Fixed electrochemical device

Abstract

A solid electrochemical device is provided, comprising: a solid electrolyte having a first main surface and a second main surface opposite the first main surface; a first electrode having a third main surface and a fourth main surface opposite the third main surface, the latter being configured such that the third main surface faces the first main surface; a first current collector having a fifth main surface and a sixth main surface opposite the fifth main surface, the latter being configured such that the fifth main surface faces the fourth main surface;and a first interconnector having a seventh main surface which is configured such that the seventh main surface is directed towards the sixth main surface, wherein the seventh main surface of the first interconnector is a flat surface, the first current collector includes a first porous metallic body having a three-dimensional network structure, and the fifth main surface has a plurality of first through-holes configured to extend along a first direction from the fifth main surface to the sixth main surface.

Description

TECHNICAL AREA

[0001] The present disclosure relates to a solid electrochemical device or a solid-state electrochemical device. This application claims priority based on Japanese patent application No. 2023-001579, filed on January 10, 2023, the entire contents of which are incorporated herein by reference. STATE OF THE ART

[0002] Conventionally, a solid electrochemical device or solid-state electrochemical device was used, which contained a solid electrolyte or...Solid electrolyte comprising a first main surface and a second main surface, which is a surface opposite the first main surface, a first electrode comprising a third main surface and a fourth main surface, which is a surface opposite the third main surface and is provided such that the third main surface is directed towards the first main surface, a first current collector comprising a fifth main surface and a sixth main surface, which is a surface opposite the fifth main surface and is provided such that the fifth main surface is directed towards the fourth main surface, and a first interconnect comprising a seventh main surface and provided such that the seventh main surface is directed towards the sixth main surface (Patent Literature 1). LITERATURE LIST PATENT LITERATURE

[0003] Patent literature 1: WO 2021 / 210231 SUMMARY OF THE INVENTION

[0004] A solid electrochemical device or electrochemical solid-state device according to one aspect of the present disclosure comprises a solid orA solid electrolyte comprising a first main surface and a second main surface, the latter being a surface opposite the first main surface; a first electrode comprising a third main surface and a fourth main surface, the latter being a surface opposite the third main surface, and arranged such that the third main surface is directed towards the first main surface; a first current collector comprising a fifth main surface and a sixth main surface, the latter being a surface opposite the fifth main surface, and arranged such that the fifth main surface is directed towards the fourth main surface; and a first interconnect comprising a seventh main surface, arranged such that the seventh main surface is directed towards the sixth main surface.The seventh main surface of the first interconnector is a flat surface. The first current collector is formed from a first metallic porous body, which exhibits a three-dimensional network structure. A multitude of first penetration holes, extending along a first direction from the fifth main surface towards the sixth main surface, are formed in the fifth main surface. BRIEF DESCRIPTION OF THE DRAWINGS Fig. Figure 1 is a schematic cross-sectional view illustrating an example of a fixed electrochemical device according to an embodiment of the present disclosure. Fig. Figure 2 is a schematic top view illustrating an example of a first current collector according to an embodiment of the present disclosure. DETAILED DESCRIPTION [Problems to be solved by the present disclosure]

[0005] Conventionally, a grooved interconnect was used in a solid electrochemical device in combination with a current collector formed from a porous metallic body with a three-dimensional network structure. The grooves of the interconnect prevent pressure loss within the device and allow fuel gas or air to diffuse easily through the current collector.

[0006] In recent years, there has been a growing demand for the miniaturization of solid electrochemical devices. For example, one method for miniaturizing a solid electrochemical device is to use a thinner interconnect, eliminating grooves or channels on its main surface and creating a flat surface. However, when this thinner interconnect is used in combination with the current collector, the pressure drop in the solid electrochemical device can increase, and its power density can be reduced due to decreased gas diffusion capacity. Therefore, in some cases, it is difficult to make the solid electrochemical device compact, minimize pressure drop, and prevent a decrease in power density.

[0007] One objective or subject of the present disclosure is to provide a solid electrochemical device or solid-state electrochemical device which is compact, excels in suppressing pressure loss and has excellent power density. [Beneficial effects of the present disclosure]

[0008] According to the present disclosure, it is possible to provide a fixed electrochemical device which is compact, excellent in suppressing a “pressure loss” and has an excellent “power density”. [Description of embodiments of the present disclosure]

[0009] First, embodiments of the present disclosure are listed and described.

[0010] [1] A fixed electrochemical device according to one aspect of the present disclosure includes a fixed orA solid electrolyte comprising a first main surface and a second main surface, the latter being a surface opposite the first main surface; a first electrode comprising a third main surface and a fourth main surface, the latter being a surface opposite the third main surface, and arranged such that the third main surface is directed towards the first main surface; a first current collector comprising a fifth main surface and a sixth main surface, the latter being a surface opposite the fifth main surface, and arranged such that the fifth main surface is directed towards the fourth main surface; and a first interconnect comprising a seventh main surface, arranged such that the seventh main surface is directed towards the sixth main surface.The seventh main surface of the first interconnector is a flat surface. The first current collector is formed from a first metallic porous body, which exhibits a three-dimensional network structure. A multitude of first penetration holes, extending along a first direction from the fifth main surface towards the sixth main surface, are formed in the fifth main surface.

[0011] According to the present disclosure, it is possible to provide a fixed electrochemical device which is compact, excellent in suppressing a “pressure loss” and has an excellent “power density”.

[0012] [2] In the above [1], in a top view of the fifth main surface, the first through-holes can each have a first width along a second direction orthogonal to the first direction and can each have a second width along a third direction orthogonal to both the first and second directions. An average value of the first width and the second width can be from 2 mm to 20 mm. This makes it possible to provide a fixed electrochemical device which is superior in suppressing pressure loss and has a superior power density.

[0013] [3] In the above [1] or [2], a first aperture ratio, which is a percentage of the total area of ​​the first through-holes relative to the area of ​​the fifth main surface, can be from 2.0% to 35%. This makes it possible to provide a fixed electrochemical device that is superior in suppressing pressure loss and has a superior power density.

[0014] [4] In any of the above [1] to [3], in each of nine first regions, which are defined by a uniform subdivision of the fifth main surface into nine parts based on an area criterion, a second opening ratio, which is a percentage of a total area of ​​the first passage holes in each of the first regions relative to an area of ​​each of the first regions, can be 2.0% to 35%. This makes it possible to provide a fixed electrochemical device which is more excellent in suppressing the “pressure loss” and has a more excellent “power density”.

