Metal supported battery and method for manufacturing metal supported battery

Abstract

In order to prevent cracks caused by thermal stress, a metal support battery and a method for manufacturing the metal support battery are provided. The metal support battery 10 is composed of a plurality of layers including an electrolyte layer (40), an electrode layer (50) and a metal support layer (60). The electrolyte layer has a compressive residual stress along the surface direction, and at least one of the layers other than the electrolyte layer has a tensile residual stress along the surface direction.

Description

Technical Field

[0001] The invention relates to a metal support battery and a method for manufacturing the metal support battery. Background Art

[0002] Traditionally, metal-supported cells (MSC) with excellent mechanical strength and rapid start-up performance have been used in solid oxide fuel cells (SOFC).

[0003] The metal support battery is composed of a plurality of layers including an electrolyte layer, an electrode layer, and a metal support layer. In the electrolyte layer formed of fragile ceramic, there is a problem of cracks caused by thermal stress.

[0004] In response to the above-mentioned problems, for example, the following patent document 1 discloses a metal-supported battery, which increases the difference in thermal shrinkage (metal support layer-electrolyte layer) compared to the chemical shrinkage of the electrolyte layer during manufacturing, maintains the internal stress of the electrolyte layer in a compressed state during sintering cooling, and suppresses cracks in the electrolyte layer.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2012-99408

[0008] However, in the metal supported battery of Patent Document 1, although cracks can be prevented during manufacturing, in the actual field of repeated operation and shutdown, there is still a possibility that cracks will be generated in the electrolyte layer due to thermal stress caused by thermal expansion and cooling contraction. Summary of the invention

[0009] An object of the present invention is to provide a metal supported battery and a method for the metal supported battery that prevent internal residual stress from being applied to an electrolyte layer due to cracks in the electrolyte layer caused by thermal stress.

[0010] The metal support battery of the present invention for achieving the above-mentioned purpose is a metal support battery stacked with multiple layers including an electrolyte layer, an electrode layer and a metal support (support) layer. The electrolyte layer has a compressive residual stress in the surface direction, and at least one of the multiple layers other than the electrolyte layer has a tensile residual stress in the surface direction. The metal support layer is composed of multiple layers. At least the surface layer of the multiple layers of the metal support layer has a compressive residual stress in the surface direction. The layers of the multiple layers of the metal support layer other than the surface layer have a tensile residual stress in the surface direction.

[0011] The manufacturing method of the metal support battery of the present invention for achieving the above-mentioned purpose is to stack a plurality of layers including an electrolyte layer, an electrode layer and a metal support layer, apply compressive residual stress along the surface direction to the electrolyte layer, and apply tensile residual stress along the surface direction to at least one of the other layers except the electrolyte layer in the plurality of layers. The metal support layer is composed of a plurality of layers. A compressive residual stress along the surface direction is applied to at least a surface layer in the plurality of layers of the metal support layer. A tensile residual stress along the surface direction is applied to the layers except the surface layer in the plurality of layers of the metal support layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 It is an exploded perspective view showing a fuel cell stack according to an embodiment of the present invention.

[0013] Figure 2 yes Figure 1 An exploded perspective view of the battery cell is shown.

[0014] Figure 3 yes Figure 2 An exploded perspective view of the metal support battery assembly is shown.

[0015] Figure 4 It is along Figure 2 A partial cross-section of the metal support battery assembly of the AA line.

[0016] Figure 5 It is a magnified representation Figure 4 A partial cross-sectional view of a metal-supported battery is shown.

[0017] Figure 6 It is a magnified representation Figure 5 A partial cross-sectional view of the electrolyte layer and anode layer of a metal-supported battery is shown.

[0018] Figure 7 It is used to illustrate Figure 5 Partial cross-sectional view and stress distribution of internal stress in each layer of the metal support cell shown.

[0019] Figure 8 This is a schematic diagram for explaining a method for manufacturing a metal support battery according to an embodiment of the present invention.

[0020] Fig. 9 It is a cross-sectional view showing the internal stress when the first anode layer is sintered and hardened in the sintering step.

[0021] Fig.10 It is a cross-sectional view showing the internal stress when the second anode layer is sintered and hardened in the sintering step.

[0022] Fig.11 It is a magnified representation Fig.10A partial cross-sectional view of the electrolyte layer and the anode layer is shown.

[0023] Fig.12 Yes means Fig.10 A graph showing the relationship between the thickness ratio of the electrolyte layer and the surface stress of the electrolyte layer in the indicated state.

[0024] Fig.13 It is a cross-sectional view showing the internal stress when the second metal supporting layer is sintered and hardened in the sintering step.

[0025] Fig.14 It is a cross-sectional view showing the internal stress when the first metal supporting layer is sintered and hardened in the sintering step.

[0026] Fig.15 This is a partial cross-sectional view for explaining the internal stress of each layer of the metal support battery according to Modification Example 1.

[0027] Fig.16A This is a partial cross-sectional view for explaining the internal stress of each layer of the metal support battery according to Modification Example 2.

[0028] Fig. 16B This is a partial cross-sectional view showing a state where the metal support battery of Modification 2 is bent.

[0029] Fig.17A This is a schematic cross-sectional view for explaining a method for manufacturing a metal support battery according to Modification 3.

[0030] Fig. 17B This is a cross-sectional view showing the internal stress of a metal support cell manufactured by the manufacturing method of Modification Example 3.

[0031] Fig.18 This is a schematic cross-sectional view for explaining a method for manufacturing a metal support battery according to Modification 4.

[0032] Fig.19 This is a schematic cross-sectional view for explaining a method for manufacturing a metal support battery according to Modification Example 6.

[0033] Fig. 20 This is a schematic cross-sectional view for explaining a method for manufacturing a metal support battery according to Modification 7. DETAILED DESCRIPTION

[0034] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In addition, the following description does not limit the technical scope of the present invention and the meaning of the terms used. In addition, the dimensional ratios of the drawings are exaggerated for the purpose of description and are sometimes different from the actual ratios. For example, the thickness of each layer shown in the figure or the dimensional ratio or shape of the constituent particles (ceramic particles or metal particles) may be different from the actual situation unless otherwise mentioned.

[0035] Reference Figures 1 to 6 , a metal support cell (MSC) 10 according to an embodiment of the present invention will be described. The metal support cell 10 of this embodiment is used for a solid oxide fuel cell (SOFC).

[0036] For the convenience of the following description, an XYZ orthogonal coordinate system is shown in the figure. The X-axis and the Y-axis represent axes parallel to the horizontal direction, and the Z-axis represents an axis parallel to the vertical direction.

