Electrochemical cells, solid oxide fuel cells, solid oxide electrolysis cells, and methods of making electrochemical cells

Abstract

The battery includes: a cell main body portion in which a first electrode layer, an electrolyte layer, and a second electrode layer are sequentially stacked; and a metal support body that supports the cell main body portion. The metal support body includes a support portion that includes a support surface that supports a main surface of the first electrode layer side of the cell main body portion and an opposite surface of the support surface, and that is communicable between the support surface and the opposite surface for passage of gas. An adhesive layer that is adhered to the support surface is provided in a region of the support surface that is opposite a peripheral edge portion of the first electrode layer. A portion of the first electrode layer that is inward of the peripheral edge portion is adhered to the support surface, and the peripheral edge portion of the first electrode layer is adhered to the adhesive layer.

Description

Technical Field

[0001] This invention relates to electrochemical cells, solid oxide fuel cells, solid oxide electrolytic cells, and methods for manufacturing electrochemical cells. Background Technology

[0002] JP6800297B discloses an electrochemical cell in which electrode layer material and electrolyte layer material are sequentially stacked on a metal support having multiple through holes, and the electrode layer and electrolyte layer are stacked on the metal support by sintering them. Summary of the Invention

[0003] However, in the JP6800297B scheme, delamination occurs at the interface between the metal support and the electrode layer during sintering, making it difficult to integrate the metal support and the electrode layer.

[0004] Therefore, the object of the present invention is to provide an electrochemical cell, a solid oxide fuel cell, a solid oxide electrolytic cell, and a method for manufacturing an electrochemical cell, thereby reducing the peeling of the metal support and the electrode layer during sintering of the material of the electrode layer disposed on the metal support.

[0005] According to one aspect of the present invention, a battery cell body is comprising a first electrode layer, an electrolyte layer, and a second electrode layer stacked sequentially, and a metal support body supporting the battery cell body. The metal support body includes a support portion, which includes a support surface supporting the main surface of the battery cell body on the side of the first electrode layer, and an opposite surface of the support surface, which can communicate with the support surface and the opposite surface to allow gas to pass through. An adhesive layer is disposed on the support surface in a region opposite to the peripheral portion of the first electrode layer. The portion of the first electrode layer that is inside the peripheral portion is bonded to the support surface, and the peripheral portion of the first electrode layer is bonded to the adhesive layer. Attached Figure Description

[0006] Figure 1 This is a cross-sectional view of the electrochemical cell of the first embodiment.

[0007] Figure 2 This is a top view of the metal support that constitutes the electrochemical cell of the first embodiment.

[0008] Figure 3 It is a diagram showing the bonding state between the fuel electrode support layer, the adhesive layer, and the support portion.

[0009] Figure 4 This is a flowchart illustrating the manufacturing process of the electrochemical cell according to the first embodiment.

[0010] Figure 5This is a diagram showing the adjacent region of the fuel electrode support layer and the adhesive layer in the sintered electrochemical cell, as well as the region outside the adjacent region of the fuel electrode support layer.

[0011] Figure 6 This is a cross-sectional view of the electrochemical cell of the first comparative example.

[0012] Figure 7 This is a cross-sectional view of the electrochemical cell of the second comparative example.

[0013] Figure 8 This is a cross-sectional view of the electrochemical cell of the second embodiment.

[0014] Figure 9 This is a schematic diagram of the electrochemical cell of this embodiment being used as a solid oxide type electrolytic cell. Detailed Implementation

[0015] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.

[0016] [First Implementation]

[0017] Figure 1 This is a cross-sectional view of the electrochemical cell of the first embodiment. Figure 2 This is a top view of the metal support 1 constituting the electrochemical cell of the first embodiment. The electrochemical cell of the first embodiment is composed of the metal support 1 and the cell body 6 (fuel electrode support layer 2 (first electrode layer), fuel electrode active layer 3 (first electrode layer), electrolyte layer 4, and air electrode layer 5 (second electrode layer)).

[0018] The main body of the battery cell 6 (electrolyte layer 4) has an affinity for oxygen ions (O2). 2- It has conductivity. In the first embodiment, the cell body 6 functions as a solid oxide fuel cell that generates electricity by supplying anode gas (hydrogen) to the first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3) and cathode gas (air, oxygen) to the second electrode layer (air electrode layer 5).

[0019] The metal support 1 has a plate shape with a specified thickness. For example... Figure 2 As shown, the metal support 1 has a rectangular shape when viewed from above, but it can also be other shapes. A plurality of through holes 123 are formed on the metal support 1, the area where the through holes 123 are formed is called the support portion 12, and the portion that forms its outer periphery is called the outer periphery portion 13.

[0020] The through hole 123 has a cross-sectional shape, for example, circular, connecting the support surface 121 and the gas flow surface 122, which is the opposite side of the support surface. Furthermore, the arrangement pattern of the through hole 123 can be arbitrarily set, but it is preferred to arrange it so that it is distributed approximately evenly in the support portion 12 when viewed from above.

[0021] The through hole 123 can be formed by machining (e.g., punching), laser processing or chemical processing (e.g., etching), but in this embodiment, it is preferably formed by fiber laser.

