Fluid container and electrochemical cell

Abstract

A fluid container (3) is provided with a first metal member (31), a second metal member (32), an adhesive section (34), a first interface (4), and a second interface (5). The first and second metal members (31, 32) contain chromium. The adhesive section (34) is configured from an oxide having chromium as the main component. The adhesive section (34) adheres the first metal member (31) and the second metal member (32) to each other. The first interface (4) is an interface between the first metal member (31) and the adhesive portion (34). The second interface (5) is an interface between the second metal member (32) and the adhesive portion (34). The first interface (4) has a first wave (41). The first corrugated section (41) is configured so as to repeat the amplitude in the thickness direction. The first corrugated section (41) extends along the outer peripheral edge of the first metal member (31).

Description

Technical Field

[0001] This invention relates to fluid containers and electrochemical single cells. Background Technology

[0002] Electrochemical single cells, such as electrolytic single cells and fuel cell single cells, have a fluid container to supply fluid to their main body. For example, the fluid container disclosed in Patent Document 1 includes: a first interconnector, a second interconnector, a separator, a fuel electrode frame, and a glass seal.

[0003] The first interconnect is connected to the air electrode of the fuel cell. The second interconnect is connected to the fuel electrode current collector of the fuel cell. A separator is connected to the solid electrolyte of the fuel cell, separating the flow paths of fuel gas and oxidant gas. A fuel electrode frame is disposed between the separator and the second interconnect. A glass seal bonds the first interconnect and the separator.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2015-156352 Summary of the Invention

[0007] In the fluid container described above, a first metal component and a second metal component are bonded together using an adhesive joint. This fluid container may experience thermal expansion differences between the first and second metal components due to thermal cycling associated with the start-up and shutdown of an electrochemical single cell, causing load concentration at the adhesive joint and potentially leading to its breakage.

[0008] The objective of this invention is to provide a fluid container and an electrochemical single cell capable of suppressing damage to the adhesive portion.

[0009] The fluid container of the first embodiment includes: a first metal component, a second metal component, an adhesive portion, a first interface, and a second interface. The first metal component contains chromium. The second metal component contains chromium. The adhesive portion is composed of an oxide primarily composed of chromium. The adhesive portion bonds the first metal component and the second metal component. The first interface is the interface between the first metal component and the adhesive portion. The second interface is the interface between the second metal component and the adhesive portion. The first interface has a first corrugated portion. The first corrugated portion is configured such that the amplitude repeats in the thickness direction. The first corrugated portion extends along the outer periphery of the first metal component.

[0010] According to this configuration, the stress generated in the adhesive portion is dispersed by the first wavy portion at the first interface of the adhesive portion, and the breakage of the adhesive portion is suppressed.

[0011] The fluid container in the second embodiment is constructed based on the fluid container in the first embodiment as follows: The second interface has a second corrugated portion. The second corrugated portion is configured such that the amplitude repeats in the thickness direction. The second corrugated portion extends along the outer periphery of the second metal component.

[0012] The fluid container involved in the third scheme is constructed based on the fluid container involved in the first or second scheme as follows: The first wavy part is constructed such that the amount of variation at its outer periphery is greater than the amount of variation at its inner periphery.

[0013] The fluid container involved in the fourth scheme is constructed based on the fluid containers involved in any of the first to third schemes, as follows: The first adhesive part has a void portion.

[0014] The fluid container involved in the fifth scheme is constructed based on the fluid container involved in any of the first to fourth schemes, as follows: The first corrugated section has a variation of more than 1 μm and less than 50 μm.

[0015] The fluid container in the sixth embodiment is constructed based on the fluid container in the second embodiment as follows: The first corrugated section has a variation of 1 μm or more and 50 μm or less. The second corrugated section has a variation of 1 μm or more and 50 μm or less.

[0016] The fluid container in the seventh embodiment, based on the fluid containers in any of the first to sixth embodiments, further includes: an internal space for fluid flow. The adhesive portion extends in a ring shape to surround the internal space.

[0017] The fluid container in the eighth embodiment, in addition to the fluid containers in any of the first to seventh embodiments, also includes: an internal space for fluid flow. The adhesive part is a seal used to close the internal space.

[0018] The electrochemical single cell involved in the ninth embodiment includes: a fluid container involved in any of the first to eighth embodiments, and a single cell body disposed on the fluid container.

[0019] The electrochemical single cell of the tenth embodiment is constructed as follows, based on the electrochemical single cell of the ninth embodiment: The fluid container has an internal space for fluid flow. The first metal component has multiple connecting holes connected to the internal space. The main body of the single cell is disposed on the first metal component in a manner that covers the multiple connecting holes.

[0020] The electrochemical single cell in the eleventh embodiment is constructed based on the electrochemical single cell in the ninth embodiment as follows: The fluid container has an internal space for fluid flow. The second metal component has multiple connecting holes connected to the internal space. The main body of the single cell is disposed on the second metal component in a manner that covers the multiple connecting holes.

[0021] Invention Effects

[0022] According to the present invention, damage to the adhesive portion can be suppressed. Attached Figure Description

[0023] Figure 1 It is a plan view of an electrolytic single cell.

