JP6298908B1 - Functional ceramic body - Google Patents

Abstract

A functional ceramic body in which diffusion of a setter component is suppressed is provided. A functional ceramic body 100 includes a first layer 101 made of ceramic and / or metal, and a second layer 102 formed on the first layer 101 and made of ceramic and / or metal. Prepare. The second layer 102 has a first protrusion 102 a that protrudes toward the opposite side of the first layer 101. [Selection] Figure 2

Description

  The technology disclosed herein relates to a functional ceramic body.

  Conventionally, a functional ceramic element utilizing the electrical, thermal, chemical, magnetic, and optical characteristics of ceramics is known (see Patent Document 1). Examples of functional ceramic elements include fuel cells, solar cells, piezoelectric / electrostrictive elements, NOx sensors, PM (Particulate Matter) sensors, PN (Particulate Number) sensors, ceramic filters, catalyst carriers, light emitting diodes, and heating elements. Etc.

  Such a functional ceramic element includes a laminated body in which a first layer composed of ceramics and / or metal and a second layer composed of ceramics and / or metal are laminated.

JP-A-10-289808

  By the way, in the manufacturing process of the functional ceramic element, when the molded body of the laminated body described above is fired, if the molded body is fired in a state where it is in contact with the setter, the setter component diffuses into the laminated body and the functionality is increased. There is a possibility of adversely affecting the performance of the ceramic element.

  Therefore, it is necessary to lay the ceramic powder as a spread powder on the surface of the setter, or to grind the surface of the laminate after firing.

  This invention is made | formed in view of the above-mentioned situation, and it aims at providing the functional ceramic body by which the spreading | diffusion of the setter component was suppressed.

  The functional ceramic body includes a first layer made of ceramic and / or metal, and a second layer made of ceramic and / or metal formed on the first layer. The second layer has a first protrusion that protrudes toward the opposite side of the first layer.

  ADVANTAGE OF THE INVENTION According to this invention, the functional ceramic body by which the spreading | diffusion of the setter component was suppressed can be provided.

Plan view of functional ceramic body AA sectional view of FIG. Sectional drawing for demonstrating the structure of the modification 1 of a functional ceramic body Sectional drawing for demonstrating the structure of the modification 2 of a functional ceramic body Sectional drawing for demonstrating the structure of the modification 3 of a functional ceramic body Sectional drawing for demonstrating the structure of the modification 4 of a functional ceramic body Sectional drawing for demonstrating the structure of the modification 5 of a functional ceramic body Sectional drawing for demonstrating the structure of the modification 6 of a functional ceramic body Sectional drawing which shows the structure of the electric power generation part of the fuel cell to which the functional ceramic body was applied Schematic diagram for explaining a method of manufacturing a power generation part of a fuel cell to which a functional ceramic body is applied Sectional drawing which shows the structure of the interconnector part of the fuel cell to which the functional ceramic body is applied Schematic diagram for explaining a method of manufacturing an interconnector part of a fuel cell to which a functional ceramic body is applied Sectional view showing the configuration of a horizontal stripe fuel cell to which a functional ceramic body is applied Sectional view showing the configuration of a horizontal stripe fuel cell to which a functional ceramic body is applied Sectional view showing the configuration of a vertical stripe fuel cell to which a functional ceramic body is applied Sample No. in Example Sectional drawing which shows the structure of 1-17 Sample No. in Example Sectional drawing which shows the structure of 1-17 Sample No. in Example Sectional drawing for demonstrating the manufacturing method of 1-17 Sample No. in Example Sectional drawing for demonstrating the manufacturing method of 1-17 Sample No. in Example Sectional drawing which shows the structure of 19-35 Sample No. in Example Sectional drawing which shows the structure of 19-35 Sample No. in Example Sectional drawing for demonstrating the manufacturing method of 19-35 Sample No. in Example Sectional drawing for demonstrating the manufacturing method of 19-35

(Configuration of functional ceramic body 100)
The configuration of the functional ceramic body 100 will be described with reference to the drawings.

  FIG. 1 is a plan view of the functional ceramic body 100. FIG. 2 is a cross-sectional view taken along the line AA of FIG. In FIG. 1, the surface 102S of the second layer 102 is viewed in plan. In FIG. 2, a cross section parallel to the thickness direction of the second layer 102 is shown.