[0022] The through hole 123 allows gas to communicate between the support surface 121 and the flow surface 122. However, the through hole 123 may not be formed. Instead, a metal support 1 is formed by a porous metal, which allows gas to be permeable and supplies gas to the fuel electrode support layer 2 and the fuel electrode active layer 3.

[0023] The diameter of the through hole 123 is preferably 100 [μm] to 500 [μm]. Furthermore, the thickness of the metal support 1 (support part 12) is preferably 50 [μm] to 500 [μm].

[0024] The metal support 1 (support part 12) is preferably Fe-Cr alloy steel (such as stainless steel such as SUS304), but Ni-Cr alloy steel or the like can also be used, and it may also contain Ti (TiO2) and Al (Al2O3).

[0025] An adhesive layer 7 is disposed on the periphery and outer periphery 13 of the support surface 121 of the support portion 12 in such a way that it surrounds (around) the inner side of the periphery and outer periphery 13. The adhesive layer 7 is bonded to the fuel electrode support layer 2 and the electrolyte layer 4, thereby fixing the fuel electrode support layer 2 and the electrolyte layer 4 to the metal support 1.

[0026] The adhesive layer 7 is preferably disposed on the support portion 12 (support surface 121) at a position further outward than the through hole 123. Furthermore, as... Figure 2 As shown, in the metal support 1, the rectangular annular region sandwiched between the rectangular dashed line representing the boundary between the support portion 12 and the outer peripheral portion 13 and the inner periphery of the adhesive layer 7 becomes the opposing region in the support portion 12 that is opposite to (bonded to) the peripheral portion of the fuel electrode support layer 2, and the rectangular annular region sandwiched between the dashed line and the outer periphery of the adhesive layer 7 becomes the region in the outer peripheral portion 13 that is bonded to the electrolyte layer 4.

[0027] The material constituting the adhesive layer 7 includes cerium oxide. Cerium oxide, for example, readily interdiffusions with the stainless steel constituting the metal support 1 compared to zirconium oxide constituting the electrolyte layer 4. Therefore, by including cerium oxide in the adhesive layer 7, the adhesive strength (peel strength) with the support portion 12 (support surface 121) of the metal support 1 is improved. The thickness of the adhesive layer 7 is not particularly limited, and can be, for example, set to 1 [μm] to 2 [μm].

[0028] The fuel electrode support layer 2 (fuel electrode layer) is supported by the support portion 12 formed on the metal support 1 and disposed on the support surface 121 of the support portion 12. Furthermore, the peripheral portion of the fuel electrode support layer 2 is placed on the upper surface of the adhesive layer 7.

[0029] The fuel electrode support layer 2 is connected to the flow surface 122 side of the support portion 12 via the through hole 123.

[0030] The fuel electrode support layer 2 is preferably porous. The porosity (100% - filling rate) of the fuel electrode support layer 2 is not particularly limited, and can be set to, for example, 20% to 70%. The thickness of the fuel electrode support layer 2 is not particularly limited as long as it is thicker than the adhesive layer 7, and can be, for example, 2 μm to 100 μm.

[0031] In the first embodiment, an anode gas (e.g., hydrogen) is supplied to the fuel electrode support layer 2, which functions as the anode of a solid oxide fuel cell.

[0032] The fuel electrode support layer 2 can be composed of composite materials such as NiO-GDC (gadolinium-doped cerium oxide), Ni-GDC, NiO-YSZ (yttrium oxide-stabilized zirconium oxide), Ni-YSZ, CuO-CeO2, and Cu-CeO2.

[0033] There are no particular restrictions on the formation method of the fuel electrode support layer 2. It can be formed by screen printing, stamping, tape casting, sintering, spraying (thermal spraying, aerosol deposition, aerosol vapor deposition, powder spraying deposition, particle spraying deposition, cold spraying, etc.), PVD (sputtering, pulsed laser deposition, etc.), CVD, etc.

[0034] The fuel electrode active layer 3 is disposed on the fuel electrode support layer 2. The thickness of the fuel electrode active layer 3 is not particularly limited, for example, it can be 1 [μm] to 100 [μm].

[0035] The fuel electrode active layer 3 preferably has oxide ion (oxygen ion) conductivity. More preferably, it has electronic conductivity. The fuel electrode active layer 3 can be composed of YSZ, GDC, SSZ (scandium-stabilized zirconium oxide), SDC (samarium-doped cerium oxide), etc. There are no particular limitations on the method of forming the fuel electrode active layer 3; it can be formed by screen printing, stamping, casting, sintering, spraying, PVD, CVD, etc.

[0036] An electrolyte layer 4 is disposed on the fuel electrode active layer 3. The electrolyte layer 4 is disposed such that it at least covers the upper surface of the fuel electrode active layer 3. Furthermore, the electrolyte layer 4 is configured to extend, when viewed from above, to a position overlapping the main surface of the outer peripheral portion 13 and toward the adhesive layer 7 disposed on the outer peripheral portion 13. Moreover, the electrolyte layer 4 surrounds the sides of the fuel electrode active layer 3 and the fuel electrode support layer 2, and is disposed and bonded to these sides. Additionally, the electrolyte layer 4 is bonded to the upper surface of the portion of the adhesive layer 7 disposed on the main surface of the outer peripheral portion 13, such that it surrounds the main surface of that portion.