[0015] [5] In any of the above [1] to [4], the first metallic porous body can be a metallic porous nickel-cobalt body. This makes it possible to provide a solid electrochemical device which has a more excellent power density.

[0016] [6] In any of the above [1] to [4], the first metallic body can be a metallic porous nickel body. This makes it possible to provide a solid electrochemical device which has a more excellent power density.

[0017] [7] In any of the above [1] to [4], the first metallic porous body can be a metallic porous nickel-tin body. This makes it possible to provide a solid electrochemical device which has a more excellent power density.

[0018] [8] In any one of the above [1] to [7], the fixed electrochemical apparatus may further comprise a second electrode having an eighth main surface and a ninth main surface, which is a surface opposite the eighth main surface, and is arranged such that the eighth main surface faces the second main surface; a second current collector having a tenth main surface and an eleventh main surface, which is a surface opposite the tenth main surface, and is arranged such that the tenth main surface faces the ninth main surface; and a second interconnector having a twelfth main surface, arranged such that the twelfth main surface faces the eleventh main surface. The twelfth main surface of the second interconnector may be a flat surface.The second current collector can be formed from a second metallic porous body exhibiting a three-dimensional network structure. A multitude of secondary through-holes, extending along a fourth direction from the tenth main surface towards the eleventh main surface, can be formed in the tenth main surface. This makes it possible to provide a solid electrochemical device that is more compact, exhibits superior pressure loss suppression, and has a higher power density.

[0019] [9] In the above [8], in a top view of the tenth main surface, the second through-holes can each have a third width along a fifth direction orthogonal to the fourth direction, and each have a fourth width along a sixth direction orthogonal to the fourth and fifth directions. An average value of the third and fourth widths can be from 2 mm to 20 mm. This makes it possible to provide a fixed electrochemical device that is more excellent at suppressing pressure loss and has a more excellent power density.

[0020]

[10] In the above [8] or [9], a third aperture ratio, which is a percentage of the total area of ​​the second through-holes relative to the area of ​​the tenth main surface, can be from 2.0% to 35%. This makes it possible to provide a fixed electrochemical device which is more excellent at suppressing the “pressure loss” and has a more excellent “power density”.

[0021]

[11] In any of the above [8] to

[10] , in each of nine second regions defined by a uniform subdivision of the tenth main surface into nine parts based on an area criterion, a fourth opening ratio, which is a percentage of a total area of ​​the second passage holes in each of the second regions relative to an area of ​​each of the second regions, can be 2.0% to 35%. This makes it possible to provide a fixed electrochemical device which is more excellent at suppressing the “pressure loss” and has a more excellent “power density”.

[0022]

[12] In any of the above [8] to

[11] , the second metallic porous body can be a metallic porous nickel-cobalt body. This makes it possible to provide a solid electrochemical device which has a more excellent power density.

[0023]

[13] In any of the above [8] to

[11] , the second metallic porous body can be a metallic porous nickel body. This makes it possible to provide a solid electrochemical device which has a more excellent power density.

[0024]

[14] In any of the above [8] to

[11] , the second metallic porous body can be a metallic porous nickel-tin body. This makes it possible to provide a solid electrochemical device which has a more excellent power density. [Details of embodiments of the present disclosure]

[0025] Specific examples of a fixed electrochemical device according to an embodiment (hereinafter also referred to as "the present embodiment") of the present disclosure will be described below with reference to the drawings. In the drawings of the present disclosure, elements that have the same reference numerals denote the same or corresponding elements. Dimensions, such as length, width, thickness, and depth, are or will be modified as appropriate for the sake of clarity and simplification of the drawings and do not necessarily represent actual dimensions.

[0026] In this description, the designation in the form of "A to B" signifies a lower limit and an upper limit of a range (i.e., A or more and B or less), and if there is no description of a unit for A and a unit is described only for B, then the unit of A and the unit of B are the same. [Design 1: Fixed electrochemical device]

[0027] A fixed electrochemical device according to an embodiment of the present disclosure is described with reference to Fig. 1 described. Fig. Figure 1 is a schematic cross-sectional view showing an example of a solid electrochemical device or solid electrochemical device according to an embodiment of the present disclosure.

[0028] A fixed electrochemical device 100 according to an embodiment (hereinafter also referred to as “embodiment 1”) of the present disclosure comprises a fixed orSolid electrolyte 11, which has a first main surface 111 and a second surface 112, which is a surface opposite the first main surface 111; a first electrode 12, which has a third main surface 121 and a fourth main surface 122, which is a surface opposite the third main surface 121, and is provided such that the third main surface 121 is directed towards the first main surface 111; a first current collector 20, which has a fifth main surface 201 and a sixth main surface 202, which is a surface opposite the fifth main surface 201, and is provided such that the fifth main surface 201 is directed towards the fourth main surface 122; and a first interconnector orInterconnector 40, which has a seventh main surface 401 and is configured such that the seventh main surface 401 faces the sixth main surface 202. The seventh main surface 401 of the first interconnector 40 is a flat surface. The first current collector 20 is formed from a first metallic porous body, which has a three-dimensional network structure. A plurality of first through-holes 21, which extend along a first direction from the fifth main surface 201 towards the sixth main surface 202, are formed in the fifth main surface.

[0029] According to the present disclosure, it is possible to provide a fixed electrochemical device that is compact, exhibits excellent pressure loss suppression, and has an excellent power density. The reason for this is considered to be as follows.

[0030] (a) The seventh main surface 401 of the first interconnector 40 is a flat surface. This makes it possible to reduce the thickness of the first interconnector 40 and thus reduce the overall size of the solid electrochemical device or electrochemical solid-state device 100.

[0031] (b) As described above, the seventh main surface 401 of the first interconnect 40 is a flat surface, and thus the solid electrochemical device 100 can be miniaturized overall. However, in a case where the seventh main surface 401 of the first interconnect 40 is a flat surface (in other words, the seventh main surface of the first interconnect 40 has no grooves or channels), the pressure drop of the solid electrochemical device 100 tends to occur. Additionally, the diffusivity of a fuel gas (hydrogen gas) and of air in the current collector tends to decrease, and the reactivity of the fuel gas (hydrogen gas) and the reactivity of air tend to decrease, which tends to slightly reduce the power density of the solid electrochemical device 100.