[0024] Figure 2 yes Figure 1 Section II-II.

[0025] Figure 3 yes Figure 1 Sectional view of line III-III.

[0026] Figure 4 It is a plan view of a fluid container.

[0027] Figure 5 This is an example of a captured image.

[0028] Figure 6 This is an enlarged cross-sectional view of the first adhesive portion in the modified example.

[0029] Figure 7 This is an enlarged cross-sectional view of the first adhesive portion in the modified example. Detailed Implementation

[0030] <Electrolytic Single Cell>

[0031] Figure 1 This is a plan view of an electrolytic single cell 100. Figure 2 yes Figure 1 Sectional view of line II-II.

[0032] like Figure 1 As shown, the electrolytic cell 100 (an example of an electrochemical cell) is formed as a plate extending along the X-axis and Y-axis directions. In this embodiment, the electrolytic cell 100 is formed as a rectangle extending along the Y-axis direction when viewed from above along the Z-axis direction, which is perpendicular to the X-axis and Y-axis directions. However, the planar shape of the electrolytic cell 100 is not particularly limited and can be a polygon, ellipse, circle, etc., other than a rectangle.

[0033] like Figure 1 and Figure 2As shown, the electrolytic single cell 100 includes a single cell body 2 and a fluid container 3.

[0034] <Single Battery Main Body>

[0035] The single-cell main body 2 is disposed on the fluid container 3. The single-cell main body 2 is supported by the metal support 31 described later in the fluid container 3. The single-cell main body 2 is disposed on the metal support 31 in such a way that it covers the plurality of through holes 313 described later. The single-cell main body 2 has: a hydrogen electrode 21 (cathode), an electrolyte 22, an anti-reaction layer 23, and an oxygen electrode 24 (anode).

[0036] The hydrogen electrode 21, electrolyte 22, anti-reaction layer 23, and oxygen electrode 24 are stacked sequentially in the Z-axis direction, starting from the side of the fluid container 3. The hydrogen electrode 21, electrolyte 22, and oxygen electrode 24 are mandatory components, while the anti-reaction layer 23 is optional.

[0037] <Hydrogen Pole>

[0038] The hydrogen electrode 21 is disposed on the first main surface 311 of the metal support 31. Feed gas is supplied to the hydrogen electrode 21 through the connecting holes 313 of the metal support 31. The feed gas contains at least water vapor (H2O). H2 is generated at the hydrogen electrode 21 during the electrolysis reaction.

[0039] When the feed gas contains only H2O, the hydrogen electrode 21 generates H2 from the feed gas according to the electrochemical reaction of water electrolysis shown in equation (1) below.

[0040] • Hydrogen pole 21: H2O + 2e － →H2+O 2－ ···(1)

[0041] When the feed gas contains H2O and CO2, the hydrogen electrode 21 generates H2, CO and O from the feed gas through a co-electrolysis electrochemical reaction as shown in equations (2), (3), and (4) below. 2－ .

[0042] • Hydrogen pole 21: CO2 + H2O + 4e － →CO + H₂ + 2O 2－ ···(2)

[0043] Electrochemical reaction of H2O: H2O + 2e － →H2+O 2－ ···(3)

[0044] • Electrochemical reaction of CO2: CO2 + 2e － →CO+O 2－ ···(4)

[0045] The H2 generated at the hydrogen electrode 21 flows out from the connecting holes 313 of the metal support 31 into the internal space 30, which will be described later.

[0046] The hydrogen electrode 21 is a porous material with electronic conductivity. The hydrogen electrode 21 contains nickel (Ni). In co-electrolysis, Ni functions as an electron conductor and also as a thermal catalyst, promoting the thermal reaction between the generated H2 and the CO2 contained in the feed gas while maintaining a suitable gas composition for metallization, Fischer-Tropsch synthesis, etc. The Ni contained in the hydrogen electrode 21 exists primarily as metallic Ni during the operation of the electrolytic cell 100; however, a portion may exist as nickel oxide (NiO).

[0047] Hydrogen electrode 21 may contain ion-conducting materials. Examples of ion-conducting materials that can be used include: yttrium-stabilized zirconium oxide (YSZ), calcium oxide-stabilized zirconium oxide (CSZ), scandium oxide-stabilized zirconium oxide (ScSZ), gadolinium-doped cerium dioxide (GDC), samarium-doped cerium dioxide (SDC), (La,Sr)(Cr,Mn)O3, (La,Sr)TiO3, Sr2(Fe,Mo)2O6, (La,Sr)VO3, (La,Sr)FeO3, and mixed materials obtained by combining two or more of these materials.

[0048] The thickness of the hydrogen electrode 21 is not particularly limited; for example, it can be greater than 1 μm and less than 100 μm. The coefficient of thermal expansion of the hydrogen electrode 21 is not particularly limited; it can be, for example, 12 × 10⁻⁶. ―6 / ℃ or above and 20×10 －6 / ℃ below.

[0049] There are no particular restrictions on the formation method of the hydrogen electrode 21. It can be formed by: firing method, spraying method (fusion deposition method, aerosol deposition method, aerosol gas deposition method, powder jet deposition method, particle jet deposition method, cold spraying method, etc.), PVD method (sputtering method, pulsed laser deposition method, etc.), CVD method, etc.