[0037] As described above, electrolyte layer 4 pairs of oxygen ions (O 2- The electrolyte layer 4 has conductivity. It also has gas barrier properties capable of suppressing the mixing of anolyte gas and cathode gas. The electrolyte layer 4 can be a multilayer structure, but preferably at least one layer is a dense layer. The porosity of the dense layer is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less. The thickness of the electrolyte layer 4 is not particularly limited, and can be, for example, from 1 μm to 10 μm.

[0038] The electrolyte layer 4 can be composed of YSZ, GDC, SSZ, SDC, LSGM, etc. There are no particular restrictions on the method of forming the electrolyte layer 4; it can be formed by screen printing, stamping, sintering, spraying, PVD, CVD, etc.

[0039] The air electrode layer 5 is disposed on top of the electrolyte layer 4. Therefore, the electrolyte layer 4 is sandwiched between the air electrode layer 5 and the fuel electrode active layer 3.

[0040] The air electrode layer 5 is formed, for example, in a manner that, when viewed from above, its shape is concealed inside the shapes of the fuel electrode support layer 2 and the fuel electrode active layer 3. Furthermore, the adhesive layer 7 is configured to separate from the region overlapping with the air electrode layer 5 (the region used for power generation reaction) when viewed from above. That is, the adhesive layer 7 is configured such that, when viewed from above, the shape of the air electrode layer 5 is concealed inside the inner periphery of the frame-shaped adhesive layer 7.

[0041] Therefore, interference between the bonding layer 7 and the power generation area between the air electrode layer 5 and the fuel electrode support layer 2 and the fuel electrode active layer 3 can be avoided, and the reduction in power generation performance can be suppressed.

[0042] The air electrode layer 5 is preferably porous. The porosity of the air electrode layer 5 is not particularly limited, and can be set to, for example, 20% to 70%. The thickness of the air electrode layer 5 is not particularly limited, and can be set to, for example, 1 μm to 100 μm.

[0043] As described above, cathode gas (air, oxygen) is supplied to the air electrode layer 5, which functions as the cathode of the solid oxide fuel cell. The air electrode layer 5 can be composed of LSCF, LSF, LSC, LNF, LSM, etc. In particular, the air electrode layer 5 preferably contains a perovskite oxide containing two or more elements selected from the group consisting of La, Sr, Sm, Mn, Co, and Fe.

[0044] There are no particular restrictions on the method of forming the air electrode layer 5. It can be formed by screen printing, stamping, sintering, spraying, PVD, CVD, etc.

[0045] [The bonding state between fuel electrode support layer 2, adhesive layer 7 and support portion 12]

[0046] Figure 3 This diagram shows the bonding state between the fuel electrode support layer 2, the adhesive layer 7, and the support portion 12.

[0047] like Figure 3 As shown, the surface (support surface 121) of the support portion 12 (metal support 1) is a smooth stainless steel plate. In contrast, the fuel electrode support layer 2 is a sintered body formed from first particles 21A, 21B, and 21C with micron-sized particles. Therefore, since the bonding area (contact area) per unit area between the support portion 12 (support surface 121) and the fuel electrode support layer 2 is small, the bonding strength is weak, and peeling is particularly prone to occur during sintering, starting from the periphery of the fuel electrode support layer 2.

[0048] On the other hand, the adhesive layer 7 is a sintered body formed from second particles 71A and 71B with submicron-sized particles. Therefore, compared with the fuel electrode support layer 2, it has a larger adhesive area per unit area with the support portion 12 (support surface 121), resulting in high adhesive strength. In addition, as described above, the diameter of the second particles 71A, etc., is smaller than that of the first particles 21A, etc. (for example, less than 1 / 10), so they can penetrate between the plurality of first particles 21A, etc., constituting the fuel electrode support layer 2.

[0049] like Figure 3 As shown, the adhesive layer 7 includes, for example, a plurality of second particles 71A disposed on the support portion 12 (support surface 121) and a plurality of second particles 71B disposed on the second particles 71A. The second particles 71A are in direct contact (adhesive) with the support portion 12 (support surface 121), and a pair of adjacent second particles 71A are also in contact (adhesive) with each other. The second particles 71B are in contact (adhesive) with the second particles 71A, and a pair of adjacent second particles 71B are in contact (adhesive) with each other.

[0050] like Figure 3As shown, the fuel electrode support layer 2 includes, for example, a first particle 21C that contacts (bonds) the support portion 12 (support surface 121) and is disposed at a position separate from the second particle 71A and the second particle 71B; a first particle 21B that contacts (bonds) the support portion 12 (support surface 121) and contacts (bonds) the second particle 71A and the second particle 71B, which form the side surface of the adhesive layer 7; and a first particle 21A that is disposed on the adhesive layer 7 and contacts (bonds) the second particle 71B (and the second particle 71A).

[0051] The first particle 21C is bonded to the support portion 12 (support surface 121) only through contact with the support portion 12 (support surface 121).