  The functional ceramic body 100 can be used for a functional ceramic element using at least one characteristic among the electrical, thermal, chemical, magnetic, and optical characteristics of ceramics. Examples of functional ceramic elements include fuel cells, solar cells, piezoelectric / electrostrictive elements, NOx sensors, PM (Particulate Matter) sensors, PN (Particulate Number) sensors, ceramic filters, catalyst carriers, light emitting diodes, and heating elements. Etc. The functional ceramic body 100 itself may function as a functional ceramic element, or may constitute a part of the functional ceramic element.

  The functional ceramic body 100 includes a first layer 101 and a second layer 102.

1. First layer 101
The main body 101 is formed in a plate shape or a layer shape. The first layer 101 is made of ceramics and / or metal. When the first layer 101 is made of ceramic, as the ceramic constituting the first layer 101, both structural ceramics and functional ceramics can be used. The ceramics constituting the first layer 101 can be selected according to the function given to the first layer 101. Specific examples of the ceramic constituting the first layer 101 include, for example, oxide ceramics (alumina, zirconia, barium titanate, lead zirconate titanate, ferrite, mullite, steatite, forsterite, cordierite, etc.) Nitride ceramics (aluminum nitride, silicon nitride, etc.), carbides (silicon carbide, etc.) and the like can be mentioned, but the invention is not limited thereto.

  When the first layer 101 is made of a metal, the metal constituting the first layer 101 is used for a member (for example, an electrode layer, a current collecting layer, and a terminal) for electrical connection in the functional ceramic element. Well-known materials can be used. Specific examples of the metal constituting the first layer 101 include gold, silver, platinum, palladium, nickel, iron, cobalt, lanthanum, strontium, manganese, and an alloy containing at least one element selected from these. Although it can be used, it is not limited to this.

  When the first layer 101 is made of ceramic and metal (that is, so-called cermet), the cermet constituting the first layer 101 is made of a mixture of the above-described structural ceramic or functional ceramic and the above-described metal. can do.

  The planar shape and planar size of the first layer 101 are not particularly limited, and can be set in consideration of the shape of the functional ceramic element, the function and strength of the first layer 101, and the like. In the present embodiment, the planar shape of the first layer 101 is a square, but may be a rectangle, a circle, an ellipse, a triangle, a pentagon or more polygon, and other shapes.

  The thickness of the first layer 101 is not particularly limited, and can be set in consideration of the function and strength of the first layer 101.

  The porosity of the first layer 101 is not particularly limited, and can be set in consideration of the function and strength of the first layer 101. The first layer 101 may be porous or dense.

2. Second layer 102
The second layer 102 is formed on the first layer 101. The second layer 102 is made of ceramics and / or metal. The second layer 102 is formed by firing a formed body made of a ceramic material and / or a metal material. The molded body can be produced by press-molding the material powder, applying a slurry or paste containing the material powder, or tape-molding the slurry containing the material powder, but is not limited thereto. It is not a thing.

  In the case where the second layer 102 is made of ceramic, as the ceramic constituting the second layer 102, both structural ceramics and functional ceramics can be used. The ceramic constituting the second layer 102 can be selected according to the function given to the second layer 102 in the functional ceramic element. The ceramic constituting the second layer 102 may be the same material as the ceramic constituting the first layer 101 or may be a different material. A specific example of the ceramic constituting the second layer 102 is the same as the specific example of the ceramic constituting the first layer 101 described above.

  When the second layer 102 is made of a metal, the metal constituting the second layer 102 may be the same as or different from the metal constituting the first layer 101. A specific example of the metal constituting the second layer 102 is the same as the specific example of the metal constituting the first layer 101 described above.

  When the second layer 102 is made of ceramics and metal (that is, so-called cermet), the cermet constituting the second layer 102 may be the same as or different from the cermet constituting the first layer 101. It may be. A specific example of the cermet constituting the second layer 102 is the same as the specific example of the cermet constituting the first layer 101 described above.

  The planar shape and planar size of the second layer 102 are not particularly limited, and can be set in consideration of the shape of the functional ceramic element, the function and strength of the second layer 102, and the like. In the present embodiment, the planar shape of the second layer 102 is a square, but may be a rectangle, a circle, an ellipse, a triangle, a pentagon or more polygon, and other shapes. In the present embodiment, the planar shape of the second layer 102 is the same as the planar shape of the first layer 101, but may be different from the planar shape of the first layer 101. In the present embodiment, the planar size of the second layer 102 is slightly smaller than the planar size of the first layer 101, but may be the same as the planar size of the first layer 101 or the first layer 101. It may be larger than the plane size.

