Figure 4B As shown, the first layer 41 of the conductive member 18 may have a plurality of first particles 411 and first pores 412 located between the plurality of first particles 411. The first pores 412 include open pores opened at the interface 410 with the second layer 42. The first layer 41 may include closed pores located inside the plurality of first particles 411 or between the plurality of first particles 411.

[0095] The first particles 411 may have an average particle diameter of, for example, 0.3 μm or more and 0.6 μm or less. The first pores 412 may have an average pore diameter of, for example, 0.3 μm or more and 1.0 μm or less.

[0096] In addition, the second layer 42 may include a plurality of second particles 421. The second particles 421 may also include second particles 421 having a particle diameter smaller than the diameter of the first pores 412 opened at the interface 410. As a result, a portion of the second particles 421 easily enters the first pores 412 opened at the interface 410, and the bonding strength between the first layer 41 and the second layer 42 increases. Therefore, the first layer 41 and the second layer 42 are not easily peeled off, so the durability of the conductive member 18 and the battery stack device 10 is improved.

[0097] In addition, the average particle size of the second particles 421 may be smaller than the average pore size of the first pores 412 included in the first layer 41. As a result, a portion of the second particles 421 easily enters the first pores 412 opened at the interface 410, and the bonding strength between the first layer 41 and the second layer 42 increases. Therefore, the first layer 41 and the second layer 42 are not easily peeled off, and thus the durability of the conductive member 18 and the battery stack device 10 is improved.

[0098] In addition, the average pore size of the second pores included in the second layer 42 may be smaller than the average pore size of the first pores 412 included in the first layer 41. As a result, the strength of the second layer 42 is increased, and cracks are less likely to occur inside the second layer 42, thereby improving the durability of the conductive member 18 and the battery stack device 10.

[0099] The average particle size of the second particles 421 may be, for example, 0.2 μm to 0.6 μm. The average pore size of the second pores included in the second layer 42 may be, for example, 0.06 μm to 0.3 μm. The second layer 42 may have a porosity of, for example, 10% to 16%.

[0100] In addition, the first layer 41 may include a first region 41a opposite to the substrate 40 and a second region 41b opposite to the second layer 42 and having a greater porosity than the first region 41a. As a result, the adhesion between the first region 41a and the substrate 40 is improved, thereby increasing the bonding strength, and the bonding strength between the second region 41b and the second layer 42 is increased. Therefore, the first region 41a and the substrate 40 are difficult to peel off, and the second region 41b and the second layer 42 are difficult to peel off, so the durability of the conductive member 18 and the battery stack device 10 is improved.

[0101] The porosity of the first region 41a may be, for example, 5% or less. In addition, the porosity of the second region 41b may be, for example, 10% or more and 30% or less. The first layer 41 may be formed, for example, by sequentially stacking a plurality of first particles 411 having different average particle diameters, or by making the time required for heat treatment different. However, the method for making the first region 41a and the second region 41b is not limited, and they may be made by any method.

[0102] In addition, the third layer 43 may include third particles 431 having an average particle diameter larger than that of the second particles 421. As a result, a portion of the second particles 421 enters the gaps between the third particles 431, and the bonding strength between the second layer 42 and the third layer 43 increases. Therefore, the second layer 42 and the third layer 43 are difficult to peel off, so the durability is improved. The third particles 431 may further include particles having a particle diameter of the same degree as the average particle diameter of the second particles 421, or may include particles having a particle diameter smaller than the average particle diameter of the second particles 421.

[0103] In addition, the average pore size of the third pores included in the third layer 43 may be larger than the average particle size of the second particles 421. As a result, the second particles 421 can easily enter the gaps between the third particles 431, and the bonding strength between the second layer 42 and the third layer 43 increases. Therefore, the second layer 42 and the third layer 43 are difficult to peel off, so the durability of the conductive member 18 and the battery stack device 10 is improved.