[0037] Figure 1 1 is an exploded perspective view showing a fuel cell stack 1 formed by stacking a plurality of battery units 1U in the vertical direction according to the first embodiment. Hereinafter, the vertical direction of the fuel cell stack 1 indicated by the Z axis in the figure is also referred to as the "stacking direction". In addition, the surface direction of each layer constituting the battery unit 1U corresponds to the XY plane direction.

[0038] (Battery unit 1U)

[0039] Figure 2 1U is an exploded perspective view of the battery unit. Figure 2 As shown, the battery unit 1U is composed of a stacked metal support battery assembly 1A, a partition plate 120 having a flow path portion 121 that divides and forms a gas flow path, and a current collecting auxiliary layer 130. In addition, a contact material may be arranged between the metal support battery assembly 1A and the current collecting auxiliary layer 130 to make the two conduction contact, or the current collecting auxiliary layer 130 may be omitted.

[0040] Figure 3 is an exploded perspective view of the metal support battery assembly 1A. Figure 4 1A is a partial cross-sectional view of the metal support battery assembly 1A. Figure 3 and Figure 4 As shown, the metal support battery assembly 1A includes a metal support battery 10 and a battery frame 113 that holds the periphery of the metal support battery 10 .

[0041] (Metal support battery 10)

[0042] Figure 5 It means to enlarge Figure 4 The metal support battery 10 shown in FIG. Figure 3 to Figure 5 As shown, the metal support battery 10 is composed of a plurality of layers including an electrolyte layer 40, electrode layers 30, 50 and a metal support layer 60. The electrode layers 30, 50 include a cathode layer 30 and an anode layer 50. Hereinafter, the cathode layer 30 and the anode layer 50 may also be collectively referred to as electrode layers 30, 50.

[0043] like Figure 5As shown, the metal support cell 10 is composed of a cathode layer 30, an electrolyte layer 40, an anode layer 50 and a metal support layer 60 stacked in sequence. The electrode layers 30, 50 and the electrolyte layer 40 constitute an electrolyte electrode assembly 20. The metal support layer 60 supports the electrolyte electrode assembly 20. The metal support cell 10 is superior to an electrolyte supported cell or an electrode supported cell in mechanical strength, rapid start-up, etc., and therefore can be more preferably applied to SOFC.

[0044] (Electrolyte Electrode Assembly 20)

[0045] like Figure 3 to Figure 5 As shown, the electrolyte electrode assembly 20 is configured by laminating a cathode layer 30 on one surface of an electrolyte layer 40 and laminating an anode layer 50 on the other surface.

[0046] (Cathode layer 30)

[0047] The cathode layer 30 is an oxidant electrode that reacts cathode gas (e.g., oxygen contained in the air) with electrons to convert oxygen molecules into oxide ions. The cathode layer 30 is resistant to oxidizing gas environments and has high gas permeability and electrical (electronic and ion) conductivity for the cathode gas to pass through. Furthermore, the cathode layer 30 has a catalytic function of converting oxygen molecules into oxygen ions.

[0048] The cathode layer 30 may be formed of, for example, an oxide composed of lanthanum, strontium, manganese, cobalt, or the like.

[0049] (Electrolyte layer 40)

[0050] The electrolyte layer 40 has the function of separating the anode gas and the cathode gas. The electrolyte layer 40 does not allow gas and electrons to pass through while allowing oxide ions to pass from the cathode layer 30 to the anode layer 50. In the case where oxygen ions are a conductor for power generation, the electrolyte layer 40 is preferably formed of a material having high oxygen ion conductivity.

[0051] The electrolyte layer 40 is formed of ceramics. The ceramics forming the electrolyte layer 40 are, for example, stabilized zirconia doped with rare earth oxides (for example, one or more selected from Y2O3, Sc2O3, Gd2O3, Sm2O3, Yb2O3, Nd2O3, etc.), colloidal solid solutions, perovskite oxides (for example, SrCeO3, BaCeO3, CaZrO3, SrZrO3, etc.) and other solid oxide ceramics. In addition, in this specification, the so-called "ceramics" refers to a broad meaning of a sintered body of an inorganic substance, and is not limited to non-metallic oxides, but also includes metal oxides.

[0052] (Anode layer 50)

[0053] The anode layer 50 is a fuel electrode, and reacts the anode gas (e.g., hydrogen) with oxide ions to generate oxides of the anode gas and extract electrons. The anode layer 50 is resistant to a reducing gas environment, and has high gas permeability and electrical (electron and ion) conductivity for the anode gas to pass through. Furthermore, the anode layer 50 has a catalytic function for reacting the anode gas with the oxide ions.

[0054] Figure 6 It is a magnified representation Figure 5 A partial cross-sectional view of the electrolyte layer and anode layer of the metal-supported battery shown in FIG. Figure 6 As shown, the anode layer 50 includes ceramic particles 210 and metal particles 220. The anode layer 50 of this embodiment includes a first anode layer 51 disposed adjacent to the electrolyte layer 40 and a second anode layer 52 disposed adjacent to the metal support layer 60.

[0055] The first anode layer 51 is mainly formed of ceramic particles 210. The second anode layer 52 is formed of a cermet composed of ceramic particles 210 and metal particles 220. Thus, the ratio of the content of the metal particles 220 to the content of the ceramic particles 210 in the anode layer 50 is formed so that the metal support layer 60 side is larger than the electrolyte layer 40 side.

[0056] As described above, the content of ceramic is high in the first anode layer 51 disposed on the electrolyte layer 40 side. Therefore, the power generation performance can be improved by improving the ion conductivity at the interface between the anode layer 50 and the electrolyte layer 40.

[0057] Anode layer 50 is a porous body having a plurality of cavities formed therein. A catalyst is impregnated in the cavities in anode layer 50. As the catalyst of anode layer 50, for example, a metal catalyst such as nickel (Ni) can be used.

[0058] As a constituent material of the ceramic particles 210 , the same material as the ceramic forming the electrolyte layer 40 can be used.

[0059] As the constituent material of the metal particles 220, the same material as the metal forming the metal support layer 60 can be used. In addition, in this specification, "metal particles 220" means the main component constituting the anode layer 50, and does not include a metal catalyst. In other words, the metal particles 220 are composed of a metal material that does not have a catalytic function or a metal material whose catalytic function is not the main function. In addition, "the metal forming the metal particles 220" and "the metal forming the metal support layer 60" do not include ceramics such as metal oxides.