[0032] In the first current collector 20 of the fixed electrochemical device 100 according to the present embodiment, the plurality of first through-holes 21, which extend along the first direction from the fifth main surface 201 towards the sixth main surface 202, are formed in the fifth main surface 201. This suppresses an increase in the pressure drop. In addition, the gas (fuel gas or air) that flows into the fixed electrochemical device 100 from a side of the fixed electrochemical device 100 on which the first interconnector 40 is located, is easily distributed in the first current collector 20, and thus a decrease in the diffusivity or distribution of the fuel gas or air is suppressed, and a decrease in the power density of the fixed electrochemical device 100 can be suppressed.

[0033] That is, according to the present disclosure, it is possible to provide the solid electrochemical device 100, which is compact, excels at suppressing “pressure loss” and has excellent “power density”. <<Feste elektrochemische Vorrichtung> >

[0034] In the present disclosure, the solid electrochemical device 100 is a concept that includes both a solid oxide fuel cell (SOFC) and a solid oxide electrolysis cell (SOEC). In the present disclosure, the solid electrochemical device, or solid electrochemical device 100, can be considered to have a sheet or sheet shape and to include a thirteenth main surface 101 and a fourteenth main surface 102.

[0035] The solid electrochemical device 100 can have a thickness of 2.1 mm or less. Here, the thickness of the solid electrochemical device 100 refers to the distance between the thirteenth main surface 101 and the fourteenth main surface 102. In this way, it is possible to provide a compact solid electrochemical device 100. An upper limit for the thickness of the solid electrochemical device 100 can be 1.8 mm or 1.5 mm. A lower limit for the thickness of the solid electrochemical device 100 is not specifically restricted and can be 1 mm, 0.75 mm, or 0.5 mm from a production standpoint.

[0036] The thickness of the solid electrochemical device 100 can be determined by the same procedure as the procedure for measuring the “thickness of the first current collector 20”, which will be described later. < <festelektrolyt>>

[0037] The solid electrochemical device 100 of the present disclosure comprises the solid electrolyte 11, which has the first main surface 111 and the second main surface 112, which is a surface opposite the first main surface 111. For example, the solid electrolyte 11 is formed from yttrium oxide-stabilized zirconium (YSZ).

[0038] The solid electrolyte 11 can have a thickness of 0.0005 mm to 0.05 mm. If the thickness of the solid electrolyte 11 is less than 0.0005 mm, it tends to become difficult for the solid electrolyte 11 to function as a solid electrolyte in the solid electrochemical device 100. If the thickness of the solid electrolyte 11 is more than 0.05 mm, it tends to become difficult for the solid electrochemical device 100 to reduce in size. The thickness of the solid electrolyte 11 can be determined by the same procedure as the procedure for measuring the thickness of the first current collector 20, which is described later. <<Erste Elektrode> >

[0039] The fixed electrochemical device 100 of the present disclosure comprises the first electrode 12, which has the third main surface 121 and the fourth main surface 122, which is a surface opposite the third main surface 121, and is arranged such that the third main surface 121 is directed towards the first main surface 111. The first electrode 12 can be a cathode or an anode. However, if the first electrode 12 is a cathode, a second electrode 13, which will be described later, is an anode. If the first electrode 12 is an anode, the second electrode 13, which will be described later, is a cathode. If the first electrode 12 is a cathode, the first electrode 12 can, for example, be formed of LSC (lanthanum (La)-strontium (Sr)-cobalt (Co) oxide).If the first electrode 12 is an anode, the first electrode 12 can, for example, be formed from a composite of YSZ and nickel oxide (Ni2O).

[0040] The first electrode 12 can have a thickness of 0.1 mm to 0.5 mm. If the thickness of the first electrode 12 is less than 0.1 mm, it tends to become difficult for the first electrode 12 to function as an electrode in the fixed electrochemical device 100. If the thickness of the first electrode 12 is more than 0.5 mm, it tends to become difficult for the fixed electrochemical device 100 to reduce its size. The thickness of the first electrode 12 can be determined by the same procedure as the procedure for measuring the thickness of the first current collector 20, which is described later. <<Erster Stromkollektor> >

[0041] The fixed electrochemical device 100 of the present disclosure includes the first current collector 20, which has the fifth main surface 201 and a sixth main surface 202, which is a surface opposite the fifth main surface 201, and is arranged such that the fifth main surface 201 is directed towards the fourth main surface 122. With regard to the first current collector 20, except as described below, the contents described in paragraphs

[0036] to

[0047] , paragraphs

[0080] to

[0084] , paragraph

[0086] , paragraph

[0087] and paragraphs

[0112] to

[0114] of International Publication WO 2021 / 153406 are incorporated in the present description by reference. However, in the present disclosure, the description "bubbles are easily released to the outside" in the above contents is described as "a diffusion capability of gas is oris easily improved and a pressure loss is easily suppressed.” In the present disclosure, the expression “sheet or sheet of a metallic porous body” in the above contents is read as the expression “first current collector.” In the present disclosure, the expression “hole” in the above contents is read as the expression “first penetration hole.” In the present disclosure, the expression “first principal surface” in the above contents is read as the expression “fifth principal surface,” and the expression “second principal surface” in the above contents is read as the expression “sixth principal surface.” In the present disclosure, the expression “width W1” in the above contents is read as the expression “first latitude,” and the expression “width W2” in the above contents is read as the expression “second latitude.”In the present disclosure, the expression “opening relationship” in the above contents is read as the expression “first opening relationship”.

[0042] The first current collector 20 can have a thickness of 0.05 mm to 0.5 mm. If the thickness of the first current collector 20 is less than 0.05 mm, it tends to become difficult for the first current collector 20 to function as a current collector in the solid electrochemical device 100. If the thickness of the first current collector 20 is more than 0.5 mm, it tends to become difficult for the solid electrochemical device 100 to reduce its size. The thickness of the first current collector 20 can be measured with a commercially available digital thickness gauge (TECLOCK Co., Ltd.). <Erstes Durchtrittsloch>

[0043] In the fixed electrochemical device 100 of the present disclosure, the plurality of first through-holes 21, which extend along the first direction from the fifth main surface 201 towards the sixth main surface 202, are formed in the fifth main surface 201. This makes it possible to suppress the pressure loss and improve the power density in the fixed electrochemical device 100.