[0050] <Electrolytes>

[0051] Electrolyte 22 is formed on hydrogen electrode 21. Electrolyte 22 is disposed between hydrogen electrode 21 and oxygen electrode 24. In this embodiment, electrolyte 22 is sandwiched between hydrogen electrode 21 and anti-reaction layer 23, and is connected to both.

[0052] Electrolyte 22 covers hydrogen electrode 21 and also covers the area of ​​the first main surface 311 of metal support 31 exposed from hydrogen electrode 21.

[0053] Electrolyte 22 is a dense body with oxide ion conductivity. Electrolyte 22 is used to convert the O generated at hydrogen electrode 21... 2－ It is transferred to the oxygen electrode 24 side. The electrolyte 22 is made of an oxide ion-conducting material. The electrolyte 22 can be made of, for example, YSZ, GDC, ScSZ, SDC, LSGM (lanthanum gallate), etc., and YSZ is particularly preferred.

[0054] The thickness of electrolyte 22 is not particularly limited; for example, it can be greater than 1 μm and less than 100 μm. The coefficient of thermal expansion of electrolyte 22 is not particularly limited; for example, it can be 10 × 10⁻⁶. ―6 / ℃ or higher and 12×10 ―6 / ℃ below.

[0055] There are no particular restrictions on the formation method of electrolyte 22, and methods such as sintering, spraying, PVD, and CVD can be used.

[0056] <Anti-reaction layer>

[0057] An anti-reaction layer 23 is disposed between the electrolyte 22 and the oxygen electrode 24. The anti-reaction layer 23 is disposed on the opposite side of the hydrogen electrode 21, with the electrolyte 22 as a reference. The anti-reaction layer 23 is used to suppress the formation of a layer with high electrical resistance due to the reaction between the constituent elements of the electrolyte 22 and the constituent elements of the oxygen electrode 24.

[0058] The anti-reaction layer 23 is made of an oxide ion-conducting material. The anti-reaction layer 23 can be made of GDC, SDC, etc.

[0059] The porosity of the anti-reaction layer 23 is not particularly limited, and can be, for example, 0.1% or more and 50% or less. The thickness of the anti-reaction layer 23 is not particularly limited, and can be, for example, 1 μm or more and 50 μm or less.

[0060] There are no particular restrictions on the method of forming the anti-reaction layer 23; methods such as firing, spraying, PVD, and CVD can be used.

[0061] <Oxygen pole>

[0062] The oxygen electrode 24 is disposed on the opposite side of the hydrogen electrode 21, with the electrolyte 22 as a reference. In this embodiment, an anti-reaction layer 23 is disposed between the electrolyte 22 and the oxygen electrode 24, therefore, the oxygen electrode 24 is connected to the anti-reaction layer 23. If the anti-reaction layer 23 is not disposed between the electrolyte 22 and the oxygen electrode 24, the oxygen electrode 24 is connected to the electrolyte 22.

[0063] Oxygen electrode 24 undergoes a chemical reaction according to the following equation (5), where O is transferred from hydrogen electrode 21 through electrolyte 22. 2－ O2 is generated.

[0064] ·Oxygen pole 24:2O2－ →O2+4e － ···(5)

[0065] The oxygen electrode 24 is a porous material with oxide ion conductivity and electronic conductivity. The oxygen electrode 24 can be composed of a composite material of one or more of the following: (La,Sr)(Co,Fe)O3, (La,Sr)FeO3, La(Ni,Fe)O3, (La,Sr)CoO3, and (Sm,Sr)CoO3 with an oxide ion conductivity material (GDC, etc.).

[0066] There are no particular limitations on the porosity of the oxygen electrode 24, which can be, for example, 20% or more and 60% or less. There are no particular limitations on the thickness of the oxygen electrode 24, which can be, for example, 1 μm or more and 100 μm or less.

[0067] There are no particular restrictions on the formation method of oxygen electrode 24, and it can be formed by: firing method, spraying method, PVD method, CVD method, etc.

[0068] <Fluid container>

[0069] like Figure 2 As shown, the fluid container 3 has an internal space 30. The raw material gas supplied to the hydrogen electrode 21 and the reducing gas generated at the hydrogen electrode 21 (H2 in this embodiment) flow into the internal space 30. It should be noted that the raw material gas and the reducing gas are examples of the fluids of the present invention.

[0070] The fluid container 3 includes: a metal support 31 (an example of a first metal component), a frame 32 (an example of a second metal component), an interconnector 33, a first adhesive portion 34 (an example of an adhesive portion), and a second adhesive portion 35. The internal space 30 is the space surrounded by the metal support 31, the frame 32, the interconnector 33, the first adhesive portion 34, and the second adhesive portion 35.

[0071] In addition, such as Figure 3 As shown, the fluid container 3 has a first interface 4 and a second interface 5. Figure 3 yes Figure 1 The cross-sectional view along line III-III is an enlarged cross-sectional view centered on the first adhesive portion 34.