[0060] (Metal Support Layer 60)

[0061] like Figure 3 and Figure 4As shown, the metal support layer 60 supports the electrolyte electrode assembly 20 from the anode layer 50 side. By supporting the electrolyte electrode assembly 20 by the metal support layer 60, the mechanical strength of the electrolyte electrode assembly 20 can be improved to suppress damage. The metal support layer 60 is formed of a porous metal having gas permeability and electron conductivity.

[0062] like Figure 5 As shown, the metal support layer 60 of this embodiment includes a first metal support layer 61 and a second metal support layer 62, the first metal support layer 61 is adjacent to the anode layer 50, and the second metal support layer 62 is adjacent to the first metal support layer 61. The second metal support layer 62 is located at the surface layer (outermost layer) of the metal support battery 10.

[0063] As the metal forming the metal support layer 60 , for example, stainless steel (SUS) containing nickel (Ni) or chromium (Cr) or the like can be used.

[0064] (Battery frame 113)

[0065] like Figure 3 and Figure 4 As shown, the battery frame 113 holds the metal supporting battery 10 from all sides. Figure 3 As shown, the battery frame 113 has an opening 113H. The metal supporting battery 10 is disposed in the opening 113H of the battery frame 113. The outer periphery of the metal supporting battery 10 is bonded to the inner edge of the opening 113H of the battery frame 113.

[0066] like Figure 3 As shown, the cell frame 113 has an anode gas inlet 113 a and an anode gas outlet 113 b through which the anode gas flows, and a cathode gas inlet 113 c and a cathode gas outlet 113 d through which the cathode gas flows.

[0067] (Partition plate 120)

[0068] like Figure 2 As shown, the flow path 121 of the partition plate 120 is formed substantially linearly so that the concavo-convex shape extends in one direction (the Y direction). Therefore, the flow direction of the gas flowing along the flow path 121 is the Y direction.

[0069] like Figure 2 As shown, the separator 120 has an anode gas inlet 125a and an anode gas outlet 125b through which the anode gas flows, and a cathode gas inlet 125c and a cathode gas outlet 125d through which the cathode gas flows.

[0070] (Current Collection Auxiliary Layer 130)

[0071] The current collecting auxiliary layer 130 forms a space for passing gas and makes the surface pressure uniform, and assists in the electrical contact between the metal supporting cell 10 and the separator 120. The current collecting auxiliary layer 130 may be formed of, for example, a metal mesh-shaped expanded metal or the like.

[0072] [Internal stress of each layer of the metal support battery 10]

[0073] Figure 7 It is a partial cross-sectional view and stress distribution for explaining the internal stress of each layer of the metal support battery 10. The metal support battery 10 is formed by a manufacturing method described later so that each layer has internal stress.

[0074] The electrolyte layer 40 has a compressive residual stress along the XY plane direction. At least one other layer other than the electrolyte layer 40 among the multiple layers constituting the metal support battery 10 has a tensile residual stress along the XY plane direction. In addition, in this specification, "internal stress" includes compressive residual stress and tensile residual stress, which means stress maintained or generated inside each layer by the material itself, regardless of external force.

[0075] In this embodiment, if Figure 7 As shown, the electrolyte layer 40, the anode layer 50 and the second metal support layer 62 have compressive residual stress along the XY plane direction. The first metal support layer 61 has tensile residual stress along the XY plane direction.

[0076] The surface layers (electrolyte layer 40 and second metal support layer 62) of the metal support battery 10 of this embodiment retain compressive residual stress. Thus, the metal support battery 10 is strengthened using the same mechanism as strengthened glass, which increases strength by retaining compressive residual stress in the surface layer.

[0077] Furthermore, the stress distribution of the metal support battery 10 is a symmetrical stress distribution in which the layers on the surface side (electrolyte layer 40, anode layer 50, and second metal support layer 62) have compressive residual stress and the center layer (first metal support layer 61) has tensile residual stress. As a result, the internal stress of the metal support battery 10 is offset. As a result, the deflection of the metal support battery 10 can be suppressed. As a result, a large compressive residual stress can be applied to the electrolyte layer 40.

[0078] In addition, the surface layer of the metal support cell 10 receives external input by contacting the current collecting auxiliary layer 130 or the separator 120. The surface layer of the metal support cell 10 has a compressive residual stress to improve strength, thereby suppressing deformation or damage due to external input.

[0079] The brittle ceramic material constituting the electrolyte layer 40 and the anode layer 50 has the characteristics of weak tensile stress and strong compressive stress. As described above, the electrolyte layer 40 and the anode layer 50 (ceramic layer) are formed in a manner to have compressive residual stress, thereby suppressing the generation of cracks in the ceramic layer (especially the electrolyte layer 40).

[0080] On the other hand, since the metal support layer 60 has ductility characteristics, the tensile stress is strong. By adopting a structure in which the first metal support layer 61 with strong tensile stress bears the reaction force to the compressive residual stress, the strength of the metal support battery 10 can be further improved.

[0081] [Linear Expansion Coefficient of Each Layer of the Metal Support Cell 10]

[0082] In the temperature range from room temperature (about 15°C to 30°C) to sintering temperature (about 1000°C to 1400°C), the linear expansion coefficient (CTE) of the metal support layer 60 composed of a metal material is generally larger than the linear expansion coefficient (CTE) of the electrolyte layer 40 and the anode layer 50 composed of a ceramic material. In addition, in the present embodiment, since the anode layer 50 is formed of a material in which the ceramic particles 210 and the metal particles 220 are mixed, the linear expansion coefficient of the anode layer 50 is larger than that of the electrolyte layer 40. Therefore, the magnitude relationship of the linear expansion coefficients of the multiple layers of the metal support battery 10 is that the linear expansion coefficient of the electrolyte layer 40 is less than the linear expansion coefficient of the anode layer 50 and less than the linear expansion coefficient of the metal support layer 60.

[0083] [Method for manufacturing metal support battery 10]

[0084] Next, refer to Figure 8 to Figure 14 , a method for manufacturing the metal support battery 10 is described.

[0085] In the following description, a method of manufacturing a half cell composed of the precursor of the metal support cell 10 , ie, the electrolyte layer 40 , the anode layer 50 , and the metal support layer 60 will be described, and a method of forming the cathode layer 30 will be omitted.

[0086] Figure 8 1 is a schematic diagram for explaining a method for manufacturing a metal support battery 10. Figure 8 As shown, the method for manufacturing the metal support battery 10 includes a slurry preparation step, a coating step, a bonding step, and a sintering step. The method for manufacturing the metal support battery 10 also includes a cooling step of cooling after the sintering step.