[0044] As this is in Fig. As illustrated in Figure 2, in a top view of the fifth main surface 201, the first through-holes 21 can each have a first width 211 along a second direction orthogonal to the first direction and can each have a second width 212 along a third direction orthogonal to both the first and second directions. An average value of the first width 211 and the second width 212 can be from 2 mm to 20 mm. The second direction is a direction in which the first width 211 is maximized. This makes it possible to further suppress an increase in pressure loss and a decrease in power density. A lower limit of the average value of the first width 211 and the second width 212 can be 2 mm, 4 mm, or 5 mm. An upper limit of the average value of the first width 211 and the second width 212 can be 20 mm, 15 mm, or 10 mm.The average value of the first width 211 and the second width 212 can be 4 mm to 15 mm, or can be 5 mm to 10 mm.

[0045] In the fixed electrochemical device 100, the average value of the first width 211 and the second width 212 can be determined by the following procedure. That is, in a top view of the fifth main surface 201 of the first current collector 20, the first width 211 and the second width 212 are measured for any one of the first through-holes 21. Next, the sum of the first width 211 and the second width 212 is divided by two to obtain a numerical value. Numerical values ​​for any four other first through-holes 21 are then obtained by the same procedure. By calculating the average of these numerical values, the average value of the first width 211 and the second width 212 can be determined.

[0046] In the fifth main surface 201, the first aperture ratio of the first through-holes 21 can be between 2.0% and 35%. The first aperture ratio is a percentage of the total area S1 of the first through-holes 21 relative to an area S2 of the fifth main surface 201. This makes it possible to further suppress an increase in pressure loss and a decrease in power density. A lower limit of the first aperture ratio of the first through-holes 21 can be 2.0%, 5%, or 10%. An upper limit of the first aperture ratio of the first through-holes 21 can be 35%, 30%, or 25%. The first aperture ratio of the first through-holes 21 can be 5% to 30%, or 10% to 25%.

[0047] In the first current collector 20, the area S1 of the first penetration holes 21 and the area S2 of the fifth main surface 201 can be determined by the following procedure. First, the fifth main surface 201 of the first current collector 20 is photographed from the first direction, thus obtaining image data of the fifth main surface 201 of the first current collector 20. Next, binarization processing is performed on the image data to identify regions where the first penetration holes 21 are formed and the other region. The area S1 of the first penetration holes 21 can then be obtained by measuring the areas of the regions where the first penetration holes 21 are formed.The area S2 of the fifth main surface 201 can be obtained by measuring an area of ​​a region which is obtained by combining the “regions where the first penetration holes 21 are formed” and the “other region”.

[0048] In each of nine first regions 203, which are set or defined by uniformly subdividing the fifth main surface 201 into nine parts based on an area criterion, a second aperture ratio of the first passage holes 21 can be between 2.0% and 35%. Here, the second aperture ratio is a percentage of the total area S1 of the first passage holes 21 in each of the first regions 203 relative to the area S3 of each of the first regions 203. This makes it possible to further suppress an increase in pressure loss and a decrease in power density. In each of the nine first regions 203, the second aperture ratio of the first passage holes 21 can be 2.0% or more, 5% or more, or 10% or more. In each of the nine first regions 203, the second aperture ratio of the first passage holes 21 can be 35% or less, 30% or less, or 25% or less.In each of the nine first regions 203, the second opening ratio of the first passage holes 21 can be 5% to 30%, or 10% to 25%.

[0049] The area S3 of the first regions 203 of the first power collector 20 can be determined by the same procedure as that for the area S2 of the fifth main surface 201, except that the first regions 203 are defined by subdividing the image data of the fifth main surface 201 of the first power collector 20 into nine equal parts based on an area criterion. If the first penetration hole 21 is arranged transversely across the plurality of first regions 203, only the area of ​​a section located within a first region to be measured by the first regions 203 is measured.

[0050] In the first current collector 20, the plurality of first penetration holes 21 can be arranged in a plurality of lines along the second direction. The plurality of first penetration holes 21 contained in each of the plurality of lines can be arranged periodically at a first spacing or interval in the second direction. Each of the plurality of lines can be arranged periodically at a second interval or spacing in the third direction. <Erster metallischer poröser Körper>

[0051] The first current collector 20 is formed from a first metallic porous body, which has a three-dimensional network structure. The term "first metallic porous body" means a porous body whose skeletal structure contains a metal element as a major component. Here, the expression "the skeletal structure contains a metal element as a major component" means that the total content of metallic elements in the skeletal structure exceeds 50% by mass.

[0052] The total metallic content of the skeletal body can be determined by the following procedure. First, a section of the skeletal body is identified, and an observational image of a cross-section perpendicular to an extending direction of the skeleton is obtained using a selective electron microscope (SEM). Next, the observed section is analyzed using an end-penetrant x-ray spectroscope (EDX) connected to the SEM. For example, the SEM used is a product available under the trade name "SUPRA35VP" from Carl Zeiss Microscopy Co., Ltd. The EDX instrument used is, for example, "octane super" (trade name), manufactured by AMETEK, Inc. A mass percentage of each of the metallic elements in the skeletal body is determined based on the atomic concentration of each element detected by the EDX instrument.Next, the “total content of metallic or metal elements” in the skeletal body can be determined by summing the “mass percentage of each of the metallic elements in the skeletal body”.

[0053] It was confirmed that there is no deviation in the measurement results even if the measurement region is arbitrarily changed, as long as the measurement is carried out in the first current collector 20 using the procedure described above.

[0054] The first metallic porous body can be a metallic porous nickel-cobalt body. This can further suppress a decrease in power density. The term "metallic porous nickel-cobalt body" means a porous body whose skeletal structure contains a nickel element and a cobalt element as its main components. Here, the expression "the skeletal structure contains a nickel element and a cobalt element as its main components" means that the skeletal structure contains both a nickel element and a cobalt element, and that the total content of the nickel element and the cobalt element exceeds 50% by mass, respectively.

[0055] The first metallic porous body can be a metallic porous nickel body. This can further suppress a decrease in power density. The term "metallic porous nickel body" means a porous body whose skeletal structure contains a nickel element as a major component. Here, the expression "the skeletal structure contains a nickel element as a major component" means that the total content of the nickel element in the skeletal structure exceeds 50% by mass.