  The thickness of the second layer 102 is not particularly limited, and can be set in consideration of the function and strength of the second layer 102.

  The porosity of the second layer 102 is not particularly limited, and can be set in consideration of the function and strength of the second layer 102. The second layer 102 may be porous or dense.

  The second layer 102 has a main body portion 102a and a convex portion 102b.

  The main body 102a is formed in a plate shape or a layer shape. The main body portion 102 a is a portion mainly responsible for the function of the second layer 102 in the second layer 102. For example, when the second layer 102 functions as an electrode layer, current flows mainly in the main body 102a.

  The convex part 102b protrudes from the main body part 102a toward the side opposite to the first layer 101. The convex part 102b is formed on the surface 102S of the main body part 102a. The convex part 102b can be formed by, for example, partially increasing the number of times of printing when forming the molded body of the second layer 102 using a screen printing method.

  Thus, by forming the convex part 102b on the surface 102S of the main body part 102a, when the molded body of the functional ceramic body 100 is fired, the molded part of the second layer 102 faces downward and the convex part 102b is used as a setter. When contacted, the main body 102a can be separated from the setter. Therefore, it is possible to suppress the setter component (hereinafter referred to as “setter component”) from diffusing into the main body 102a. Further, even if the setter component diffuses into the convex portion 102b, the setter component can be concentrated inside the convex portion 102b. As a result, it is possible to suppress the setter component from adversely affecting the function of the main body 102a. In addition, although a setter component is based on the constituent material of a setter, Al element, Y element, Zr element etc. are mentioned, for example.

  Furthermore, by causing the projection 102b to contact the setter and separating the main body 102a from the setter, the constituent component of the main body 102a (hereinafter referred to as “second layer component”) diffuses into the setter and enters the main body 102a. Generation | occurrence | production of a composition shift can be suppressed.

  As shown in FIG. 1, the convex part 102b is formed so that it may extend linearly along a predetermined direction. However, the planar shape of the convex portion 102b is not limited to this, and may be, for example, a curved shape, a wavy shape, a circular shape, or a polygonal shape.

  Further, as shown in FIG. 1, the convex portion 102 b is disposed at a position shifted from the center of the second layer 102. However, the position of the convex portion 102 b is not limited to this, and may be arranged at the center of the second layer 102 or at one end portion of the second layer 102. In particular, when the convex portion 102b is disposed on the outer edge of the second layer 102, the setter component can be prevented from diffusing into the central portion of the main body portion 102a, and thus adversely affects the function of the main body portion 102a. Can be further suppressed.

  The cross-sectional shape of the protrusion 102b is not particularly limited, but is preferably tapered toward the tip as shown in FIG. Thereby, when baking in the state which made the convex part 102b contact | abut to a setter, the area | region which contact | abuts a setter among the convex parts 102b can be narrowed. Therefore, it is possible to further suppress the setter component from diffusing into the convex portion 102b as compared with the case where the tip of the convex portion 102b is flat.

  The convex portion 102b is different from minute irregularities (so-called texture) formed on the surface 102S of the second layer 102. For example, when the second layer 102 is formed by using the screen printing method, unevenness of about 1 μm to 3 μm may be formed on the surface 102S. However, the height H of the convex portion 102b is smaller than those minute unevenness. Is also big.

  Here, the ratio (W / H) of the width W to the height H of the protrusion 102b is not particularly limited, but can be 0.5 or more. The ratio of the width W to the height H of the convex portion 102b is preferably 1 or more. Thereby, when baking in the state which made the convex part 102b contact | abut to a setter, it can suppress that a crack arises in the convex part 102b.

  The height H of the convex portion 102b is not particularly limited, but can be, for example, 5 μm or more and 100 μm or less. The height H of the convex portion is preferably 80 μm or less. Thereby, when baking with the convex part 102b contact | abutted to the setter, it can suppress more that a crack arises in the convex part 102b. Further, the height H of the convex portion is preferably 8 μm or more. Thereby, when baking with the convex part 102b contact | abutted to the setter, it can suppress more that a setter component diffuses to the main-body part 102a.

  The width H of the convex portion 102 b is not particularly limited, and can be set as appropriate according to the width A of the second layer 102. The width W of the convex portion 102 b is preferably less than 20% of the width A of the second layer 102. Thereby, since the area which the convex part 102b occupies in the surface 102S of the main-body part 102a is suppressed, the functionality of the main-body part 102a is securable. For example, as will be described later, when the second layer 102 corresponds to the electrolyte layer of the fuel cell, the oxygen ion conductivity of the electrolyte layer is ensured, so that the initial output of the fuel cell can be improved.