[0087] In the present embodiment, the internal stress of the metal support cell 10 is controlled by adjusting both the sintering and hardening time of each layer in the sintering process and the cooling shrinkage rate of each layer in the cooling process caused by the linear expansion coefficient (CTE). By controlling both the sintering and hardening time and the linear expansion coefficient (CTE), the internal stress of the manufactured metal support cell 10 can be more reliably adjusted.

[0088] (Slurry Preparation Process)

[0089] First, in the slurry preparation step, slurry raw materials are mixed to prepare electrolyte slurry, first anode slurry, second anode slurry, first metal support slurry, and second metal support slurry. A known stirring device can be appropriately selected to mix the slurry raw materials.

[0090] The electrolyte slurry is formed by mixing ceramic as a main component with a slurry raw material containing a solvent, a sintering aid, and a binder.

[0091] The first anode slurry is formed by mixing a slurry raw material containing a solvent, a sintering aid and a binder with ceramic (ceramic particles 210) as the main component. The second anode slurry is formed by mixing a slurry raw material containing a solvent, a sintering aid and a binder with ceramic (ceramic particles 210) and metal (metal particles 220) as the main components.

[0092] The first metal support paste and the second metal support paste are formed by mixing a paste raw material containing a solvent, a sintering aid, and a binder with a metal as a main component.

[0093] In the manufacturing method of this embodiment, by adjusting the amount of the sintering aid, the sintering and hardening time of each layer is controlled in the sintering process of the subsequent process. Specifically, the amount of the sintering aid is adjusted to electrolyte slurry> first anode slurry> second anode slurry> first metal support slurry, and the second metal support slurry> first metal support slurry. Therefore, in the sintering process, the order of electrolyte slurry→first anode slurry→second anode slurry→first metal support slurry can be followed, and the order of second metal support slurry→first metal support slurry can be followed to harden and shrink. The sintering process is described in detail later.

[0094] There are no particular restrictions on the solvent used for the slurry, but examples of the solvent include water and / or alcohol, ethanol, 1-propanol (NPA), 2-propanol, ethylene glycol, propylene glycol and other alcohol solvents, N-methyl-2-pyrrolidone (NMP) and other organic solvents. These solvents may be used alone or in combination of two or more. When the slurry is formed into a sheet, it is preferred to adjust the amount of the solvent so that its viscosity is suitable for forming.

[0095] The binder added to the slurry can be appropriately selected from known organic binders for use. As the organic binder, for example, celluloses such as ethylene copolymers, styrene copolymers, acrylate copolymers, methacrylate copolymers, polyvinyl butyral resins, vinyl acetal resins, vinyl ethyl resins, vinyl alcohol resins, and ethyl cellulose.

[0096] Furthermore, a plasticizer, a dispersant, etc. may be added to each slurry as necessary.

[0097] (Coating process)

[0098] Next, in the coating process, a sheet forming method such as a scraper forming method using a coating device such as a scraper or a scraper is used to form each slurry prepared in the above-mentioned slurry preparation process into a thin sheet. By heating the obtained sheet-shaped slurry as needed after drying, an electrolyte sheet, a first anode electrode sheet, a second anode electrode sheet, a first metal support sheet, and a second metal support sheet can be obtained. The electrolyte sheet, the first anode electrode sheet, the second anode electrode sheet, the first metal support sheet, and the second metal support sheet are generally referred to as raw sheets.

[0099] (Bonding process)

[0100] Next, in the bonding step, the electrolyte sheet, the first anode electrode sheet, the second anode electrode sheet, the first metal support sheet, and the second metal support sheet are sequentially stacked and bonded to form a stacked body.

[0101] (Sintering process)

[0102] Next, refer to Figures 9 to 14 The sintering process will be described. Fig. 9 It is a cross-sectional view showing the internal stress when the first anode layer 51 is sintered and hardened in the sintering step. Fig.10 It is a cross-sectional view showing the internal stress when the second anode layer 52 is sintered and hardened in the sintering step. Fig.11 It is a magnified representation Fig.10 A partial cross-sectional view of the electrolyte layer 40 and the anode layer 50 is shown. Fig.12 Yes means Fig.10 A graph showing the relationship between the thickness ratio of the electrolyte layer 40 and the surface stress of the electrolyte layer 40 in the illustrated state. Fig.13 It is a cross-sectional view showing the internal stress when the second metal supporting layer 62 is sintered and hardened in the sintering step. Fig.14 It is a cross-sectional view showing the internal stress when the first metal supporting layer 61 is sintered and hardened in the sintering step.

[0103] In the sintering process, the internal stress of the metal support battery 10 is controlled by controlling the sintering and hardening time of each layer. Specifically, at least one of the electrolyte layer 40, the anode layer 50 (electrode layer), and the metal support layer 60 is sintered and hardened and shrunk, and compressive residual stress is applied to the layer adjacent to the sintered layer. Furthermore, tensile residual stress is applied to the layer sintered as a reaction force to the compressive residual stress.

[0104] Assuming that the sintering and hardening time of each layer is the same, each layer shrinks simultaneously during sintering. In this case, it is also possible to consider controlling the internal stress by setting a difference in the sintering shrinkage rate of each layer. However, the difference in shrinkage caused by the difference in sintering shrinkage rate when each layer shrinks simultaneously is smaller than the difference in shrinkage when only one of the adjacent layers shrinks. Therefore, controlling the sintering and hardening time can apply a greater compressive residual stress than controlling the sintering shrinkage rate.

[0105] In the sintering process, the above-mentioned stack is degreased and co-sintered. For example, the sintering temperature can be 1000°C to 1400°C. As described above, the order of electrolyte slurry → first anode slurry → second anode slurry → first metal support slurry, and the order of second metal support slurry → first metal support slurry is used to harden and shrink (burn and press). In this embodiment, the amount of the sintering aid is adjusted in a manner that the sintering and hardening is carried out in the order of electrolyte slurry → first anode slurry → second anode slurry → second metal support slurry → first metal support slurry.

[0106] First, the electrolyte slurry is sintered and hardened to form the electrolyte layer 40. Next, as Fig. 9 As shown, the first anode slurry is sintered and hardened to form the first anode layer 51. At this time, the first anode layer 51 hardens and shrinks, exerting compressive residual stress on the adjacent electrolyte layer 40. Tensile residual stress is exerted on the first anode layer 51 as a reaction force to the compressive residual stress of the electrolyte layer 40.