[0072] <Metal Support>

[0073] like Figure 2 As shown, the metal support 31 supports the main body 2 of the single battery. In this embodiment, the metal support 31 is formed in the shape of a plate. The metal support 31 is only required to support the main body 2 of the single battery, and its thickness is not particularly limited. For example, it can be 0.1 mm or more and 2.0 mm or less.

[0074] The metal support 31 has: multiple connecting holes 313, a first main surface 311 and a second main surface 312.

[0075] Each connecting hole 313 extends from the first main surface 311 to the second main surface 312 through the metal support 31. Each connecting hole 313 is open on both the first main surface 311 and the second main surface 312. Each connecting hole 313 is covered by the single cell body 2. Specifically, the opening on the first main surface 311 side of each connecting hole 313 is covered by the hydrogen electrode 21. The opening on the second main surface 312 side of each connecting hole 313 is connected to the internal space 30.

[0076] Each connecting hole 313 can be formed by machining (e.g., punching), laser processing, or chemical processing (e.g., etching).

[0077] In this embodiment, each connecting hole 313 is formed in a straight line along the Z-axis direction. However, each connecting hole 313 may be inclined relative to the Z-axis direction, or it may not be straight. In addition, the connecting holes 313 may be connected to each other.

[0078] The first main surface 311 is located on the opposite side of the second main surface 312. A single battery body 2 is disposed on the first main surface 311. A frame 32 is joined to the second main surface 312 by means of a first adhesive part 34.

[0079] The metal support 31 is made of an alloy containing Cr (chromium). Examples of such alloys include Fe-Cr alloy steels (stainless steel, etc.) and Ni-Cr alloy steels. There is no particular limitation on the Cr content in the metal support 31, which can be 4% by mass or more and 30% by mass or less.

[0080] The metal support 31 may contain Ti (titanium) or Zr (zirconium). There is no particular limitation on the Ti content in the metal support 31; it can be above 0.01 mol% and below 1.0 mol%. There is no particular limitation on the Zr content in the metal support 31; it can be above 0.01 mol% and below 0.4 mol%. The metal support 31 may contain Ti in the form of TiO2 (titanium dioxide) or Zr in the form of ZrO2 (zirconium oxide).

[0081] <Frame>

[0082] The frame 32 serves as a bushing for forming the internal space 30. The frame 32 is formed in a ring shape in top view (Z-axis view). The frame 32 is joined to the metal support 31 by means of a first adhesive portion 34, and to the interconnect 33 by means of a second adhesive portion 35. The thickness of the frame 32 is not particularly limited and can be, for example, 0.1 mm or more and 2.0 mm or less.

[0083] The frame 32 has a first main surface 321 and a second main surface 322. The first main surface 321 of the frame 32 is the surface facing the metal support 31. The second main surface 322 of the frame 32 is the surface facing the interconnector 33.

[0084] The frame 32 is made of an alloy containing Cr. Examples of such alloys include Fe-Cr alloy steel and Ni-Cr alloy steel. There is no particular limitation on the Cr content in the frame 32; it can be 4% by mass or more and 30% by mass or less. The composition of the frame 32 can be the same as or different from that of the metal support 31.

[0085] <Interconnector>

[0086] The interconnector 33 is disposed on the opposite side of the metal support 31 with reference to the frame 32. The interconnector 33 is a component for electrically connecting the electrolytic cell 100 to an external power source or other electrolytic cells.

[0087] The interconnect 33 is formed in the shape of a plate. The interconnect 33 is attached to the frame 32 by means of the second adhesive portion 35. The thickness of the interconnect 33 is not particularly limited and can be, for example, more than 0.1 mm and less than 2.0 mm.

[0088] The interconnect 33 is made of a Cr-containing alloy. Examples of such alloys include Fe-Cr alloy steel and Ni-Cr alloy steel. The Cr content in the interconnect 33 is not particularly limited and can be between 4% and 30% by mass. The composition of the interconnect 33 can be the same as or different from that of the metal support 31. The composition of the interconnect 33 can be the same as or different from that of the frame 32.

[0089] <First Adhesive Part>

[0090] The first adhesive portion 34 is disposed between the metal support 31 and the frame 32. The first adhesive portion 34 bonds the metal support 31 and the frame 32. Specifically, the first adhesive portion 34 is engaged with both the metal support 31 and the frame 32.

[0091] The first adhesive portion 34 seals the gap between the metal support 31 and the frame 32. This prevents the raw material gas supplied to the hydrogen electrode 21 and the reducing gas generated at the hydrogen electrode 21 from leaking to the outside through the gap between the metal support 31 and the frame 32.

[0092] The first adhesive portion 34 is disposed between the metal support 31 and the frame 32. The first adhesive portion 34 is held between the metal support 31 and the frame 32. The first adhesive portion 34 extends in a ring shape to surround the internal space 30. The first adhesive portion 34 functions as a seal to close the internal space 30. That is, the first adhesive portion 34 extends continuously in a ring shape.