(Modification of functional ceramic body 100)
1. Modification 1
Next, Modification 1 of the functional ceramic body 100 will be described. FIG. 3 is a cross-sectional view of a functional ceramic body 100a according to the first modification.

  In the functional ceramic body 100a according to the first modification, the first layer 101 has a main body portion 101a and a convex portion 101b. The main body 101a is formed in a plate shape or a layer shape. The convex part 101b is arrange | positioned on the main-body part 101a. The protrusion 101b protrudes toward the second layer 102 side. The convex portion 101 b of the first layer 101 is located inside the convex portion 102 c of the second layer 102.

  The convex portion 101b can be formed by, for example, partially increasing the number of times of printing when the molded body of the main body portion 101a is formed using a screen printing method.

  By forming such protrusions 101b in the first layer 101 in advance, the protrusions 102c of the second layer 102 can be naturally formed following the shape of the protrusions 101b of the first layer 101. Therefore, for example, when the formed body of the second layer 102 is formed by a screen printing method, the convex portion 102c can be formed without partially increasing the number of times of printing.

2. Modification 2
FIG. 4 is a cross-sectional view of a functional ceramic body 100b according to Modification 2. In the functional ceramic body 100 b according to the second modification, the width A of the second layer 102 is about ¼ of the width B of the first layer 101. Thus, when the second layer 102 is considerably smaller than the first layer 101, one end portion of the first layer 101 comes into contact with the setter when firing with the convex portion 102d in contact with the setter. It will be. Therefore, the diffusion of the setter component into the main body 102a of the second layer 102 can be further suppressed, and the diffusion of the second layer component into the setter can be further suppressed.

3. Modification 3
FIG. 5 is a plan view of a functional ceramic body 100c according to Modification 3. Similar to the functional ceramic body 100, the functional ceramic body 100 c includes a first layer 101 and a second layer 102. However, the second layer 102 has a convex portion 102e having a rectangular annular shape in plan view. The convex part 102e is formed in a continuous annular shape, and is rectangular as a whole.

  The convex portion 102e forms a closed region in plan view. The closed region is a region surrounded by the convex portion 102e in the plan view of the second layer 102. In this way, by forming a closed region with the convex portion 102e, the convex portion 102e functions as a hill when firing with the convex portion 102e in contact with the setter. Can be improved.

  In the third modification, the convex portion 102 e is disposed along the outer edge of the second layer 102. Therefore, the stability at the time of baking can be improved more. However, the convex part 102e may be arrange | positioned inside the outer edge of the 2nd layer 102. FIG.

4). Modification 4
FIG. 6 is a plan view of a functional ceramic body 100d according to Modification 4. Similar to the functional ceramic body 100, the functional ceramic body 100 d includes a first layer 101 and a second layer 102. However, the 2nd layer 102 has the convex part 102f whose planar shape is C-shaped. The convex portion 102f is formed in an intermittent annular shape. Thus, the convex part of the 2nd layer 102 does not need to be connected in at least one part.

5. Modification 5
FIG. 7 is a plan view of a functional ceramic body 100e according to Modification 5. Similar to the functional ceramic body 100, the functional ceramic body 100 e includes a first layer 101 and a second layer 102. However, the 2nd layer 102 has the convex part 102g whose planar shape is a lattice form. Thus, the convex part of the second layer 102 may be partially provided with an opening.

6). Modification 6
FIG. 8 is a plan view of a functional ceramic body 100f according to Modification 6. Similar to the functional ceramic body 100, the functional ceramic body 100 f includes a first layer 101 and a second layer 102. However, the 2nd layer 102 has the convex part 102h containing several dotted | punctate convex parts. The dot-like convex portions are separated from each other. Thus, the convex part of the 2nd layer 102 may be an aggregate of a plurality of convex parts.

(Application example of fuel cell to power generation section)
The case where the functional ceramic body 100 described above is applied to a power generation unit of a fuel cell will be described with reference to the drawings. In the power generation unit 10 described below, the “solid electrolyte layer 12” corresponds to the “first layer 101”, and the “barrier layer 13” corresponds to the “second layer 102”.