[0107] Next, if Fig.10 As shown, the second anode slurry is sintered and hardened to form the second anode layer 52. The second anode layer 52 is hardened and shrunk, and compressive residual stress is applied to the adjacent first anode layer 51. In addition, compressive residual stress is further applied to the electrolyte layer 40 via the first anode layer 51.

[0108] Reference Fig.11 In the ceramic layers (electrolyte layer 40 and anode layer 50), by sequentially sintering in the stacking direction from the side away from the metal support layer 60 to the side close to the metal support layer 60, a large compressive residual stress can be applied to the electrolyte layer 40.

[0109] As in the present embodiment, even when the first anode layer 51 without a metal skeleton exists in the anode layer 50 in order to improve the power generation performance, the internal stress of the fragile first anode layer 51 of the ceramic body is set to a compressive state by the second anode layer 52 having a metal skeleton (metal particles 220) with high fracture toughness and rigidity starting to harden and shrink from the back. Furthermore, the reaction force of the compressive residual stress of the first anode layer 51 can be supported by the second anode layer 52 having a metal skeleton with strong tensile stress.

[0110] Here, reference Fig.12 , the relationship between the thickness ratio of the electrolyte layer 40 and the surface stress of the electrolyte layer 40 is discussed. Assuming that, at a sintering temperature of 1200° C., the Young's modulus of the electrolyte layer 40 is 150 GPa, the Young's modulus of the anode layer 50 is 55 GPa, and the strain difference due to the substantial sintering shrinkage of the electrolyte layer 40 and the anode layer 50 is 0.5%. Fig.10 As shown, in the state where the electrolyte layer 40 and the anode layer 50 are sintered and hardened, Fig.12 The relationship between the thickness ratio of the electrolyte layer 40 and the surface stress (surface compressive residual stress) of the electrolyte layer 40 is shown. Here, the thickness ratio of the electrolyte layer 40 is the ratio of the thickness of the electrolyte layer 40 to the total thickness of the electrolyte layer 40 and the anode layer 50. Fig.12 In the graph shown, the compressive residual stress on the surface of the electrolyte layer 40 is represented by a negative value. Since the magnitude of the compressive residual stress is an absolute value, the more negative the vertical axis is, the higher the value is.

[0111] from Fig.12 The results shown show that by making the thickness ratio of the electrolyte layer 40 less than 0.3 or more than 0.5, the compressive residual stress on the surface of the electrolyte layer 40 can be further increased. From the viewpoint of reducing the resistance to improve the power generation performance, the thickness ratio of the electrolyte layer 40 is preferably less than 0.3. From the viewpoint of increasing the compressive residual stress on the surface of the electrolyte layer 40, the thickness ratio of the electrolyte layer 40 is preferably more than 0.5.

[0112] Next, if Fig.13 As shown, the second metal support slurry is sintered and hardened to form a second metal support layer 62 .

[0113] Then, if Fig.14As shown, the first metal support slurry is sintered and hardened to form the first metal support layer 61. By causing the first metal support layer 61 having the greatest fracture toughness and rigidity in the metal support battery 10 to harden and shrink last, compressive residual stress is applied to the adjacent second anode layer 52 and the second metal support layer 62. As a result, the tensile residual stress of the second anode layer 52 is converted into compressive residual stress. In addition, compressive residual stress is further applied to the electrolyte layer 40 via the first anode layer 51. The tensile residual stress is applied to the first metal support layer 61 as a reaction force to the compressive residual stress of the second anode layer 52 and the second metal support layer 62.

[0114] As described above, the metal support layer 60 is sintered sequentially in the stacking direction from the side away from the ceramic layer (electrolyte layer 40 and anode layer 50) toward the side close to it. As a result, a portion of the metal support layer 60 on the surface layer side that is easily exposed to external input has compressive residual stress, thereby improving the strength against external input.

[0115] like Fig.14 As shown, by using the above sintering process, it is possible to achieve a stress state in which all layers including the ceramic in the metal support battery 10 (electrolyte layer 40 and anode layer 50) have compressive residual stress, and only the first metal support layer 61 has tensile residual stress. As a result, the internal stress of the metal support battery 10 is offset and the structure is more stable.

[0116] Furthermore, by dividing the metal support layer 60 into two parts, the first metal support layer 61 is hardened and shrunk last, and compressive residual stress can be applied to the second metal support layer 62 as the surface layer of the metal support battery 10. As a result, a symmetrical stress distribution is achieved in which the upper and lower surface layers of the metal support battery 10 have compressive residual stress and only the center layer has tensile residual stress. As a result, the bending moment inside the metal support battery 10 is offset, the deflection of the metal support battery 10 can be suppressed, and a larger compressive residual stress can be applied to the electrolyte layer 40.

[0117] (Cooling process)

[0118] Finally, in the cooling step, the metal support battery 10 is cooled. The cooling step is to leave the battery at room temperature (15°C to 30°C) to cool naturally. In addition, the natural cooling step may be performed in a reducing gas environment or in the air to prevent oxidation.

[0119] As described above, in the temperature range from room temperature to the sintering temperature, the magnitude relationship of the linear expansion coefficients of the plurality of layers is such that the linear expansion coefficient of the electrolyte layer 40 is less than the linear expansion coefficient of the anode layer 50 and less than the linear expansion coefficient of the metal support layer 60. Therefore, the magnitude relationship of the shrinkage rate in the cooling process is such that the shrinkage rate of the electrolyte layer 40 is less than the shrinkage rate of the anode layer 50 and less than the shrinkage rate of the metal support layer 60. Thus, in the temperature range from room temperature to the operating temperature (about 600 to 800° C.) in the practical range, compressive residual stress can be applied to the electrolyte layer 40 having a relatively small linear expansion coefficient.

[0120] Next, the effects of this embodiment will be described.

[0121] The metal support battery 10 of the present embodiment is a metal support battery in which a plurality of layers including an electrolyte layer 40, electrode layers 30 and 50, and a metal support layer 60 are stacked. The electrolyte layer 40 has a compressive residual stress along the XY plane direction, and at least one of the plurality of layers other than the electrolyte layer 40 has a tensile residual stress along the XY plane direction.

[0122] In addition, in the manufacturing method of the metal support battery 10 of the present embodiment, a plurality of layers including an electrolyte layer 40, electrode layers 30, 50 and a metal support layer 60 are stacked, a compressive residual stress along the surface direction is applied to the electrolyte layer 40, and a tensile residual stress along the surface direction is applied to at least one of the plurality of layers other than the electrolyte layer 40.