[0056] The first metallic porous body can be a metallic porous nickel-tin body. This can further suppress a decrease in power density. The term "metallic porous nickel-tin body" means a porous body whose skeletal structure contains a nickel element and a tin element as its main components. Here, the expression "the skeletal structure contains a nickel element and a tin element as its main components" means that the skeletal structure contains both a nickel element and a tin element, and that the total content of the nickel element and the tin element exceeds 50% by mass.

[0057] The average pore diameter of the first metallic porous body is not particularly restricted or limited and can, for example, be 100 µm to 1000 µm, 200 µm to 900 µm, or 400 µm to 800 µm. With regard to the average pore diameter, the specifications described in International Publication WO 2021 / 153406 are incorporated into this description by reference. <<Erster Interkonnektor> >

[0058] The fixed electrochemical device 100 of the present disclosure includes the first interconnector 40, which has the seventh main surface 401 and is configured such that the seventh main surface 401 faces the sixth main surface 202. The seventh main surface 401 of the first interconnector 40 is a flat surface. Here, the expression "the seventh main surface 401 is a flat surface" means that "no groove is formed in the seventh main surface 401." This makes it possible to reduce the thickness of the first interconnector 40 and thus the size of the fixed electrochemical device 100. For example, the first interconnector 40 is made of an iron-chromium (FeCr) alloy.

[0059] The first interconnect 40 can have a thickness of 0.1 mm to 0.4 mm. If the thickness of the first interconnect 40 is less than 0.1 mm, it tends to become difficult for the first interconnect 40 to function as an interconnect in the fixed electrochemical device 100. If the thickness of the first interconnect 40 is more than 0.4 mm, it tends to become difficult for the fixed electrochemical device 100 to reduce its size. The thickness of the first interconnect 40 can be determined by the same procedure as the procedure for measuring the thickness of the first current collector 20, which is described above. <<Zweite Elektrode> >

[0060] The fixed electrochemical device 100 of the present disclosure can further include the second electrode 13, which has an eighth main surface 131 and a ninth main surface 132, the latter being a surface opposite the eighth main surface 131, and is arranged such that the eighth main surface 131 is directed towards the second main surface 112. If the second electrode 13 is a cathode, the second electrode 13 can, for example, be formed from LSC (lanthanum (La)-strontium (Sr)-cobalt (Co) oxide). If the second electrode 13 is an anode, the second electrode 13 can, for example, be formed from a composite of YSZ and nickel oxide (Ni2O).

[0061] The second electrode 13 can have a thickness of 0.1 mm to 0.5 mm. If the thickness of the second electrode 13 is less than 0.1 mm, it tends to become difficult for the second electrode 13 to function as an electrode in the fixed electrochemical device 100. If the thickness of the second electrode 13 is more than 0.5 mm, it tends to become difficult to reduce the size of the fixed electrochemical device 100. The thickness of the second electrode 13 can be determined by the same procedure as the procedure for measuring the thickness of the current collector 20, which is described above. <<Zweiter Stromkollektor> >

[0062] The fixed electrochemical device 100 of the present disclosure may further include a second current collector 30, which has a tenth main surface 301 and an eleventh main surface 302, which is a surface opposite the tenth main surface 301, and is provided such that the tenth main surface 301 is directed towards the ninth main surface 132. With regard to the second current collector 30, except as described below, the contents described in paragraphs

[0036] to

[0047] , paragraphs

[0080] to

[0084] , paragraph

[0086] , paragraph

[0087] and paragraphs

[0112] to

[0114] of International Publication WO 2021 / 153406 are incorporated in the present description by reference. However, in the present disclosure, the description "bubbles are easily released to the outside" in the above contents is described as "a diffusion capability of gas is oris easily improved and a pressure loss is easily suppressed.” In the present disclosure, the expression “sheet or sheet of a metallic porous body” in the above contents is read as the expression “second current collector.” In the present disclosure, the expression “hole” in the above contents is read as the expression “second passage hole.” In the present disclosure, the “first principal surface” in the above contents is read as the “tenth principal surface,” and the “second principal surface” in the above contents is read as the “eleventh principal surface.” In the present disclosure, the “first direction” in the above contents is read as the “fourth direction,” the “second direction” in the above contents is read as the “fifth direction,” and the “third direction” in the above contents is read as the “sixth direction.”In the present revelation, the expression "width W1" in the above content is read as the expression "third width," and the expression "width W2" in the above content is read as the expression "fourth width." In the present revelation, the expression "opening ratio" in the above content is read as the expression "third opening ratio."

[0063] The second current collector 30 can have a thickness of 0.05 mm to 0.5 mm. If the thickness of the second current collector 30 is less than 0.05 mm, it tends to become difficult for the second current collector 30 to function as a current collector in the fixed electrochemical device 100. If the thickness of the second current collector 30 is more than 0.5 mm, it tends to become difficult for the fixed electrochemical device 100 to reduce its size. The thickness of the second current collector 30 can be determined by the same procedure as the procedure for measuring the thickness of the first current collector 20, which is described above. <Zweites Durchtrittsloch>

[0064] In the fixed electrochemical device 100 of the present disclosure, a plurality of second through-holes 31, extending along a fourth direction from the tenth main surface 301 towards an eleventh main surface 302, may or may not be formed in the tenth main surface 301. This makes it possible to further suppress an increase in pressure loss and a decrease in power density.

[0065] In a top view of the tenth main surface, the second through-holes 31 can each have a third width 311 along a fifth direction orthogonal to the fourth direction, and each can have a fourth width along a sixth direction orthogonal to both the fourth and fifth directions. An average value of the third width 311 and the fourth width can be from 2 mm to 20 mm. The fifth direction is a direction in which the third width 311 is maximized. This makes it possible to further suppress an increase in pressure loss and a decrease in power density. A lower limit of the average value of the third width 311 and the fourth width can be 2 mm, 4 mm, or 5 mm. An upper limit of the average value of the third width 311 and the fourth width can be 20 mm, 15 mm, or 10 mm.The average value of the third width is 311 and the fourth width can be 4 mm to 15 mm, or 5 mm to 10 mm.

[0066] In the fixed electrochemical device 100, the average values ​​of the third width 311 and the fourth width can be determined by the following procedure. That is, in a top view of the tenth main surface 301 of the second current collector 30, the third width 311 and the fourth width are measured for any one of the second through-holes 31. Next, the sum of the third width 311 and the fourth width is divided by two to obtain a numerical value. Numerical values ​​for any four other second through-holes 31 are then obtained by the same procedure. By calculating the average of these numerical values, the average values ​​of the third width 311 and the fourth width can be determined.