[0052] The first particle 21B is bonded to the support portion 12 (support surface 121), and is then fixed to the support portion 12 via the second particles 71A and 71B, which form the side surfaces of the adhesive layer 7. Therefore, the adhesive strength (peel strength) of the first particle 21B relative to the support portion 12 is higher than that of the first particle 21C.

[0053] The first particle 21A is separated from the support portion 12 (or may come into contact (adhere)), but is fixed to the metal support 1 via the second particles 71A and 71B. Furthermore, the number of first particles 21C that come into contact (adhere) with the second particles 71A and 71B is greater than that of the first particle 21B, and the bonding area of ​​the first particle 21C relative to the second particles 71A and 71B is larger than that of the first particle 21B. Therefore, the adhesive strength (peel strength) of the first particle 21A relative to the support portion 12 is higher than that of the first particle 21B.

[0054] Therefore, the peripheral portion of the fuel electrode support layer 2 is bonded to the adhesive layer 7 and fixed to the support portion 12 (support surface 121) via the adhesive layer 7, thereby reducing the peeling of the fuel electrode support layer 2 from the support portion 12 (support surface 121) starting from the peripheral portion of the fuel electrode support layer 2. In addition, the adhesive layer 7 can be configured to continuously surround (around) the opposing region of the support portion 12 opposite to the peripheral portion of the fuel electrode support layer 2, or multiple layers can be discretely arranged at predetermined intervals to surround (around) the opposing region.

[0055] [Manufacturing process of electrochemical cells]

[0056] Figure 4 This is a flowchart illustrating the manufacturing process of the electrochemical cell according to the first embodiment.

[0057] like Figure 4 As shown, the manufacturing process of the electrochemical cell in this embodiment consists of steps S1 to S4.

[0058] As step S1, a plurality of through holes 123 are formed in the support portion 12 of the metal support 1. The through holes 123 are formed, for example, by irradiating the support surface 121 of the support portion 12 with a fiber laser to carve from the support surface 121 to the flow surface 122, or by performing a stamping-based stamping process in which a stamping member with the inner diameter of the through hole 123 as the outer diameter passes through from the support surface 121 to the flow surface 122.

[0059] As step S2, an adhesive layer 7, a fuel electrode support layer 2, a fuel electrode active layer 3, and an electrolyte layer 4 are sequentially laminated on the support portion 12. Each layer can be formed using any method such as screen printing, casting, or spraying. The adhesive layer 7 is configured as a rectangular ring covering the periphery of the support surface 121 and the main surface of the outer peripheral portion 13, and adjacent to the inner region of the support surface 121. Figure 2 Furthermore, the fuel electrode support layer 2 and the fuel electrode active layer 3 are disposed on the support surface 121 in a shape that mimics the outline of the support surface 121. At this time, the peripheral portion of the fuel electrode support layer 2 is disposed on the adhesive layer 7. Additionally, the electrolyte layer 4 is configured to cover the upper surface of the fuel electrode active layer 3, surround (around) the sides of the fuel electrode active layer 3 and the sides of the fuel electrode support layer 2, and then surround (around) the portion of the adhesive layer 7 disposed on the outer periphery 13 and connect (adhere to) that portion.

[0060] As step S3, the fuel electrode support layer 2, the fuel electrode active layer 3, and the electrolyte layer 4 are sintered at high temperature (1000 [°C] to 1500 [°C]). At this time, by sintering under an inert gas (nitrogen, argon) or a reducing atmosphere (hydrogen atmosphere), deformation caused by high-temperature oxidation of stainless steel is suppressed.

[0061] As step S4, for example, an air electrode layer 5 is laminated on the electrolyte layer 4 by screen printing and heat-treated at a specified temperature, thereby curing the air electrode layer 5.

[0062] In steps S2 and S3, the fuel electrode support layer 2 can be stacked on the support surface 121 and sintered; the fuel electrode active layer 3 can be stacked on the sintered fuel electrode support layer 2 and sintered; and the electrolyte layer 4 can be stacked on the sintered fuel electrode active layer 3 and sintered. Alternatively, in steps S2 to S4, the fuel electrode support layer 2, the fuel electrode active layer 3, the electrolyte layer 4, and the air electrode layer 5 can be stacked sequentially and then sintered simultaneously.

[0063] [Sintered fuel electrode support layer 2]

[0064] Figure 5This is a diagram showing the adjacent region 22 of the fuel electrode support layer 2 adjacent to the adhesive layer 7 and the region other than the adjacent region 22 of the fuel electrode support layer 2 in the sintered electrochemical cell.

[0065] The material constituting the adhesive layer 7 (second particle 71A, etc.) Figure 3 The shrinkage rate during sintering is greater than that of the material constituting the fuel electrode support layer 2 (first particle 21A, etc.). Figure 3 The shrinkage rate during sintering is high. Therefore, in the adjacent region 22 of the fuel electrode support layer 2 adjacent to the adhesive layer 7, with the shrinkage caused by the sintering of the adhesive layer 7, the particles (first particle 21A, etc.) Figure 3 The spacing of the gas pole support layer 2 is narrower than that of other regions besides the adjacent region 22, resulting in a decrease in porosity (increased filling rate).

[0066] like Figure 5 As shown, the adjacent area 22 is formed in such a way that it covers the upper surface and side surface of the adhesive layer 7, and is connected to the support surface 121 of the support portion 12 and the inner side surface of the electrolyte layer 4.