[0123] According to the metal support battery 10 and the method for manufacturing the metal support battery 10 described above, since the electrolyte layer 40 has compressive residual stress in the surface direction, cracks in the electrolyte layer 40 caused by thermal stress in the actual area can be prevented. In addition, since the layers other than the electrolyte layer 40 receive tensile residual stress as a reaction force to the compressive residual stress, the internal stress of the metal support battery 10 is offset, the structure is more stable, and the strength can be improved.

[0124] In addition, at least one of the anode layer 50 (electrode layer) and the metal support layer 60 has tensile residual stress in the surface direction. Since the anode layer 50 (electrode layer) and the metal support layer 60 other than the electrolyte layer 40 are subjected to tensile residual stress, the internal stress of the metal support battery 10 is offset, the structure can be more stable, and the strength is improved.

[0125] In addition, at least one of the anode layer 50 (electrode layer) and the metal support layer 60 has a compressive residual stress in the surface direction. In the case where the anode layer 50 including ceramic has a compressive residual stress in the surface direction, cracks in the anode layer 50 caused by thermal stress can be prevented. When the metal support layer 60 has a compressive residual stress in the surface direction, a symmetrical stress distribution is formed in which the surface layers (electrolyte layer 40 and metal support layer 60) of the metal support battery 10 have a compressive residual stress and only the center layer (anode layer 50) has a tensile residual stress. The internal stress of the metal support battery 10 is offset. This can suppress the deflection of the metal support battery 10. As a result, a large compressive residual stress can be applied to the electrolyte layer 40.

[0126] In addition, the metal support layer 60 is also composed of a first metal support layer 61 and a second metal support layer 62 (multiple layers). The second metal support layer 62, which is at least one surface layer among the multiple layers of the metal support layer 60, has a compressive residual stress along the XY plane direction. The first metal support layer 61, which is a layer other than the surface layer among the multiple layers of the metal support layer 60, has a tensile residual stress along the XY plane direction.

[0127] According to the above structure, by dividing the metal support layer 60 into two parts, the first metal support layer 61 is hardened and shrunk last, and compressive residual stress can be applied to the second metal support layer 62 located in the surface layer. As a result, a symmetrical stress distribution is formed in which the upper and lower surface layers of the metal support battery 10 have compressive residual stress and only the center layer has tensile residual stress. As a result, the bending moment inside the metal support battery 10 is offset, the deflection of the metal support battery 10 can be suppressed, and a larger compressive residual stress can be applied to the electrolyte layer 40. In addition, since the second metal support layer 62 that is easy to receive input from the outside has compressive residual stress, the strength against external input can be improved.

[0128] The magnitude relationship of the linear expansion coefficients of the multiple layers of the metal support battery 10 is that the linear expansion coefficient of the electrolyte layer 40 is less than the linear expansion coefficient of the anode layer 50 (electrode layer) and less than the linear expansion coefficient of the metal support layer 60. Therefore, the magnitude relationship of the shrinkage rate in the cooling process is that the shrinkage rate of the electrolyte layer 40 is less than the shrinkage rate of the anode layer 50 and less than the shrinkage rate of the metal support layer 60. As a result, compressive residual stress can be applied to the electrolyte layer 40 having a relatively small linear expansion coefficient.

[0129] In addition, according to the manufacturing method of the metal support battery 10, the internal stress of the metal support battery 10 is controlled by controlling the sintering and hardening time. At least one layer of the electrolyte layer 40, the anode layer 50 (electrode layer) and the metal support layer 60 is sintered and hardened and shrunk, and a compressive residual stress is applied to the layer adjacent to the sintered layer, and a tensile residual stress is applied to the sintered layer as a reaction force to the compressive residual stress. By controlling the sintering and hardening time of each layer, a larger compressive residual stress can be applied than in the case of controlling only the sintering shrinkage rate.

[0130] In addition, in the control of the sintering and hardening time, the anode layer 50 (electrode layer) and the electrolyte layer 40 are sequentially sintered from the side away from the metal support layer 60 to the side close to the metal support layer 60 in the stacking direction. As a result, a large compressive residual stress can be applied to the electrolyte layer 40 away from the metal support layer 60.

[0131] In addition, under the control of the sintering and hardening time, the metal support layer 60 is sintered after the anode layer 50 (electrode layer) and the electrolyte layer 40. As a result, the metal support layer 60 with strong tensile stress can be structured to receive tensile residual stress as a reaction force to compressive residual stress. Therefore, the internal stress of the metal support battery 10 is offset, the structure is more stable, and the strength can be further improved.

[0132] In addition, under the control of the sintering and hardening time, the metal support layer 60 is sequentially sintered from the side away from the electrolyte layer 40 to the side close to the electrolyte layer 40 in the stacking direction. As a result, a portion of the metal support layer 60 on the surface layer side that is easily exposed to external input has compressive residual stress, thereby improving the strength against external input.

[0133] In addition, the anode layer 50 (electrode layer) has: a first anode layer 51 (first electrode layer) including ceramics and catalysts; a second anode layer 52 (second electrode layer) including ceramics, metals and catalysts and arranged closer to the metal support layer 60 than the first anode layer 51. Under the control of the sintering and hardening time, the electrolyte layer 40, the first anode layer 51, the second anode layer 52, and the metal support layer 60 are sintered in this order. Thus, by sintering the second anode layer 52 from the back and hardening and shrinking it, the internal stress of the first anode layer 51, which is a fragile ceramic body, can be put into a compressed state. Furthermore, the reaction force of the compressive residual stress of the first anode layer 51 can be supported by the second anode layer 52 having a metal skeleton with strong tensile stress.

[0134] Next, a modification of the present embodiment will be described.

[0135] [Modification of Metal Support Battery]

[0136] The following describes a modification of the metal support battery. The structure of the metal support battery of this embodiment can be appropriately changed as long as at least the electrolyte layer has a compressive residual stress in the surface direction and at least one of the multiple layers other than the electrolyte layer has a tensile residual stress in the surface direction. In the following modification 1 and modification 2, an example of the multiple modes included in the present invention is described, but the present invention is not limited to the above-mentioned embodiment and modification. In addition, for the same structure as the above-mentioned embodiment, the same symbols are applied and their descriptions are omitted.

[0137] <Modification 1>

[0138] Fig.15 It is a partial cross-sectional view for explaining the internal stress of each layer of the metal support battery according to Modification 1. The metal support battery according to Modification 1 is different from the above-mentioned embodiment in that the metal support layer 160 is composed of a single layer and has no internal stress.