[0104] In addition, the third layer 43 may also contain at least one of the metal elements contained in the second layer 42. As a result, the affinity between the second layer 42 and the third layer 43 becomes higher, and the bonding strength between the second layer 42 and the third layer 43 becomes greater. Therefore, it is difficult for the second layer 42 and the third layer 43 to be peeled off. Therefore, the metal elements contained in the third layer 43 and the second layer 42 can be determined, for example, by performing point analysis, line analysis, mapping, etc. of each element in the cross section of the conductive member 18 using HAADF-STEM (high-angle annular dark field scanning transmission electron microscope), FIB-SEM (focused ion beam scanning electron microscope) or EPMA (electron probe microanalyzer).

[0105] The material of the third layer 43 may have the same crystal structure as the material of the second layer 42. The material of the third layer 43 may have the same composition as the material of the second layer 42. If the material of the third layer 43 has the same crystal structure or the same composition as the material of the second layer 42, the affinity between the second layer 42 and the third layer 43 will be further increased, and the bonding strength between the second layer 42 and the third layer 43 will be further increased.

[0106] The average particle size of the third particles 431 included in the third layer 43 may be, for example, 0.25 μm or more and 6.5 μm or less. In addition, the average pore size of the third pores may be, for example, 0.1 μm or more and 0.9 μm or less. It should be noted that the third layer 43 may include third particles 431 having a smaller particle size than the average particle size of the second particles 421.

[0107] In this way, the conductive member 18 has the first layer 41, the second layer 42, and the third layer 43, thereby increasing the bonding strength within the conductive member 18 and improving durability. In addition, by bonding the conductive member 18 to the air electrode 8 using the third layer 43 of the conductive member 18, the bonding strength between the conductive member 18 and the air electrode 8 is increased. As a result, the durability of the battery stack device 10 can be improved.

[0108] It should be noted that the average particle size of each particle of the first layer 41, the second layer 42 and the third layer 43, the porosity of the first layer 41, the second layer 42 and the third layer 43, and the average pore size of each pore of the first layer 41, the second layer 42 and the third layer 43 can be measured based on the results obtained by observing the cross section of the conductive component 18 with a SEM (Scanning Electron Microscope).

[0109] <Components>

[0110] Next, use Figure 5 The components of the embodiment of the present disclosure using the above-described battery stack device 10 will be described. Figure 5 1 is a perspective view showing the appearance of the components of the first embodiment. Figure 5 , a state is shown in which the front and rear surfaces, which are part of the storage container 101, are removed and the cell stack device 10 of the fuel cell stored inside is taken out toward the rear.

[0111] like Figure 5 As shown, the assembly 100 includes a storage container 101 and a battery stack device 10 stored in the storage container 101. In addition, a reformer 102 is arranged above the battery stack device 10.

[0112] The reformer 102 reforms the raw fuel such as natural gas and kerosene to generate fuel gas and supplies it to the battery 1. The raw fuel is supplied to the reformer 102 through the raw fuel supply pipe 103. It should be noted that the reformer 102 may also include a gasification unit 102a and a reforming unit 102b for gasifying water. The reforming unit 102b includes a reforming catalyst (not shown) to reform the raw fuel into fuel gas. Such a reformer 102 can perform a highly efficient reforming reaction, namely, steam reforming.

[0113] Then, the fuel gas generated by the reformer 102 is discharged to the gas flow path 2a (see FIG. 2 ) of the cell 1 through the gas flow pipe 20, the gas tank 16, and the support member 14. Figure 1A )supply.

[0114] 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 battery 1 generates power.

[0115] In such an assembly 100 , as described above, by accommodating the battery stack device 10 capable of improving durability, it is possible to obtain an assembly 100 capable of improving durability.

[0116] <Component storage device>

[0117] Figure 6 1 is an exploded perspective view showing an example of a component storage device according to the first embodiment. The component storage device 110 of this embodiment includes an outer casing 111, Figure 5 The assembly 100 shown in the figure and the auxiliary machine not shown in the figure. The auxiliary machine operates the assembly 100. The assembly 100 and the auxiliary machine are accommodated in the outer casing 111. It should be noted that Figure 6 Part of the structure is omitted and shown.