[0067] Therefore, the bonding area per unit area of ​​the peripheral portion of the fuel electrode support layer 2 relative to the adhesive layer 7, the bonding area per unit area of ​​the electrolyte layer 4, and the bonding area per unit area of ​​the support surface 121 increases, thereby increasing the bonding strength (peel strength) between the peripheral portion of the fuel electrode support layer 2 and the adhesive layer 7, the bonding strength (peel strength) with the inner side surface of the electrolyte layer 4, and the bonding strength (peel strength) with the support surface 121. Here, the bonding strength (peel strength) between the peripheral portion of the fuel electrode support layer 2 and the adhesive layer 7 is higher than the bonding strength (peel strength) between the peripheral portion of the fuel electrode support layer 2 and the inner side surface of the electrolyte layer 4, and the bonding strength (peel strength) between the peripheral portion of the fuel electrode support layer 2 and the support surface 121.

[0068] Therefore, by using the sintered fuel electrode support layer 2 and adhesive layer 7, it is possible to effectively reduce the peeling from the support portion 12 starting from the peripheral portion (adjacent area 22) on the support portion 12 side.

[0069] [Comparative Example]

[0070] Figure 6 This is a cross-sectional view of the electrochemical cell of the first comparative example. Figure 7 This is a cross-sectional view of the electrochemical cell of the second comparative example.

[0071] like Figure 6 As shown, the first comparative example omits the adhesive layer 7 in the first embodiment. In this structure, as described above, the first particles 21A and 21B (which constitute the fuel electrode support layer 2) Figure 3The bonding area between the fuel electrode support layer 2 and the support surface 121 is relatively low at the periphery and inside of the fuel electrode support layer 2. Therefore, in the first comparative example, it is difficult to reduce the peeling of the fuel electrode support layer 2 from the support portion 12 (support surface 121) starting from the periphery of the fuel electrode support layer 2.

[0072] like Figure 7 As shown, in the second comparative example, a fuel electrode support layer 2 and a fuel electrode active layer 3 are sequentially stacked on the support portion 12 (support surface 121). Then, an adhesive layer 7 is stacked in such a way that it covers the upper surface of the fuel electrode active layer 3, the fuel electrode support layer 2, and the side surface of the fuel electrode active layer 3 and is connected to the main surface of the outer periphery 13 of the metal support 1. Then, an electrolyte layer 4 is stacked in such a way that it covers the upper surface and side surface of the adhesive layer 7, and an air electrode layer 5 is stacked on top of the electrolyte layer 4.

[0073] In the second comparative example, for the side of the sintered fuel electrode support layer 2 that contacts the adhesive layer 7, the adhesive strength relative to the support surface 121 can also be considered improved, as described above. However, in the second comparative example, since the periphery of the fuel electrode support layer 2 is not disposed on the upper surface of the adhesive layer 7 as in the first embodiment, the improvement in adhesive strength is limited.

[0074] In addition, in the second comparative example, the adhesive layer 7 is disposed as a layer between the fuel electrode active layer 3 and the electrolyte layer 4, and the adhesive layer 7 exists as an ohmic resistor between the fuel electrode active layer 3 and the air electrode layer 5, resulting in a decrease in power generation efficiency.

[0075] However, in this embodiment, as described above, the fuel electrode support layer 2 is arranged such that its peripheral portion is placed on the adhesive layer 7. Figure 1 Thus, the periphery of the fuel electrode support layer 2 is firmly bonded to the adhesive layer 7 which is firmly bonded to the support portion 12 (support surface 121), thereby effectively reducing the peeling of the fuel electrode support layer 2 from the support portion 12 (support surface 121) starting from the periphery of the fuel electrode support layer 2.

[0076] In addition, in this embodiment, the adhesive layer 7 is configured to separate from the area that overlaps with the air electrode layer 5 when viewed from above (the area used for power generation reaction), thus also suppressing the reduction in power generation efficiency.

[0077] [Second Implementation]

[0078] Figure 8 This is a cross-sectional view of the electrochemical cell of the second embodiment.

[0079] In the second embodiment, the portion of the electrolyte layer 4 that is bonded to the adhesive layer 7 further extends in such a way that it is bonded to the side surface of the adhesive layer 7 and the upper surface of the outer peripheral portion 13. Thus, the electrolyte layer 4, having a dense structure, covers the adhesive layer 7 at the bonding location between the adhesive layer 7 and the outer peripheral portion 13, thereby reducing gas leakage from the adhesive layer 7 or the interface between the adhesive layer 7 and the outer peripheral portion 13.

[0080] In the second embodiment, a coating 111 (passivation coating) of an oxide of at least one of Al (aluminum), Co (cobalt), Mn (manganese), Cu (copper), Zr (zirconium), Si (silicon), and Ce (cerium) is formed on the support surface 121 of the support portion 12 and the main surface of the outer peripheral portion 13 of the metal support 1. The coating 111 is applied by surface coating based on sputtering, spraying, electroplating, etc. If an adhesive layer 7 and a fuel electrode support layer 2 are disposed on the coating 111, the adhesion strength between the support portion 12 and the adhesive layer 7, and the adhesion strength between the support portion 12 and the fuel electrode support layer 2 are improved. Therefore, gas leakage at the interface between the support portion 12 (support surface 121) and the adhesive layer 7, and at the interface between the support portion 12 (support surface 121) and the fuel electrode support layer 2, can be suppressed, thereby improving the yield.