[0139] The electrolyte layer 40 and the first anode layer 51 have compressive residual stress along the XY plane direction. The second anode layer 52 has a tensile residual stress along the XY plane direction as a reaction force to the compressive residual stress. Since the fragile electrolyte layer 40 and the first anode layer 51 of the ceramic body have compressive residual stress, the generation of cracks caused by thermal stress in the actual area can be suppressed. In addition, the second anode layer 52 having a metal skeleton with strong tensile stress is subjected to tensile residual stress, so the internal stress of the metal support battery is offset, the structure can be more stable, and the strength is improved.

[0140] <Modification 2>

[0141] Fig.16A 1 is a partial cross-sectional view for explaining the internal stress of each layer of the metal supporting battery according to Modification 2. The metal supporting battery according to Modification 2 is different from the above-mentioned embodiment in that the metal supporting layer 160 is composed of a single layer and has tensile residual stress.

[0142] Since the metal material is the main component, the metal support layer 160 which has the strongest tensile stress among the multiple layers of the metal support battery is subjected to tensile residual stress, so the internal stress of the metal support battery is offset, the structure can be more stable, and the strength is improved.

[0143] However, in the metal supported battery of Modification 2, since the internal stress distribution is asymmetric, deflection may occur. Fig. 16B: is a partial cross-sectional view showing the bending state of the metal support battery of Modification Example 2. In the electrolyte layer 40 having compressive residual stress in the XY plane direction, it is deformed in the direction extending along the XY plane direction, and in the metal support layer 160 having tensile residual stress in the XY plane direction, it is deformed in the direction compressed along the XY plane direction. Fig. 16B Therefore, from the viewpoint of suppressing the bending, the internal stress distribution of the metal support battery is preferably symmetrical as in the above-mentioned embodiment.

[0144] [Variation of the method for producing a metal-supported battery]

[0145] Next, a modification of the method for manufacturing a metal support battery is described. The method for manufacturing a metal support battery of the present invention can be appropriately changed as long as a compressive residual stress can be applied to the electrolyte layer in the surface direction, and a tensile residual stress can be applied to at least one of the multiple layers other than the electrolyte layer in the surface direction. In the following modification 3 and modification 4, an example of a structure included in the present invention is described, but the present invention is not limited to the above-mentioned embodiment and modification. In addition, for the same structure as the above-mentioned embodiment, the same symbol is applied and its description is omitted.

[0146] <Variation 3>

[0147] Fig.17A This is a schematic cross-sectional view for explaining a method for manufacturing a metal support battery according to Modification 3. Fig. 17B 2 is a cross-sectional view showing the internal stress of a metal support battery manufactured by the manufacturing method of Modification 3. The manufacturing method of the metal support battery of Modification 3 is different from the above-mentioned embodiment in that the metal support battery of Modification 2 is manufactured.

[0148] like Fig.17A As shown, in the sintering process, after the electrolyte layer 40 and the anode layer 150 are sintered and hardened in this order, the metal support layer 160 is sintered and hardened. As a result, compressive residual stress is applied to the ceramic layers (electrolyte layer 40 and anode layer 150), and tensile residual stress is applied to the metal support layer 160 as its reaction force.

[0149] like Fig. 17B As shown, since the electrolyte layer 40 has compressive residual stress along the surface direction, cracks in the electrolyte layer 40 caused by thermal stress in the actual area can be prevented. In addition, since the metal support layer 160 with strong tensile stress receives tensile residual stress as a reaction force to the compressive residual stress, the internal stress of the metal support battery is offset, the structure can be more stable, and the strength is improved.

[0150] <Variation 4>

[0151] Fig.18 1 is a schematic cross-sectional view for explaining a method for manufacturing a metal support battery according to Modification 4. The method for manufacturing a metal support battery according to Modification 4 is different from the above-mentioned embodiment in that the electrolyte layer 40 and the metal support layer 160 are first hardened and shrunk, and finally the anode layer 50 is hardened and shrunk.

[0152] By the above manufacturing method, compressive residual stress can be applied to the electrolyte layer 40 and the metal support layer 160. Since the anode layer 50 has a metal skeleton with strong tensile stress, it can withstand tensile residual stress. In addition, since the overall stress distribution of the metal support battery is nearly symmetrical, the overall deflection of the metal support battery can be reduced.

[0153] (Variation of the method of controlling the sintering hardening time)

[0154] In the above embodiment, the amount of the sintering aid is adjusted to control the sintering and hardening time, but the method of controlling the sintering and hardening time is not limited to this. For example, there can be listed a method of adjusting the amount of the sintering inhibitor of each layer, a method of controlling the sintering and hardening temperature, thermal conductivity, heating rate, etc. of each layer, and a method of controlling the sintering temperature of each layer according to manufacturing requirements. In the following Modifications 5 to 7, several examples of the above methods are described.

[0155] <Variation 5>

[0156] In the method for manufacturing a metal supported battery of Modification 5, the sintering and hardening time is controlled by adjusting the amount of the sintering inhibitor (delay) agent in each layer. In the slurry preparation step, the sintering inhibitor is added to each slurry instead of the sintering auxiliary agent. By adjusting the amount of the sintering inhibitor, the sintering and hardening time of each layer can be controlled.

[0157] Specifically, the amount of the sintering inhibitor is adjusted to electrolyte slurry < first anode slurry < second anode slurry < first metal support slurry, and second metal support slurry < first metal support slurry. Thus, in the sintering process, as in the above embodiment, hardening and shrinkage can be performed in the order of electrolyte slurry → first anode slurry → second anode slurry → first metal support slurry, and in the order of second metal support slurry → first metal support slurry.

[0158] <Variation 6>

[0159] Fig.19 It is a schematic cross-sectional view for explaining the method for manufacturing a metal support cell according to Modification 6. In the method for manufacturing a metal support cell according to Modification 6, the sintering and laminating are repeated in the sintering step while the layers are overlapped and sintered to control the sintering and hardening time.

[0160] First, the electrolyte layer 40 is stacked on the anode layer 50 and sintered. Then, the electrolyte layer 40 and the anode layer 50 hardened by sintering are stacked on the metal support layer 160 and sintered.

[0161] Thus, the metal support layer 160 can be sintered and hardened after the electrolyte layer 40 and the anode layer 50. Thus, the ceramic layer (electrolyte layer 40 and anode layer 50) can maintain compressive residual stress as a whole.

[0162] <Variation 7>

[0163] Fig. 20 It is a schematic cross-sectional view for explaining the method for manufacturing a metal support cell according to Modification 7. In the method for manufacturing a metal support cell according to Modification 7, the sintering and hardening time is controlled by using a PVD (physical vapor deposition) method.