[0118] Figure 6 The outer casing 111 of the component 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 parts. The space above the partition plate 114 in the outer casing 111 is a component storage chamber 115 for storing the component 100, and the space below the partition plate 114 in the outer casing 111 is an auxiliary machine storage chamber 116 for storing the auxiliary machine of the component 100. It should be noted that Figure 6 In the figure, the auxiliary machines accommodated in the auxiliary machine accommodation chamber 116 are omitted and shown.

[0119] Partition plate 114 has air flow opening 117 for allowing air in auxiliary machine storage chamber 116 to flow toward module storage chamber 115. External plate 113 constituting module storage chamber 115 has exhaust opening 118 for exhausting air in module storage chamber 115.

[0120] In such a component housing device 110 , as described above, by providing the component housing chamber 115 with the component 100 capable of improving durability, the component housing device 110 can be provided with improved durability.

[0121] In addition, in the above-mentioned embodiment, the case where a hollow flat-plate-type support substrate is used is exemplified, but it is also applicable to a battery stack device using a cylindrical-type support substrate.

[0122] [Second embodiment]

[0123] Fig. 7A It is a cross-sectional view showing an example of the electrochemical cell according to the second embodiment. Figure 7B It is a cross-sectional view showing another example of the electrochemical cell according to the second embodiment.

[0124] like Fig. 7A , Figure 7B As shown, the battery 1A has an element portion 3A and a support substrate 2 in which a fuel electrode 5, a solid electrolyte layer 6, and an air electrode 8 are stacked. The support substrate 2 has a through hole or pores at a portion of the element portion 3A that contacts the fuel electrode 5, and has a member 120 located outside the gas flow path 2a. The support substrate 2 enables gas to flow between the gas flow path 2a and the element portion 3A. The support substrate 2 may also be composed of one or more metal plates, for example. The material of the metal plate may contain chromium. The metal plate may have a conductive covering layer.

[0125] The conductive member 18 electrically connects the adjacent batteries 1A to each other. The conductive member 18 has a connection portion 18a connected to the battery 1a of one of the adjacent batteries 1 and a connection portion 18b connected to the battery 1b of the other of the adjacent batteries 1.

[0126] Fig. 8A , Figure 8B It is along Fig. 7A The enlarged view of the cross section of the DD line is shown. Fig. 8A , Figure 8B Can also be applied to Figure 7B Example.

[0127] like Fig. 8AAs shown, the connection portion 18a of the conductive member 18 includes: a substrate 40 containing chromium; a first layer 41 located on the substrate 40 and containing first particles of a conductive oxide; and a second layer 42 located on the first layer 41 and containing second particles of a conductive oxide. The first layer 41 has open pores that open at the interface with the second layer 42. The second particles include particles having a particle size smaller than the diameter of the open pores possessed by the first layer 41. As a result, a portion of the second particles easily enters the open pores that open at the interface between the first layer 41 and the second layer 42, and the bonding strength between the first layer 41 and the second layer 42 increases. Therefore, the first layer 41 and the second layer 42 are difficult to peel off, and thus the durability of the conductive member 18 and the battery stack device 10A is improved.

[0128] In addition, the conductive member 18 may include a third layer 43 located on the second layer 42. The third layer 43 includes, for example, third particles having an average particle size larger than that of the second particles. The air electrode 8 of the battery 1a is bonded to the third layer 43. As a result, the conductive member 18 and the battery 1a are unlikely to be separated, thereby improving the durability of the battery stack device 10A.

[0129] like Figure 8B As shown, the connection portion 18b of the conductive member 18 includes: a substrate 40 containing chromium; a first layer 41 located on the substrate 40 and containing first particles of a conductive oxide; and a second layer 42 located on the first layer 41 and containing second particles of a conductive oxide. The first layer 41 has open pores that open at the interface with the second layer 42. The second particles include particles having a particle size smaller than the diameter of the open pores of the first layer 41. As a result, a portion of the second particles easily enters the open pores that open at the interface between the first layer 41 and the second layer 42, and the bonding strength between the first layer 41 and the second layer 42 increases. Therefore, the first layer 41 and the second layer 42 are difficult to peel off, so the durability of the conductive member 18 and the battery stack device 10A is improved.