[0093] The first adhesive portion 34 is composed of an oxide with Cr as its main component (hereinafter referred to as "Cr oxide"). Accordingly, during the manufacture or operation of the electrolytic cell 100, the diffusion of Cr from the metal support 31 and the frame 32 to the first adhesive portion 34 can be suppressed. Furthermore, even if Cr diffuses from the metal support 31 and the frame 32 to the first adhesive portion 34, the impact on the composition of the first adhesive portion 34 is relatively small; therefore, the reduction in the strength of the first adhesive portion 34 can also be suppressed. In addition, since the metal support 31, the frame 32, and the first adhesive portion 34 all contain Cr, their adhesion to each other can be improved. Accordingly, the adhesion between the metal support 31 and the frame 32 can be maintained for a long period.

[0094] It should be noted that in this embodiment, Cr as the main component means that, when the composition of the Cr oxide constituting the first adhesive part 34 is analyzed using an energy dispersive spectrophotometer (EDS), the Cr content among the metal elements is the highest. There is no particular limitation on the Cr content in the Cr oxide; for example, it can be 20 mol% or more and 100 mol% or less among the metal elements.

[0095] The Cr content in the Cr oxide constituting the first adhesive portion 34 is preferably 50 mol% or more in the metal element. Accordingly, the diffusion of Cr contained in the metal support 31 and the frame 32 into the first adhesive portion 34 can be significantly suppressed.

[0096] The Cr oxide constituting the first adhesive portion 34 is preferably composed of at least one of chromium oxide and chromium-manganese oxide. These oxides have the property that Cr is particularly difficult to diffuse, thus improving the durability of the first adhesive portion 34.

[0097] Examples of chromium oxides include Cr₂O₃. Examples of chromium-manganese oxides include MnCr₂O₄ (spinel) and Mn₂O₃. 1，5 Cr 1，5 O4 (spinel), etc.

[0098] The Cr oxide constituting the first adhesive portion 34 is preferably crystalline. Accordingly, even if the electrolytic cell 100 operates for a long time, damage to the first adhesive portion 34 due to the phase transition of the Cr oxide from amorphous to crystalline can be avoided.

[0099] The Cr oxide constituting the first adhesive portion 34 preferably has a spinel-type or corundum-type crystalline structure. These crystalline structures have high symmetry, thus improving the thermal stress resistance of the first adhesive portion 34.

[0100] The first adhesive portion 34 can be formed as follows: a paste containing Cr oxide is applied to the surface of at least one of the metal support 31 and the frame 32, and then heat treatment is performed to ensure that the metal support 31 and the frame 32 are tightly bonded, thereby forming the first adhesive portion 34. The heat treatment conditions can be appropriately set, for example, 600°C or higher and 1100°C or lower, for 0.5 hours or higher and 24 hours or lower.

[0101] <Second Adhesive Part>

[0102] The second adhesive portion 35 is disposed between the frame 32 and the interconnect 33. The second adhesive portion 35 bonds the frame 32 and the interconnect 33. In detail, the second adhesive portion 35 is engaged with the frame 32 and the interconnect 33 respectively.

[0103] The second adhesive portion 35 seals the gap between the frame 32 and the interconnect 33. This prevents the raw material gas supplied to the hydrogen electrode 21 and the reducing gas generated at the hydrogen electrode 21 from leaking to the outside through the gap between the frame 32 and the interconnect 33.

[0104] The structure of the second adhesive portion 35 is substantially the same as that of the first adhesive portion 34 described above. Therefore, the description of the structure of the second adhesive portion 35 is omitted in this embodiment.

[0105] <First and Second Interfaces>

[0106] like Figure 3 As shown, the first interface 4 is the interface between the metal support 31 and the first adhesive portion 34. The first interface 4 has a first corrugated portion 41. The first corrugated portion 41 is configured to repeatedly vibrate in the thickness direction (Z-axis direction). That is, the first corrugated portion 41 vibrates from the side towards the metal support 31 ( Figure 3 The protruding part on the upper side and the part on the side of the first adhesive part 34 ( Figure 3 The lower side of the metal support 31 is recessed. The convex and concave portions constituting the first wavy portion 41 are arranged alternately along the outer periphery of the metal support 31.

[0107] The second interface 5 is the interface between the frame 32 and the first adhesive portion 34. The second interface 5 has a second wavy portion 51. The second wavy portion 51 is configured to repeatedly vibrate in the thickness direction (Z-axis direction). That is, the second wavy portion 51 extends from the side towards the first adhesive portion 34 (…). Figure 3 The protruding part on the upper side and the part on the side of the frame 32 ( Figure 3 The lower side of the frame 32 is recessed. The convex and concave portions constituting the second wavy portion 51 are arranged alternately along the outer periphery of the frame 32.

[0108] Figure 4 This is a plan view of fluid container 3. (See diagram below.) Figure 4As shown, the first adhesive portion 34 has at least one straight portion in a top view (Z-axis direction view). That is, both the first interface 4 and the second interface 5 have at least one straight portion in the top view. It should be noted that in this embodiment, the first interface 4 and the second interface 5 each have four straight portions. Specifically, the first interface 4 and the second interface 5 each have: a pair of straight portions extending along the X-axis direction and a pair of straight portions extending along the Y-axis direction. The first interface 4 and the second interface 5 extend in a rectangular shape in the top view.