[0081] Furthermore, in the second embodiment, when forming stainless steel as the material of the metal support 1, by doping the stainless steel base material with at least one (one or more metals) of Al (aluminum), Co (cobalt), Mn (manganese), Cu (copper), Zr (zirconium), Si (silicon), and Ce (cerium), a coating 111 (passivation coating) formed of the dopant material (oxide of the dopant material) can also be formed on the surface of the stainless steel. Additionally, as described above, the electrochemical cell of the first embodiment uses stainless steel as the material, and a coating 111 (passivation coating) formed of chromium oxide is formed on its surface. Figure 1 (Not shown in the image).

[0082] [Solid oxide type electrolytic cell]

[0083] Figure 9 This is a schematic diagram of the electrochemical cell of this embodiment being used as a solid oxide type electrolytic cell.

[0084] The electrochemical cell of this embodiment can also be used as a solid oxide type electrolytic cell. Figure 9 This refers to a solid oxide type electrolytic cell using the electrochemical cell of the first embodiment, but the electrochemical cell of the second embodiment can also be used.

[0085] like Figure 9As shown, water is supplied to the fuel electrode support layer 2 side, and a DC voltage is applied to the main body of the battery cell. At this time, the air electrode layer 5 is set as the positive side of the DC voltage, and the metal support 1 (fuel electrode support layer 2 and fuel electrode active layer 3) is set as the negative side of the DC voltage.

[0086] Water molecules (2H₂O) are decomposed into hydrogen ions (4H₂O) in fuel electrode support layer 2 or fuel electrode active layer 3. + ) and oxygen ions (2O 2- ).

[0087] Hydrogen ions (4H) + The hydrogen molecules (2H2) are formed by being supplied with electrons in the fuel electrode support layer 2 or the fuel electrode active layer 3.

[0088] Oxygen ions (2O) 2- The electrons are conducted in the electrolyte layer 4 to reach the air electrode layer 5, where they are stripped of electrons and become oxygen molecules (O2).

[0089] [Effects of this implementation method]

[0090] The electrochemical cell of this embodiment includes: a cell body 6, on which a first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3), an electrolyte layer 4, and a second electrode layer (air electrode layer 5) are sequentially stacked; a metal support 1, which supports the cell body 6; the metal support 1 includes: a support surface 121, which is the main surface supporting the first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3) of the cell body 6; and the opposite surface of the support surface 121 (flow surface 122); the metal support 1 can... The support surface 121 is connected to the opposite surface (flow surface 122) to allow gas to pass through. An adhesive layer 7 is disposed in the area of ​​the support surface 121 opposite to the periphery of the first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3), which is bonded to the support surface 121. The portion of the first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3) that is inside the periphery is bonded to the support surface 121, and the periphery of the first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3) is bonded to the adhesive layer 7.

[0091] According to the above structure, the periphery of the first electrode layer (fuel electrode support layer 2) is fixed to the support surface 121 via the adhesive layer 7, thereby reducing the peeling of the first electrode layer (fuel electrode support layer 2) from the support portion 12 (support surface 121) starting from the periphery of the first electrode layer (fuel electrode support layer 2).

[0092] In this embodiment, the adhesive layer 7 is configured to (continuously) surround (around) the relative area.

[0093] According to the above structure, the periphery of the first electrode layer (fuel electrode support layer 2) can be bonded to the adhesive layer 7 without omission, thus effectively reducing the peeling of the first electrode layer (fuel electrode support layer 2) from the support portion 12 (support surface 121) starting from the periphery of the first electrode layer (fuel electrode support layer 2).

[0094] In this embodiment, the support portion 12 has a through hole 123 that allows gas to pass through by communicating between the support surface 121 and the opposite surface (flow surface 122).

[0095] Based on the above structure, the support part 12 can be constructed with a simple structure.

[0096] In this embodiment, the particle size of the material constituting the adhesive layer 7 (such as the second particle 71A) is smaller than the particle size of the material constituting the first electrode layer (such as the first particle 21A) of the fuel electrode support layer 2.

[0097] According to the above structure, compared with the first electrode layer (fuel electrode support layer 2), the adhesive layer 7 has a larger adhesive area per unit area with the support portion 12 (support surface 121), resulting in higher adhesive strength. Furthermore, while the periphery of the first electrode layer (fuel electrode support layer 2) is fixed to the support portion 12 (support surface 121) via the adhesive layer 7, multiple materials constituting the adhesive layer 7 (second particles 71A, etc.) are inserted between the materials constituting the first electrode layer (fuel electrode support layer 2), thus supporting the materials constituting the first electrode layer (fuel electrode support layer 2). Therefore, the adhesive strength of the periphery of the first electrode layer (fuel electrode support layer 2) relative to the adhesive layer 7 is stronger than the adhesive strength of the region of the first electrode layer (fuel electrode support layer 2) further inward relative to the support portion 12 (support surface 121). Therefore, the periphery of the first electrode layer (fuel electrode support layer 2) can be firmly fixed to the support portion 12 (support surface 121) via the adhesive layer 7.