[0067] In the tenth main surface 301, the third aperture ratio of the second through-holes 31 can be between 2.0% and 35%. The third aperture ratio is a percentage of the total area S4 of the second through-holes 31 relative to an area S5 of the tenth main surface 301. This makes it possible to further suppress an increase in pressure loss and a decrease in power density. A lower limit of the third aperture ratio of the second through-holes 31 can be 2.0%, 5.0%, or 10%. An upper limit of the third aperture ratio of the second through-holes 31 can be 35%, 30%, or 25%. The third aperture ratio of the second through-holes 31 can be 5% to 30%, or 10% to 25%.

[0068] In the second current collector 30, the area S4 of the second penetration holes 31 and the area S5 of the tenth main surface 301 can be determined by the following procedure. First, the tenth main surface 301 of the second current collector 30 is photographed from the fourth direction, thus obtaining image data of the tenth main surface 301 of the second current collector 30. Next, binarization processing is performed on the image data to identify regions where the second penetration holes 31 are formed and the other region. Finally, the area S4 of the second penetration holes 31 can be obtained by measuring the areas of the regions where the second penetration holes 31 are formed.The area S5 of the tenth main surface 301 can be obtained by measuring an area of ​​a region which is obtained by combining the “regions where the second penetration holes 31 are formed” and the “other region”.

[0069] In each of nine second regions, which are set or defined by uniformly subdividing the tenth main surface 301 into nine parts based on an area criterion, a fourth aperture ratio of the second passage holes 31 can be between 2.0% and 35%. Here, the fourth aperture ratio is a percentage of the total area S4 of the second passage holes 31 in each of the second regions relative to the area S6 of each of the second regions. This makes it possible to further suppress an increase in pressure loss and a decrease in power density. In each of the nine second regions, the fourth aperture ratio of the second passage holes 31 can be 2.0% or more, 5% or more, or 10% or more. In each of the nine second regions, the fourth aperture ratio of the second passage holes 31 can be 35% or less, 30% or less, or 25% or less.In each of the nine second regions, the fourth opening ratio of the second passage holes can be 31.5% to 30%, or 10% to 25%.

[0070] The area S6 of the second regions of the second power collector 30 can be determined by the same procedure as that for the area S5 of the tenth main surface 301, except that the second regions are defined by subdividing the image data of the tenth main surface 301 of the second power collector 30 into nine equal parts based on an area criterion. If the second penetration holes 31 are arranged transversely across the plurality of second regions, only the area of ​​a section located within a second region to be measured is measured.

[0071] In the second current collector 30, the plurality of second through-holes 31 can be arranged in a plurality of lines along the fifth direction. The plurality of second through-holes 31 contained in each of the plurality of lines can be arranged periodically at a third spacing or interval in the fifth direction. Each of the plurality of lines can be arranged periodically at a fourth interval or spacing in the sixth direction. <Zweiter metallischer poröser Körper>

[0072] The second current collector 30 can be formed from a second metallic porous body, which has a three-dimensional network structure. The term "second metallic porous body" means a porous body whose skeletal structure contains a metal element as a major component. Here, the expression "the skeletal structure contains a metal element as a major component" means that the total content of metal elements in the skeletal structure exceeds 50% by mass. The "total content of metal elements" in the skeletal structure can be determined by the same procedure as in the measurement of the "total content of metal elements" in the "first metallic porous body".

[0073] It was confirmed that there is no deviation in the measurement results even if the measurement region is arbitrarily changed, as long as the measurement is carried out in the same second current collector 30 using the procedure described above.

[0074] The second metallic porous body can be a metallic porous nickel-cobalt body. This can further suppress a decrease in power density. The definition of the metallic porous nickel-cobalt body is the same as that of the metallic porous nickel-cobalt body according to the first metallic porous body.

[0075] The second metallic porous body can be a metallic porous nickel body. This can further suppress a decrease in power density. The definition of the metallic porous nickel body is the same as that of the metallic porous nickel body according to the first metallic porous body.

[0076] The second metallic porous body can be a metallic porous nickel-tin body. This can further suppress a decrease in power density. The definition of the metallic porous nickel-tin body is the same as that of the metallic porous nickel-tin body according to the first metallic porous body.

[0077] The average pore diameter of the second metallic porous body is not particularly restricted or limited and may, for example, be 100 µm to 1000 µm, 200 µm to 900 µm, or 400 µm to 800 µm. With regard to the average pore diameter, the contents of International Publication WO 2021 / 153406 are incorporated into this description by reference. <<Zweiter Interkonnektor> >

[0078] The fixed electrochemical device 100 of the present disclosure can further include a second interconnect 50, which has a twelfth main surface 501 and is configured such that the twelfth main surface 501 faces the eleventh main surface 302. For example, the second interconnect 50 is made of an iron-chromium (FeCr) alloy. Additionally, the twelfth main surface of the second interconnect 50 can be a flat surface, or it may or need not be a flat surface. Here, the expression "the twelfth main surface 501 is a flat surface" means that "no groove is formed in the twelfth main surface 501." The twelfth main surface 501 of the second interconnect 50 can be a flat surface. This makes it possible to further reduce the size of the fixed electrochemical device 100.

[0079] The second interconnect 50 can have a thickness of 0.1 mm to 0.4 mm. If the thickness of the second interconnect 50 is less than 0.1 mm, it will tend to be difficult for the second interconnect 50 to function as an interconnect in the fixed electrochemical device 100. If the thickness of the second interconnect 50 is greater than 0.4 mm, it will tend to be difficult to reduce the size of the fixed electrochemical device 100. The thickness of the second interconnect 50 can be determined by the same procedure as the procedure for measuring the thickness of the first current collector 20, which is described above. < <zelle>>

[0080] In the present disclosure, a structure comprising the solid electrolyte 11, the first electrode 12, and the second electrode 13 is defined as a cell. The cell can have a thickness of 0.2005 mm to 1.05 mm. If the cell thickness is less than 0.2005 mm, it tends to be difficult for the cell to function as a cell in the solid electrochemical device 100. If the cell thickness is more than 1.05 mm, it tends to be difficult to reduce the size of the solid electrochemical device 100. A lower limit for the cell thickness can be 0.25 mm, 0.3 mm, or 0.35 mm. An upper limit for the cell thickness can be 0.9 mm, 0.8 mm, or 0.7 mm. The cell thickness can be 0.3 mm to 0.8 mm, or 0.35 mm to 0.7 mm.