[0109] Each straight section is formed by a first wavy portion 41. That is, each straight section is formed by four first wavy portions 41. In other words, the first wavy portions 41 are formed around the entire circumference of the first interface 4.

[0110] like Figure 3 As shown, in at least one of the first corrugated portions 41, the variation V1 can be 1 μm or more and 50 μm or less. It should be noted that the variation V1 of each first corrugated portion 41 can be measured as follows: First, a cross-sectional surface is created along the direction in which the first corrugated portion 41 to be measured extends. This cross-sectional surface is created at the center of the width direction of the first corrugated portion 41. It should be noted that the width direction of the first corrugated portion 41 refers to a direction orthogonal to the direction in which the first corrugated portion 41 extends. For example, the width direction of the first corrugated portion 41 extending along the X-axis direction is the Y-axis direction, and the width direction of the first corrugated portion 41 extending along the Y-axis direction is the X-axis direction.

[0111] Furthermore, the cross-section is photographed using an electron microscope (SEM) at a magnification of 1000 to 10000. Preferably, the entire first wavy portion 41 is included in the photographed image. If the first wavy portion 41 is not completely included in a single photographed image, multiple photographed images are created in such a way that the entire first wavy portion 41 is captured.

[0112] Furthermore, as a pretreatment step for measurement, a moving average line is created for the first wavy section 41. Specifically, the coordinates in the height direction (Z-axis direction) of the first interface 4 are measured every 10 μm along the direction in which the first wavy section 41 extends, and the average value of 10 adjacent points is set as the height of its center (the exact center between points 5 and 6). This operation is performed point by point to create... Figure 3 The moving average line of the first wavy section 41 shown.

[0113] Based on the moving average line of the first wave-shaped portion 41 created above, the difference between the vertices of adjacent concave portions and convex portions is measured through image analysis and used as the variation V1 of the first wave-shaped portion 41. The average value of the measured variation V1 can be set as the variation V1 of the first wave-shaped portion 41. In this embodiment, since there are 4 first wave-shaped portions 41, 4 variation V1s can be calculated.

[0114] Regarding the amount of variation in the first wavy portion 41, the amount of variation at the outer peripheral edge is greater than the amount of variation at the inner peripheral edge. When measuring the amount of variation in the first wavy portion 41 at the outer peripheral edge, the cross-section is created at a position closer to the outer peripheral edge than the center portion in the width direction of the first wavy portion 41. Similarly, when measuring the amount of variation in the first wavy portion 41 at the inner peripheral edge, the cross-section is created at a position closer to the inner peripheral edge than the center portion in the width direction of the first wavy portion 41.

[0115] The ratio (L1 / L0) of the actual length (L1) of each first wavy portion 41 to the distance (L0) between the two ends of the first wavy portion 41 can be, for example, 1.01 or more and 3.00 or less. It should be noted that the aforementioned ratio (L1 / L0) of each first wavy portion 41 can be determined based on the moving average of the first wavy portion 41. That is, the distance between the two ends and the actual length of the first wavy portion 41 within the captured image are measured, and the ratio is calculated based on each measured value.

[0116] The second wave-shaped portion 51 constitutes each straight portion. That is, each straight portion is constituted by four second wave-shaped portions 51. In other words, the second wave-shaped portions 51 are formed around the entire circumference of the second interface 5.

[0117] In at least one of the second wave-shaped portions 51, the variation V2 can be more than 1 μm and less than 50 μm. It should be noted that the variation V2 of each second wave-shaped portion 51 can be calculated based on the captured image described above, using the same method as for the variation V1 of the first wave-shaped portion 41. That is, a moving average line of the second wave-shaped portion 51 can be created, and the difference between the apex of the concave portion and the apex of the convex portion adjacent to the moving average line of the second wave-shaped portion 51 can be measured as the variation V2 of the second wave-shaped portion 51. The average value of the measured variation V2 is then set as the variation V2 of the second wave-shaped portion 51. In this embodiment, there are four second wave-shaped portions 51; therefore, four variation V2s can be calculated.

[0118] Regarding the amount of variation in the second wavy portion 51, the amount of variation at the outer peripheral edge is greater than the amount of variation at the inner peripheral edge. When measuring the amount of variation in the second wavy portion 51 at the outer peripheral edge, a cross-sectional surface is created at a position closer to the outer peripheral edge than the center portion in the width direction of the second wavy portion 51. Similarly, when measuring the amount of variation in the second wavy portion 51 at the inner peripheral edge, a cross-sectional surface is created at a position closer to the inner peripheral edge than the center portion in the width direction of the second wavy portion 51.

[0119] The ratio (L2 / L0) of the actual length (L2) of each second wave portion 51 to the distance (L0) between the two ends of the second wave portion 51 can be, for example, 1.01 or more and 3.00 or less. It should be noted that the above-mentioned ratio (L2 / L0) of each second wave portion 51 can be determined based on the moving average of the second wave portion 51 described above.