[0130] In addition, the conductive component 18 may include a third layer 43a located on the second layer 42. The third layer 43a, for example, includes third particles having an average particle size larger than that of the second particles. The component 120 of the battery 1b is bonded to the third layer 43a. As a result, the conductive component 18 and the battery 1a are difficult to peel off, thereby improving the durability of the battery stack device 10A. It should be noted that the material of the third layer 43a may be the same as or different from the material of the third layer 43.

[0131] exist Fig. 7A 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. Figure 7BAs shown, the side of the fuel electrode 5 may be covered and sealed by a dense sealing material 9. The sealing material 9 covering the side of the fuel electrode 5 may also have electrical insulation. The material of the sealing material 9 may be glass or ceramic, for example.

[0132] Figure 8C FIG. 2 is an enlarged cross-sectional view showing another example of the conductive member of the second embodiment. Figure 8C As shown, the member 120 supporting the substrate 2 may include: a substrate 50 containing chromium; a first layer 51 located on the substrate 50 and containing first particles of a conductive oxide; and a second layer 52 located on the first layer 51 and containing second particles of a conductive oxide. The substrate 50 may include a first substrate portion 50a and a second substrate portion 50b having a higher chromium content than the first substrate portion 50a. The first layer 51 may have open pores opened at the interface with the second layer 52. The second particles may include particles having a particle size smaller than the diameter of the open pores of the first layer 51. As a result, a part of the second particles easily enters the open pores opened at the interface between the first layer 51 and the second layer 52, and the bonding strength between the first layer 51 and the second layer 52 increases. Therefore, the first layer 51 and the second layer 52 are difficult to be peeled off, so the durability of the member 120 and the battery stack device 10A is improved. It should be noted that the materials of the substrate 50 , the first layer 51 , and the second layer 52 may be the same as or different from the materials of the substrate 40 , the first layer 41 , and the second layer 42 .

[0133] [Third Embodiment]

[0134] Fig. 9 FIG. 1 is a cross-sectional view showing an example of an electrochemical cell device according to the third embodiment. Fig. 9 As shown, the gas flow path 2a of the support substrate 2 can also be replaced Fig. 7A The conductive member 18 shown is formed of a member 120 having projections and depressions. The member 120 is an example of the conductive member 18 for electrically connecting adjacent batteries 1B to each other.

[0135] Fig.10 yes Fig. 9 The enlarged view of area E is shown. Fig.10As shown, the component 120 as the conductive component 18 includes: a substrate 40 containing chromium; a first layer 41, which is located on the substrate 40 and includes first particles of a conductive oxide; and a second layer 42, which is located on the first layer 41 and includes second particles of a conductive oxide. The first layer 41 has open pores that open at the interface with the second layer 42. The second particles include particles with a particle size smaller than the diameter of the open pores of the first layer 41. As a result, a part of the second particles easily enters the open pores that open at the interface between the first layer 41 and the second layer 42, and the bonding strength between the first layer 41 and the second layer 42 increases. Therefore, the first layer 41 and the second layer 42 are difficult to peel off, so the durability of the component 120 and the battery stack device 10B is improved.

[0136] In addition, the member 120 may include a third layer 43 located on the second layer 42. The third layer 43 includes, for example, third particles having an average particle size larger than that of the second particles. The air electrode 8 of the battery 1a is bonded to the third layer 43. As a result, the conductive member 18 and the battery 1a are unlikely to be separated, thereby improving the durability of the battery stack device 10B.

[0137] It should be noted that the third layer 43 may be located on the entire surface 121 facing the battery 1 a , or may be located only on the junction portion with the air electrode 8 .