[0081] In the solid electrochemical device 100, the thickness of the cell can be determined by calculating the sum of the “thickness of the solid electrolyte 11”, the “thickness of the first electrode 12” and the “thickness of the second electrode 13”. <<Verfahren für ein Herstellen der festen elektrochemischen Vorrichtung> >

[0082] The solid electrochemical device 100 according to the present embodiment can be produced by a suitable or corresponding use of a known method. EXAMPLE

[0083] The method for manufacturing the solid electrochemical device 100 will be specifically described based on an example in the present disclosure, however, the present invention is not limited or restricted to the following example. <<Herstellung der festen elektrochemischen Vorrichtung> >

[0084] To prepare fixed electrochemical devices for samples 1 to 12, 101, and 102, the following were prepared: first interconnects, first current collectors, first electrodes, solid electrolytes, second electrodes, second current collectors, and second interconnects, all listed in Table 1. The dimensions of the flat surface of the first interconnects, first current collectors, first electrodes, solid electrolytes, second electrodes, second current collectors, and second interconnects were all 100 mm × 100 mm.The description "FeCr" in the "Composition" column of the "First Interconnector" column in Table 1 means that the first interconnect of the sample is made of an iron-chromium (FeCr) alloy. The description "NiCo" in the "Composition" column of the "First Current Collector" column in Table 1 means that the first current collector of the sample is made of a metallic porous nickel-cobalt (NiCo) body. The description "LSC" in the "Composition" column of the "First Electrode" column in Table 1 means that the first electrode of the sample is made of LSC (lanthanum (La)-strontium (Sr)-cobalt (Co) oxide). The description "YSZ" in the "Composition" column of the "Solid Electrolyte" column in Table 1 means that the solid electrolyte of the sample is made of yttrium-stabilized zirconium (YSZ).The description "Ni + YSZ" in the "Composition" column of the "Second Electrode" column in Table 1 means that the second electrode of the sample is formed from a composite of YSZ and nickel oxides (Ni₂O). The description "Ni" in the "Composition" column of the "Second Current Collector" column in Table 1 means that the second current collector of the sample is formed from a metallic porous nickel body. The description "FeCr" in the "Composition" column of the "Second Interconnector" column in Table 1 means that the second interconnect of the sample is formed from an iron-chromium (FeCr) alloy.

[0085] Next, the solid electrochemical devices or electrochemical solid-state devices for samples 1 to 12, 101 and 102 were manufactured using a known method, except that the first interconnects listed in Table 1, the first current collectors listed in Table 1, the first electrodes listed in Table 1, the solid electrolytes listed in Table 1, the second electrodes listed in Table 1, the second current collectors listed in Table 1, and the second interconnects listed in Table 1 were combined. [Table 1] <<Beurteilung der Merkmale der festen elektrochemischen Vorrichtung> ><Dicke der Zelle>

[0086] The thickness of the cell of the solid electrochemical device for each sample was measured using the method described in embodiment 1. The results obtained are listed in the "Thickness [mm]" column of the "Cell" column in Table 1. <Dicke der festen elektrochemischen Vorrichtung>

[0087] For the solid electrochemical device of each sample, the thickness of the solid electrochemical device was determined using the method described in embodiment 1. The results obtained are listed in the column "Thickness of solid electrochemical device [mm]" in Table 1. If the "Thickness of solid electrochemical device [mm]" is 2.10 mm or less, this indicates that the solid electrochemical device is compact. Table 1 shows that the solid electrochemical devices for sample 1 through sample 12 and sample 102 are significantly more compact than the solid electrochemical device for sample 101. <druckverlust>

[0088] For the fixed electrochemical apparatus of each sample, the degree of pressure drop of the fixed electrochemical apparatus was determined for each of samples 1 through 12 and sample 101 by the following procedure, where the degree of pressure drop of the fixed electrochemical apparatus for sample 102 was set to 100. That is, atmospheric gas or gaseous air was allowed to flow from a central section of the first current collector at a rate of 0.5 l / min, and the pressure at the central section, as the atmospheric gas or gaseous air flowed radially from the central section, was measured using a testo512 differential pressure gauge, manufactured by Testo KK. The degree of pressure drop corresponding to a pressure for sample 102 was set to 100, and the degree of pressure drop corresponding to a pressure for each sample was determined as a relative value.The results obtained are listed in the "Pressure Loss" column of Table 1. If the degree of pressure loss of the solid electrochemical device for sample 102 is set to 100, then a pressure loss of less than 100 for each sample indicates that the solid electrochemical device performs excellently in suppressing pressure loss. Table 1 shows that the solid electrochemical devices for samples 1 through 12 are significantly better than the solid electrochemical device for sample 102 in terms of pressure loss suppression. <Maximale Leistungsdichte und maximale Leistungsdichte pro Einheitsdicke der festen elektrochemischen Vorrichtung>

[0089] A maximum power density was determined by setting an operating temperature of 750 °C, a hydrogen fuel gas flow rate of 0.2 l / min to one anode of the fixed electrochemical apparatus for each sample, and an air flow rate of 0.3 l / min to one cathode. In the fixed electrochemical apparatus for each sample, the first current collector was used as the cathode and the second current collector as the anode. The results obtained are shown in the column "Maximum power density [mW / cm²]". 2 ]" listed in Table 1.

[0090] Next, a maximum power density per unit thickness was determined for each sample's solid electrochemical device by dividing the maximum power density of the device by its thickness. The results are shown in the column "Maximum power density per unit thickness [mW / cm²]". 2 / mm]" listed in Table 1.

[0091] This means that if the maximum power density is "100 mW / cm²", then... 2 or more" and the maximum power density per unit thickness "50 mW / cm²" 2 / mm or more" means that the solid electrochemical device is excellent in terms of power density.

[0092] When comparing the power densities of the solid electrochemical devices for samples 1 to 12 and sample 102, which can be miniaturized, the solid electrochemical devices for samples 1 to 12 exhibit a significantly higher maximum power density and a significantly higher maximum power density per unit thickness than the solid electrochemical device for sample 102. That is, the solid electrochemical devices for samples 1 to 12 can exhibit a significantly superior power density compared to the solid electrochemical device for sample 102.