[0098] In this embodiment, the metal support 1 further includes an outer peripheral portion 13 forming the outer periphery of the support portion 12. The adhesive layer 7 is arranged to extend from the opposite region to the outer peripheral portion 13 and to (continuously) surround (around) the outer peripheral portion 13. The electrolyte layer 4 surrounds (around) and covers the side of the first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3), and surrounds (around) and is bonded to the adhesive layer 7 arranged on the outer peripheral portion 13.

[0099] According to the above structure, the gas leakage at the interface between the first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3), the first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3) and the adhesive layer 7, and the interface between the electrolyte layer 4 and the adhesive layer 7 can be reduced by the electrolyte layer 4 having a dense structure.

[0100] In this embodiment, the electrolyte layer 4 (completely) covers the adhesive layer 7 disposed on the outer peripheral portion 13 and (continuously) surrounds (around) the outer region of the outer peripheral portion 13 that is outside the electrolyte layer 4 and is adhered to the outer region.

[0101] According to the above structure, the electrolyte layer 4 with a dense structure can reduce gas leakage at the interface between the adhesive layer 7 and the outer peripheral portion 13 (metal support 1).

[0102] In this embodiment, the material constituting the adhesive layer 7 includes cerium oxide.

[0103] According to the above structure, for example, interdiffusion is more likely to occur between the zirconium oxide constituting the electrolyte layer 4 and the stainless steel constituting the metal support 1. Therefore, by including cerium oxide in the adhesive layer 7, the adhesion strength (peel strength) with the support portion 12 (support surface 121) of the metal support 1 can be improved.

[0104] In this embodiment, a coating 111, including at least one oxide selected from aluminum, chromium, silicon, manganese, cobalt, and nickel, is formed on the main surface of the metal support 1 on the side where the battery cell body 6 is disposed.

[0105] According to the above structure, when the adhesive layer 7 and the first electrode layer (fuel electrode support layer 2) are disposed on the coating 111, the adhesion between the support portion 12 and the adhesive layer 7, as well as the adhesion between the support portion 12 and the first electrode layer (fuel electrode support layer 2), is improved. Therefore, gas leakage at the interface between the support portion 12 (support surface 121) and the adhesive layer 7, and at the interface between the support portion 12 (support surface 121) and the fuel electrode support layer 2, can be suppressed, thereby improving the yield.

[0106] In this embodiment, the porosity of the adjacent region 22 of the first electrode layer (fuel electrode support layer 2) adjacent to the adhesive layer 7 is lower than the porosity of the region outside the adjacent region 22 of the first electrode layer (fuel electrode support layer 2).

[0107] In the above structure, the material constituting the adhesive layer 7 (second particle 71A, etc.) Figure 3 The shrinkage rate during sintering is higher than that of the material constituting the first electrode layer (fuel electrode support layer 2) (first particle 21A, etc.). Figure 3The shrinkage rate during sintering is high. Therefore, in the adjacent region 22 of the first electrode layer (fuel electrode support layer 2) adjacent to the adhesive layer 7, as the adhesive layer 7 shrinks due to sintering, the particles (first particles 21A, etc.) Figure 3 The spacing between the layers becomes narrower than in areas other than the adjacent region 22 of the first electrode layer (fuel electrode support layer 2), resulting in a decrease in porosity (increased filling rate). Therefore, with the above structure, the bonding area per unit area of ​​the first electrode layer (fuel electrode support layer 2) relative to the adhesive layer 7 increases, and the bonding strength (peel strength) between the periphery of the first electrode layer (fuel electrode support layer 2) and the adhesive layer 7 increases. Therefore, through the sintered first electrode layer (fuel electrode support layer 2) and adhesive layer 7, peeling from the support portion 12, starting from the periphery (adjacent region 22) on the support portion 12 side, can be effectively reduced.

[0108] In this embodiment, the second electrode layer (air electrode layer 5) is configured such that, when viewed from above, the shape of the second electrode layer (air electrode layer 5) is more inward than the shape of the first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3), and the adhesive layer 7 is configured to separate from the area overlapping with the second electrode layer (air electrode layer 5) when viewed from above.

[0109] According to the above structure, interference between the bonding layer 7 and the power generation area between the air electrode layer 5, the fuel electrode support layer 2, and the fuel electrode active layer 3 can be avoided, and the reduction in power generation performance can be suppressed.

[0110] The solid oxide fuel cell of this embodiment is a solid oxide fuel cell using the above-described electrochemical cell. The electrolyte layer 4 is composed of oxygen-ion conductive oxide. Cathode gas (air, oxygen) is supplied to the second electrode layer (air electrode layer 5), and anode gas (hydrogen) is supplied to the first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3) via the support portion 12. Thus, the cell body 6 can generate electricity.

[0111] Based on the above structure, solid oxide fuel cells can be constructed with a simple structure.