[0138] [Fourth Embodiment]

[0139] Fig.11A It is a perspective view showing an electrochemical cell according to a fourth embodiment. Fig. 11B yes Fig.11A A partial cross-sectional view of an electrochemical cell is shown.

[0140] like Fig.11A As shown, a battery 1C as a flat-plate type electrochemical battery has an element portion 3C in which a fuel electrode 5, a solid electrolyte layer 6, and an air electrode 8 are stacked. In a battery stack device in which a plurality of flat-plate type batteries are stacked, for example, a plurality of batteries 1C are electrically connected by conductive members 91 and 92, which are metal layers adjacent to each other. The conductive members 91 and 92 electrically connect adjacent batteries 1C to each other and have a gas flow path for supplying gas to the fuel electrode 5 or the air electrode 8.

[0141] like Fig. 11BAs shown, in this embodiment, the conductive member 92 as the conductive member 18 has a gas flow path 93 for supplying gas to the air electrode 8. The conductive member 92 includes: a substrate 40 containing chromium; a first layer 41 located on the substrate 40 and containing first particles of a conductive oxide; and a second layer 42 located on the first layer 41 and containing second particles of a conductive oxide. The first layer 41 has open pores opened at the interface with the second layer 42. The second particles include particles having a particle size smaller than the diameter of the open pores of the first layer 41. As a result, a part of the second particles easily enters the open pores opened at the interface between the first layer 41 and the second layer 42, and the bonding strength between the first layer 41 and the second layer 42 increases. Therefore, the first layer 41 and the second layer 42 are difficult to be peeled off, so the durability of the conductive member 92 and the battery 1C is improved.

[0142] In addition, the conductive member 92 may include a third layer 43 located on the second layer 42. The third layer 43 includes, for example, third particles having an average particle size larger than that of the second particles. The air electrode 8 of the battery 1C is bonded to the third layer 43. As a result, the conductive member 92 and the element portion 3C are unlikely to be separated, thereby improving the durability of the battery stack device.

[0143] It should be noted that the conductive member 92 may be in contact with the element portion 3C without the third layer 43. In other words, in the present embodiment, the third layer 43 may not be used, and the second layer 42 may be directly connected to the element portion 3C.

[0144] [Other embodiments]

[0145] Next, electrochemical cell devices according to other embodiments will be described.

[0146] In the above-mentioned embodiments, as an example of "electrochemical cell", "electrochemical cell device", "assembly" and "assembly storage device", a fuel cell unit, a fuel cell stack device, a fuel cell assembly and a fuel cell device are shown, but as other examples, an electrolytic cell, an electrolytic cell stack device, an electrolytic assembly and an electrolytic device may be used respectively. The electrolytic cell has an anode (oxygen electrode) as a first electrode and a cathode as a second electrode, and decomposes water vapor into hydrogen and oxygen or decomposes carbon dioxide into carbon monoxide and oxygen by supplying electricity. In addition, in the above-mentioned embodiments, as an example of an electrolyte material of an electrochemical cell, an oxide ion conductor or a hydrogen ion conductor is shown, but it may also be a water oxide ion conductor.

[0147] As mentioned above, although this disclosure was demonstrated in detail, this disclosure is not limited to the said embodiment, Various changes, improvements, etc. can be made within the range which does not deviate from the summary of this disclosure.

[0148] In one embodiment, (1) the conductive member has:

[0149] a substrate containing chromium;

[0150] A first layer, which is located on the substrate and comprises first particles of a conductive oxide; and

[0151] a second layer, which is located on the first layer and comprises second particles of a conductive oxide,

[0152] The first layer has open pores opening at an interface with the second layer,

[0153] The second particles include particles having a particle diameter smaller than the diameter of the open pores.

[0154] (2) In the conductive member of (1) above, the average particle diameter of the second particles may be smaller than the average pore diameter of the first pores included in the first layer.

[0155] (3) In the conductive member of (1) or (2) above, an average pore diameter of the second pores included in the second layer may be smaller than an average pore diameter of the first pores included in the first layer.