[0093] As described above, the solid electrochemical devices for sample 1 to sample 12 were found to be compact, excellent in "pressure loss suppression" and excellent in "power density".

[0094] Although the first current collector is used as an air electrode current collector in all samples, it is considered that the same effects can be obtained even if the first current collector is used as a fuel electrode current collector instead of the air electrode current collector. This is because it is common technical knowledge among those skilled in the art that if the power density is improved by improving the diffusivity of air entering from one side of the fixed electrochemical device on which the air electrode is located, the power density is also improved by improving the diffusivity of hydrogen gas entering from the same side of the fixed electrochemical device on which the fuel electrode is located.

[0095] Although the embodiments and examples of the present invention have been described above, the original or main intention is to combine the configurations of the embodiments and examples described above in a suitable or appropriate manner.

[0096] It should be understood that the embodiments disclosed herein are illustrative in all aspects and should not be considered or perceived as limiting. The scope of the present invention is defined more by the scope of the claims than by the above description, and it is intended to include all modifications or variations within the meaning and scope of equivalence of the claims. REFERENCE MARK LIST 11 solid electrolyte 111 first main surface 112 second main surface 12 first electrode 121 third main surface 122 fourth main surface 13 second electrode 131 eighth main surface 132 ninth main surface 20 first power collector 201 fifth main surface 202 sixth main surface 203 first region 21 first passage hole 211 first latitude 212 second latitude 30 second power collector 301 tenth main surface 302 eleventh main surface 31 second passage hole 311 third latitude 40 first interconnector 401 seventh main surface 50 second interconnector 501 twelfth main surface 100 fixed electrochemical devices or electrochemical solid or solid-state devices 101 thirteenth main surface 102 fourteenth main surface QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] JP 2023-001579

[0001] WO 2021 / 210231

[0003] WO 2021 / 153406 [0041, 0057, 0062, 0077]< / druckverlust> < / zelle> < / festelektrolyt>

Claims

[1] Fixed electrochemical apparatus comprising: a solid electrolyte which has a first main surface and a second main surface which is a surface opposite the first main surface; a first electrode having a third principal surface and a fourth principal surface which is a surface opposite the third principal surface, wherein the first electrode is arranged such that the third principal surface is directed towards the first principal surface; a first current collector having a fifth main surface and a sixth main surface, which is a surface opposite the fifth main surface, wherein the first current collector is arranged such that the fifth main surface is directed towards the fourth main surface; and a first interconnector having a seventh main surface, wherein the first interconnector is configured such that the seventh main surface is directed towards the sixth main surface, where the seventh main surface of the first interconnector is a flat surface, wherein the first current collector is formed from a first metallic porous body which has a three-dimensional network structure, and wherein a plurality of first penetration holes is formed in the fifth main surface, wherein the plurality of first penetration holes extends along a first direction from the fifth main surface towards the sixth main surface. [2] Fixed electrochemical device according to claim 1, wherein, in a top view of the fifth principal surface, the first penetration holes each have a first width along a second direction orthogonal to the first direction and each have a second width along a third direction orthogonal to the first and second directions, and where the average value of the first width and the second width is 2 mm to 20 mm. [3] Fixed electrochemical device according to claim 1 or claim 2, wherein a first opening ratio, which is a percentage of a total area of ​​the first through-holes relative to an area of ​​the fifth main surface, is 2.0% to 35%. [4] Fixed electrochemical device according to any one of claims 1 to 3, wherein, in each of nine first regions defined by a uniform subdivision of the fifth main surface into nine parts based on an area criterion, a second opening ratio, which is a percentage of a total area of ​​the first through-holes in each of the first regions relative to an area of ​​each of the first regions, is 2.0% to 35%. [5] Fixed electrochemical device according to any one of claims 1 to 4, wherein the first metallic porous body is a metallic porous nickel-cobalt body. [6] Fixed electrochemical device according to any one of claims 1 to 4, wherein the first metallic porous body is a metallic porous nickel body. [7] Fixed electrochemical device according to any one of claims 1 to 4, wherein the first metallic porous body is a metallic porous nickel-tin body. [8] Fixed electrochemical device according to any one of claims 1 to 7, further comprising: a second electrode having an eighth main surface and a ninth main surface, which is a surface opposite the eighth main surface, wherein the second electrode is provided such that the eighth main surface is directed towards the second main surface; a second current collector having a tenth main surface and an eleventh main surface, which is a surface opposite the tenth main surface, wherein the second current collector is arranged such that the tenth main surface is directed towards the ninth main surface; and a second interconnector having a twelfth main surface, wherein the second interconnector is configured such that the twelfth main surface is directed towards the eleventh main surface, where the twelfth main surface of the second interconnector is a flat surface, wherein the second current collector is formed from a second metallic porous body which has a three-dimensional network structure, and wherein a plurality of second penetration holes is formed in the tenth main surface, wherein the plurality of second penetration holes extends along a fourth direction from the tenth main surface towards the eleventh main surface. [9] Fixed electrochemical device according to claim 8, wherein, in a top view of the tenth main surface, the second passage holes each have a third width along a fifth direction orthogonal to the fourth direction and each have a fourth width along a sixth direction orthogonal to the fourth and fifth directions, and where an average value for the third width and the fourth width is 2 mm to 20 mm. [10] Fixed electrochemical device according to claim 8 or claim 9, wherein a third opening ratio, which is a percentage of a total area of ​​the second through-holes relative to an area of ​​the tenth main surface, is 2.0% to 35%. [11] Fixed electrochemical device according to any one of claims 8 to 10, wherein, in each of nine second regions defined by a uniform subdivision of the tenth main surface into nine parts based on an area criterion, a fourth opening ratio, which is a percentage of a total area of ​​the second passage holes in each of the second regions relative to an area of ​​each of the second regions, is 2.0% to 35%. [12] Fixed electrochemical device according to any one of claims 8 to 11, wherein the second metallic porous body is a metallic porous nickel-cobalt body. [13] Fixed electrochemical device according to any one of claims 8 to 11, wherein the second metallic porous body is a metallic porous nickel body. [14] Fixed electrochemical device according to any one of claims 8 to 11, wherein the second metallic porous body is a metallic porous nickel-tin body.

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