[0112] The solid oxide type electrolytic cell of this embodiment is a solid oxide type electrolytic cell using the electrochemical cell. The electrolyte layer 4 is composed of oxygen ion conductive oxide. Water is supplied to the first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3) via the support portion 12. By applying a voltage between the first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3) and the second electrode layer (air electrode layer 5), the water supplied to the first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3) can be electrolyzed.

[0113] Based on the above structure, solid oxide type electrolytic cells can be constructed using a simple structure.

[0114] In the manufacturing method of the electrochemical cell of this embodiment, the electrochemical cell is formed by sequentially stacking a first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3), an electrolyte layer 4, and a second electrode layer (air electrode layer 5) on a metal support 1. The metal support 1 includes a support surface 121 that supports the first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3) and an opposite surface (flow surface 122) of the support surface 121, which can communicate with the opposite surface (flow surface 122) to allow gas to pass through. An adhesive layer 7 is stacked on the periphery of the support surface 121, and the first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3) is stacked on the support surface 121 and arranged such that the periphery of the first electrode layer (fuel electrode support layer 2, fuel electrode active layer 3) is placed on the adhesive layer 7.

[0115] By means of the above method, the periphery of the first electrode layer (fuel electrode support layer 2) is fixed to the support surface 121 via the adhesive layer 7, thereby reducing the peeling of the first electrode layer (fuel electrode support layer 2) from the support portion 12 (support surface 121) starting from the periphery of the first electrode layer (fuel electrode support layer 2).

[0116] The embodiments of the present invention have been described above. However, the above embodiments are merely examples of applications of the present invention and are not intended to limit the technical scope of the present invention to the specific structures of the above embodiments.

Claims

1. An electrochemical battery cell, characterized in that, include: The main body of the battery cell has a first electrode layer, an electrolyte layer, and a second electrode layer stacked in sequence. A metal support body that supports the main body of the battery cell; The metal support includes a support portion, which comprises a support surface supporting the main surface of the first electrode layer side of the battery cell body, and an opposite surface to the support surface, and is capable of communicating with the support surface and the opposite surface to allow gas to pass through. An adhesive layer is disposed on the support surface in a region opposite to the periphery of the first electrode layer. The portion of the first electrode layer that is closer to the periphery than the inner side is bonded to the support surface. The periphery of the first electrode layer is bonded to the adhesive layer.

2. The electrochemical cell according to claim 1, characterized in that, The adhesive layer is configured to surround the opposite region.

3. The electrochemical cell according to claim 1, characterized in that, The support portion has a through hole that allows gas to pass through and connects the support surface with the opposite surface.

4. The electrochemical cell according to claim 1, characterized in that, The particle size of the material constituting the adhesive layer is smaller than the particle size of the material constituting the first electrode layer.

5. The electrochemical cell according to claim 1, characterized in that, The metal support also includes an outer peripheral portion forming the outer periphery of the support portion. The adhesive layer is configured to extend from the opposing region toward the outer periphery and surround the outer periphery. The electrolyte layer surrounds and covers the side of the first electrode layer, and surrounds and is bonded to the adhesive layer disposed on the outer periphery.

6. The electrochemical cell according to claim 5, characterized in that, The electrolyte layer covers the adhesive layer disposed on the outer periphery, and surrounds and is adhered to the outer region of the outer periphery that is outside the electrolyte layer.

7. The electrochemical cell according to claim 1, characterized in that, The materials constituting the adhesive layer include cerium oxide.

8. The electrochemical cell according to claim 1, characterized in that, The main surface of the metal support on the side where the main body of the battery cell is disposed is coated with a film including at least one oxide selected from aluminum, chromium, silicon, manganese, cobalt and nickel.

9. The electrochemical cell according to claim 1, characterized in that, The porosity of the adjacent region of the first electrode layer adjacent to the adhesive layer is lower than the porosity of the region outside the adjacent region of the first electrode layer.

10. The electrochemical cell according to claim 1, characterized in that, The second electrode layer is configured such that, when viewed from above, its shape is more inward than that of the first electrode layer. The adhesive layer is configured to separate from the region overlapping with the second electrode layer when viewed from above.

11. A solid oxide fuel cell, using the electrochemical cell according to any one of claims 1 to 9, characterized in that, The electrolyte layer is composed of oxygen ion conductive oxide. Cathode gas is supplied to the second electrode layer, and anode gas is supplied to the first electrode layer via the support portion, thereby enabling the main body of the battery cell to generate electricity.

12. A solid oxide type electrolytic cell, using the electrochemical cell according to any one of claims 1 to 9, characterized in that, The electrolyte layer is composed of oxygen ion conductive oxide. Water is supplied to the first electrode layer via the support portion, and the water supplied to the first electrode layer can be electrolyzed by applying a voltage between the first electrode layer and the second electrode layer.

13. A method for manufacturing an electrochemical battery cell, wherein the electrochemical battery cell is formed by sequentially stacking a first electrode layer, an electrolyte layer, and a second electrode layer on a metal support, and the metal support includes a support surface supporting the first electrode layer and an opposite surface of the support surface, capable of communicating between the support surface and the opposite surface to allow gas passage, characterized in that... An adhesive layer is laminated at the periphery of the support surface. The first electrode layer is stacked on the support surface and arranged such that the periphery of the first electrode layer is placed on the adhesive layer.

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