[0156] (4) In any one of the above-mentioned (1) to (3), the first layer may include a first region facing the substrate and a second region facing the second layer and having a porosity greater than that of the first region.

[0157] (5) In the conductive member according to any one of (1) to (4) above, the conductive member may include a third layer located on the second layer and including third particles having an average particle size larger than that of the second particles.

[0158] (6) In the conductive member of (5) above, an average pore diameter of third pores included in the third layer may be larger than an average particle diameter of the second particles.

[0159] (7) In the conductive member of (5) or (6) above, the third layer may contain at least one element among the metal elements contained in the second layer.

[0160] In one embodiment, (8) an electrochemical cell device comprises:

[0161] The conductive member of any one of (5) to (7) above; and

[0162] An electrochemical cell having a first electrode,

[0163] The first electrode is bonded to the third layer.

[0164] (9) A component comprising:

[0165] The electrochemical cell device of (8) above; and

[0166] A storage container stores the electrochemical battery device.

[0167] (10) A component storage device comprising:

[0168] Components of (9) above;

[0169] Auxiliary machines for operating the components; and

[0170] An outer casing houses the components and the auxiliary machine.

[0171] The embodiments disclosed herein are illustrative in all aspects and are not restrictive. In fact, the above embodiments can be implemented in many ways. In addition, the above embodiments can be omitted, replaced, and changed in various ways without departing from the attached technical solutions and their main purpose.

[0172] Description of reference numerals:

[0173] 1. 1A, 1B, 1C battery

[0174] 2Support base plate

[0175] 3. 3A, 3B, 3C components

[0176] 4 Interconnectors

[0177] 5 Fuel pole

[0178] 6Solid electrolyte layer

[0179] 7 Middle Layer

[0180] 8 Air electrode

[0181] 10, 10A, 10B battery stack device

[0182] 11 Battery stack

[0183] 12Fixed components

[0184] 13. Fixing materials

[0185] 14 Supporting member

[0186] 15 Support

[0187] 16 Gas tanks

[0188] 17 End current collecting member

[0189] 18 Conductive components

[0190] 40 base material

[0191] 41 First floor

[0192] 42 Second Floor

[0193] 43 Third Floor

[0194] 100 components

[0195] 110 component containment device.

Claims

1. A conductive member, wherein: The conductive member comprises: a substrate containing chromium; A first layer, which is located on the substrate and comprises first particles of a conductive oxide; and a second layer, which is located on the first layer and comprises second particles of a conductive oxide, The first layer has open pores opening at an interface with the second layer, The second particles include particles having a particle diameter smaller than the diameter of the open pores.

2. The conductive member according to claim 1, wherein The average particle diameter of the second particles is smaller than the average pore diameter of the first pores included in the first layer.

3. The conductive member according to claim 1 or 2, wherein: The average pore diameter of the second pores included in the second layer is smaller than the average pore diameter of the first pores included in the first layer.

4. The conductive member according to any one of claims 1 to 3, wherein The first layer has a first region facing the substrate and a second region facing the second layer and having a porosity greater than that of the first region.

5. The conductive member according to any one of claims 1 to 4, wherein The conductive member includes a third layer located on the second layer and including third particles having an average particle diameter larger than that of the second particles.

6. The conductive member according to claim 5, wherein: An average pore diameter of third pores included in the third layer is larger than an average particle diameter of the second particles.

7. The conductive member according to claim 5 or 6, wherein: The third layer contains at least one element among the metal elements contained in the second layer.

8. An electrochemical cell device, wherein: The electrochemical cell device comprises: The conductive member according to any one of claims 5 to 7; and An electrochemical cell having a first electrode, The first electrode is bonded to the third layer.

9. A component, wherein: The components include: The electrochemical cell device of claim 8; and A storage container stores the electrochemical battery device.

10. A component receiving device, wherein: The component receiving device comprises: The assembly of claim 9; Auxiliary machines for operating the components; and An outer casing houses the components and the auxiliary machine.

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