[0120] The thickness t1 of the first adhesive portion 34 is not particularly limited, for example, it is 1 μm or more and 100 μm or less. The thickness t1 of the first adhesive portion 34 is the distance between the first interface 4 and the second interface 5. The thickness t1 of the first adhesive portion 34 can be measured based on the moving average of the first wavy portion 41 and the second wavy portion 51 described above. Specifically, as... Figure 5 As shown, the thickness t1 of the first adhesive portion 34 can be measured at points where the moving average line of the first wavy portion 41 and the second wavy portion 51 is divided into eight equal parts in the direction in which the first adhesive portion 34 extends. The average value of these measurements is taken as the thickness of the first adhesive portion 34. The ratio (t2 / t1) of the thickness t2 of the metal support 31 to the thickness t1 of the first adhesive portion 34 can be, for example, 500 or less.

[0121] <Manufacturing Method>

[0122] The manufacturing method of the first interface 4, the second interface 5, and the first adhesive portion 34 will be described below. First, the metal support 31 is subjected to bending processing such as pressing, thereby setting the area of ​​the second main surface 312 of the metal support 31 that is bonded to the first adhesive portion 34, i.e., the area constituting the first interface 4, as described above, into the waveform described above. It should be noted that even if the second main surface 312 of the metal support 31 is thinned by cutting, etching, or laser ablation, the shape described above can still be achieved.

[0123] Similarly, the frame 32 is subjected to bending processes such as pressing, thereby setting the area in the first main surface 321 of the frame 32 that is bonded to the first adhesive portion 34, i.e. the area constituting the second interface 5, to the waveform described above.

[0124] Furthermore, a paste containing a crystalline metal oxide is applied to the surface of at least one of the metal support 31 and the frame 32, and then heat treatment is performed to ensure that the metal support 31 and the frame 32 are tightly bonded, thereby forming the first adhesive portion 34. The heat treatment conditions can be appropriately set, for example, to 600°C or higher and 1100°C or lower, and for 0.5 hours or higher and 24 hours or lower.

[0125] (Modifications of the implementation method)

[0126] The embodiments of the present invention have been described above. However, the present invention is not limited to these embodiments, and various modifications can be made as long as they do not depart from the spirit of the present invention.

[0127] (a) In the first and second embodiments described above, the frame 32 and the interconnector 33 are separate components; however, the frame 32 and the interconnector 33 can be an integral component. In this case, the fluid container 3 does not have the second adhesive portion 35.

[0128] (b) In the first and second embodiments described above, the metal support 31 and the frame 32 are separate components; however, the metal support 31 and the frame 32 can be an integral component. In this case, the fluid container 3 does not have the first adhesive portion 34.

[0129] (c) In the above embodiments, a metal support 31 is shown as an example of a first metal component, and a frame 32 is shown as an example of a second metal component. However, the configuration of the fluid container 3 is not limited to this. For example, the frame 32 may be an example of a first metal component, and the metal support 31 may be an example of a second metal component.

[0130] (d) In the above embodiment, the first wave-shaped portion 41 is formed around the entire circumference of the first interface 4; however, the configuration of the first interface 4 is not limited thereto. For example, of the four straight portions of the first interface 4, only one straight portion is composed of the first wave-shaped portion 41, and the remaining straight portions may be planar rather than wave-shaped. In detail, the first wave-shaped portion 41 may be formed in the portion of the four straight portions that is prone to stress. In addition, the first wave-shaped portion 41 does not need to constitute the entirety of the straight portion; it may constitute only a part of the straight portion. It should be noted that the second interface 5 is the same.

[0131] (e) The second interface 5 may not have the second wavy portion 51. That is, as shown in the image. Figure 6 As shown, only the first interface 4 may have a first wavy portion 41.

[0132] (f) such as Figure 7 As shown, the first adhesive portion 34 may have a gap 341 inside it. In this case, the gap 341 is not formed in the entire width direction ( Figure 7(in the X direction).

[0133] (g) In the above embodiments, an electrolytic single cell is used as an example of an electrochemical single cell for explanation; however, electrochemical single cells are not limited to electrolytic single cells. An electrochemical single cell refers to a combination of components that have a pair of electrodes configured to generate an electromotive force based on an overall redox reaction, in order to convert electrical energy into chemical energy, and components used to convert chemical energy into electrical energy. Therefore, electrochemical single cells also include, for example, fuel cells that use oxide ions or protons as carriers.

[0134] (h) In the above embodiments, the application of the fluid container of the present invention to an electrochemical single cell has been described; however, the fluid container can be used for various applications. For example, the fluid container can be used in a metallization reactor for the synthesis of methane from hydrogen and carbon dioxide.

[0135] Example

[0136] The embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments described below.