[0164] First, the anode layer 50 is sintered and hardened. Then, the electrolyte layer 40 is formed on the sintered and hardened anode layer 50 through a PVD process. Finally, the electrolyte layer 40 and the anode layer 50 are stacked on the metal support slurry and sintered to form the metal support layer 160. Thus, compressive residual stress can be applied to the entire ceramic layer (electrolyte layer 40 and anode layer 50).

[0165] Although the metal support battery and the method for producing the metal support battery of the present invention have been described above by using the embodiments and the modified examples, the present invention is not limited to the contents described in the embodiments and can be modified appropriately based on the contents described in the claims.

[0166] For example, the method of generating compressive residual stress in the electrolyte layer is not limited to the method of adjusting the sintering hardening time or the linear expansion coefficient (CTE). For example, compressive residual stress can be generated in the electrolyte layer by surface treatment such as surface quenching and shot peening.

[0167] In addition, in the above embodiment, the internal stress is controlled by controlling the sintering and hardening time, but the sintering shrinkage rate can also be further adjusted. Under the premise of controlling the sintering and hardening time as in the above embodiment, the magnitude relationship of the sintering shrinkage rate is set to the shrinkage rate of the electrolyte layer < the shrinkage rate of the anode layer < the shrinkage rate of the metal support layer, which can apply a greater compressive residual stress to the ceramic layer (electrolyte layer and anode layer). In addition, the sintering shrinkage rate can be controlled by adjusting the binder amount of each slurry and the particle size of the material.

[0168] In addition, the stacking configuration of the anode layer and the cathode layer may be reversed. In this case, the cathode layer may have the same configuration as the anode layer in the above-mentioned embodiment and the modified example.

[0169] This application is based on Japanese Patent Application No. 2018-07551 filed on April 13, 2018, the disclosure of which is incorporated herein by reference in its entirety.

[0170] Explanation of symbols

[0171] 1: Fuel cell stack

[0172] 1U: Battery Unit

[0173] 1A: Metal-supported battery assembly

[0174] 10: Metal-supported battery

[0175] 20: Electrolyte electrode junction

[0176] 30: Cathode layer

[0177] 40: Electrolyte layer

[0178] 50, 150: Anode layer

[0179] 51: First anode layer

[0180] 52: Second anode layer

[0181] 60, 160: Metal support layer

[0182] 61: First metal support layer

[0183] 62: Second metal support layer

[0184] 113: Battery frame

[0185] 120: Divider

[0186] 130: Collector auxiliary layer

[0187] 210: Ceramic particles

[0188] 220: Metal particles

Claims

1. A metal support battery, comprising: an electrode layer of one of a cathode layer and an anode layer, an electrolyte layer, an electrode layer of the other of the cathode layer and the anode layer, and a metal support layer, which are sequentially stacked, characterized in that: The electrolyte layer has a compressive residual stress along the surface direction, At least one of the other electrode layer and the metal support layer has a tensile residual stress in a surface direction, The metal support layer is composed of multiple layers. At least one layer of the plurality of layers of the metal support layer, which is farthest from the electrode layer, has a compressive residual stress in the surface direction. The layers of the plurality of layers of the metal support layer other than the layer farthest from the electrode layer have tensile residual stress in the surface direction, The in-plane direction is defined as the plane direction relative to the stacking direction of the layers.

2. The metal support battery according to claim 1, characterized in that: At least one of the electrode layer and the metal support layer has a tensile residual stress in a surface direction.

3. The metal support battery according to claim 1 or 2, characterized in that: At least one of the electrode layer and the metal support layer has compressive residual stress along a surface direction.

4. The metal support battery according to claim 1 or 2, characterized in that: The magnitude relationship of the linear expansion coefficients is: the linear expansion coefficient of the electrolyte layer < the linear expansion coefficient of the electrode layer < the linear expansion coefficient of the metal support layer.

5. A method for manufacturing a metal-supported battery, An electrode layer of one of a cathode layer and an anode layer, an electrolyte layer, an electrode layer of the other of the cathode layer and the anode layer, and a metal support layer are sequentially stacked. applying compressive residual stress along the surface direction to the electrolyte layer, A tensile residual stress is applied to at least one of the other electrode layer and the metal support layer in a surface direction, characterized in that: The metal support layer is composed of multiple layers. applying compressive residual stress in a surface direction to at least the layer farthest from the electrode layer among the multiple layers of the metal support layer, applying a tensile residual stress in a plane direction to the layers other than the layer farthest from the electrode layer among the plurality of layers of the metal support layer, The in-plane direction is defined as the plane direction relative to the stacking direction of the layers.

6. The method for manufacturing a metal support battery according to claim 5, characterized in that: A tensile residual stress in a surface direction is applied to at least one of the electrode layer and the metal support layer.

7. The method for manufacturing a metal support battery according to claim 5 or 6, characterized in that: A compressive residual stress in a surface direction is applied to at least one of the electrode layer and the metal support layer.

8. The method for manufacturing a metal support battery according to claim 5 or 6, characterized in that: The magnitude relationship of the linear expansion coefficients is: the linear expansion coefficient of the electrolyte layer < the linear expansion coefficient of the electrode layer < the linear expansion coefficient of the metal support layer.

9. The method for manufacturing a metal support battery according to claim 5 or 6, characterized in that: sintering at least one of the electrolyte layer, the electrode layer, and the metal support layer to harden and shrink the layer, and applying the compressive residual stress to a layer adjacent to the sintered layer, A tensile residual stress is applied to the sintered layer as a reaction force to the compressive residual stress.

10. The method for manufacturing a metal support battery according to claim 9, characterized in that: The electrode layer and the electrolyte layer are sintered in sequence from a side away from the metal support layer toward a side close to the metal support layer in a stacking direction.

11. The method for manufacturing a metal support battery according to claim 9, wherein: After sintering the electrode layer and the electrolyte layer, the metal support layer is sintered.

12. The method for manufacturing a metal support battery according to claim 9, wherein: The metal supporting layer is sintered in sequence from a side away from the electrolyte layer toward a side close to the electrolyte layer in a stacking direction.

13. The method for manufacturing a metal support battery according to claim 9, wherein: The electrode layer has: A first electrode layer comprising ceramic and a catalyst; The second electrode layer includes ceramic, metal and catalyst, and is disposed closer to the metal support layer than the first electrode layer. The electrolyte layer, the first electrode layer, the second electrode layer, and the metal support layer are sintered in this order.

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