[0137] Make 21 Figure 2 The electrolytic single cell 100 is shown. Specifically, NiO-GDC (porosity: 35%, thickness: 25μm, thermal expansion coefficient: 12.7ppm / K) is used as the hydrogen electrode 21; YSZ (porosity: 0.6%, thickness: 8μm, thermal expansion coefficient: 10.0ppm / K) is used as the electrolyte 22; GDC (porosity: 25%, thickness: 8μm, thermal expansion coefficient: 12.3ppm / K) is used as the anti-reaction layer 23; and LSCF (porosity: 45%, thickness: 30μm, thermal expansion coefficient: 15.0ppm / K) is used as the oxygen electrode 24. It should be noted that the overall dimensions of the single cell body 2 are 130mm square. Crofer22APU (overall dimensions: 150mm square, thickness: 200μm, thermal expansion coefficient: 12.7ppm / K) is used as the metal support plate 31, frame 32, and interconnector 33. Furthermore, the internal dimensions of the frame 32 are 130mm square. The first adhesive part 34 and the second adhesive part 35 are made of chromium oxide.

[0138] Each electrolytic cell 100 is manufactured with different variations in the first corrugated portion 41 and the second corrugated portion 51 of the first adhesive portion 34. The variations in the first corrugated portion 41 and the second corrugated portion 51 are shown in Table 1. It should be noted that in electrolytic cells 100 No. 1 to No. 2, the second interface 5 does not have the second corrugated portion 51. Furthermore, in electrolytic cell 100 No. 21, the first interface 4 does not have the first corrugated portion 41, and the second interface 5 also does not have the second corrugated portion 51. It should be noted that all conditions except for the variations are the same in each electrolytic cell 100.

[0139] <Evaluation Methods>

[0140] For each electrolytic cell 100, a thermal cycling test was conducted to investigate whether peeling or cracking occurred at the first bonding portion 34. Specifically, each electrolytic cell 100 was placed in an electric furnace and subjected to repeated heating and cooling cycles from room temperature to 800°C at a rate of 200°C / hr 10 times. Afterward, it was removed from the furnace, and the presence or absence of peeling or cracking at the first bonding portion 34 was investigated. The presence or absence of peeling was determined by visual inspection. The presence or absence of cracking was determined by SEM observation at 5000x magnification. These results are shown in Table 1.

[0141] Table 1

[0142]

[0143] <Evaluation Results>

[0144] As shown in Table 1, it can be seen that having a wavy portion in at least one of the first interface 4 and the second interface 5 can prevent peeling from occurring at the first adhesive portion 34, or suppress it to partial peeling. Furthermore, it can be seen that having a wavy portion in at least one of the first interface 4 and the second interface 5, and setting the variation of the wavy portion to 1 to 50 μm, can prevent peeling from occurring at the first adhesive portion 34. Additionally, it can be seen that having a first wavy portion 41 in the first interface 4 and a second wavy portion 52 in the second interface 5, and setting the variation of each wavy portion to 1 to 50 μm, can prevent peeling from occurring at the first adhesive portion 34 and can also prevent the occurrence of micro-cracks.

[0145] Symbol Explanation

[0146] 2: Single battery main body

[0147] 3: Fluid container

[0148] 30: Interior Space

[0149] 31: Metal support

[0150] 32: Frame

[0151] 34: First adhesive part

[0152] 4: First Interface

[0153] 41: First wave-shaped part

[0154] 5: Second Interface

[0155] 51: Second wave-shaped part

[0156] 100: Electrolytic single cell

Claims

1. A fluid container, characterized in that, have: A first metal component, the first metal component containing chromium; A second metal component, the second metal component containing chromium; An adhesive portion, which is composed of an oxide with chromium as the main component, bonds the first metal component and the second metal component together; The first interface is the interface between the first metal component and the adhesive portion; as well as The second interface is the interface between the second metal component and the adhesive portion. The first interface has a first wavy portion that repeatedly vibrates in the thickness direction and extends along the outer periphery of the first metal component.

2. The fluid container according to claim 1, characterized in that, The second interface has a second wavy portion that repeats the amplitude in the thickness direction and extends along the outer periphery of the second metal component.

3. The fluid container according to claim 1, characterized in that, The first wavy portion is configured such that the amount of variation at its outer periphery is greater than the amount of variation at its inner periphery.

4. The fluid container according to claim 1, characterized in that, The first adhesive portion has a void portion.

5. The fluid container according to claim 1, characterized in that, The first wavy portion has a variation of more than 1 μm and less than 50 μm.

6. The fluid container according to claim 2, characterized in that, The first wavy portion has a variation of more than 1 μm and less than 50 μm. The second wavy portion has a variation of more than 1 μm and less than 50 μm.

7. The fluid container according to claim 1, characterized in that, The fluid container also includes an internal space for fluid flow. The adhesive portion extends in a ring shape to surround the internal space.

8. The fluid container according to claim 1, characterized in that, The fluid container also includes an internal space for fluid flow. The adhesive part is a seal used to close the internal space.

9. An electrochemical single cell, characterized in that, have: The fluid container of claim 1; and A single-cell main body is disposed on the fluid container.

10. The electrochemical single cell according to claim 9, characterized in that, The fluid container has an internal space for fluid flow. The first metal component has: a plurality of connecting holes connected to the internal space. The single battery body is disposed on the first metal component in such a way that it covers the plurality of connecting holes.

11. The electrochemical single cell according to claim 9, characterized in that, The fluid container has an internal space for fluid flow. The second metal component has: a plurality of connecting holes connected to the internal space. The single battery body is disposed on the second metal component in such a way that it covers the plurality of connecting holes.

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