  FIG. 9 is a cross-sectional view of the power generation unit 10. The power generation unit 10 includes a fuel electrode 11, a solid electrolyte layer 12, a barrier layer 13, and an air electrode 14. The power generation unit 10 can be applied to various fuel cells such as a horizontal stripe type, a vertical stripe type, a fuel electrode support type, an electrolyte flat plate type, and a cylindrical type.

1. Fuel electrode 11
The anode 11 includes an anode current collecting layer 11a and an anode active layer 11b.

The anode current collecting layer 11a has a porosity for allowing the fuel gas to permeate to the anode active layer 11b and an electron conductivity for collecting electricity. The anode current collecting layer 11a can be composed of a transition metal and a ceramic material. Ni (nickel) is preferred as the transition metal. At least a part of Ni (nickel) may be in the form of NiO (nickel oxide). Examples of the ceramic material include 8YSZ (yttria stabilized zirconia), Y ₂ O ₃ (yttria), CSZ (calcium zirconate), and the like.

  The porosity of the anode current collecting layer 11a is not particularly limited, but can be 25% to 50%. The conductivity of the anode current collecting layer 11a is not particularly limited, but can be 300 S / cm or more. The thickness of the anode current collecting layer 11a is not particularly limited, but when the anode current collecting layer 11a is used as a support substrate, it can be 2 mm to 10 mm, and the anode current collecting layer 11a is formed on the support substrate. In some cases, the thickness may be 50 μm to 500 μm.

  The anode active layer 11 b is disposed between the anode current collecting layer 11 a and the solid electrolyte layer 12. The anode active layer 11b has porosity, electron conductivity, and oxygen ion conductivity. The anode active layer 11b can be made of a transition metal and a ceramic material. Ni (nickel) is preferred as the transition metal. At least a part of Ni (nickel) may be in the form of NiO (nickel oxide). Examples of the ceramic material include 8YSZ and GDC (gadolinium doped ceria).

  The porosity of the anode active layer 11b is not particularly limited, but can be 25% to 50%. The thickness of the fuel electrode active layer 11b is not particularly limited, but can be 1 μm to 30 μm.

2. Solid electrolyte layer 12
The solid electrolyte layer 12 is disposed between the fuel electrode 11 and the air electrode 14. The solid electrolyte layer 12 is disposed on the fuel electrode 11. The solid electrolyte layer 4 has an ion conductivity for conducting oxygen ions from the air electrode 14 to the fuel electrode 11 and a leak between the fuel gas supplied to the fuel electrode 11 and the oxygen-containing gas supplied to the air electrode 14. And denseness to prevent. The solid electrolyte layer 12 can be composed of a dense ceramic material. Examples of the ceramic material include 3YSZ, 8YSZ, ScSZ (scandia stabilized zirconia) and the like.

  The porosity of the solid electrolyte layer can be 20% or less, and preferably 10% or less. The thickness of the solid electrolyte layer 12 is not particularly limited, but can be 1 μm to 50 μm.

3. Barrier layer 13
The barrier layer 13 is disposed between the solid electrolyte layer 12 and the air electrode 14. The barrier layer 13 is disposed on the solid electrolyte layer 12. The barrier layer 13 suppresses diffusion of elements from the air electrode 14 to the solid electrolyte layer 12. The barrier layer 13 is made of an oxide having an element diffusion suppressing function. Examples of such an oxide include GDC and SDC (samarium-doped ceria).

  The porosity of the barrier layer 13 can be 20% or less, and is preferably 10% or less. The thickness of the reaction preventing film 13 is not particularly limited, but may be 1 μm to 50 μm.

4). The convex part of the barrier layer 13 The barrier layer 13 has a first convex part 131 and a second convex part 132.

  The first protrusion 131 protrudes toward the opposite side of the fuel electrode 11. The first protrusion 131 is formed on the surface 13S of the barrier layer 13 opposite to the solid electrolyte layer 12. By forming the first protrusion 131 on the barrier layer 13, it becomes difficult for the barrier layer 13 to come into contact with the setter in the firing step of the barrier layer 13 to be described later, so that the setter component can be prevented from diffusing into the solid electrolyte layer 12. At the same time, it is possible to prevent the electrolyte component from diffusing into the setter and causing a composition shift in the solid electrolyte layer 12.

  The position of the first protrusion 131 on the surface 13S is not particularly limited, but is preferably separated from the center of the surface 13S. The 1st convex part 131 is formed in the one end part of the surface 13S. This makes it difficult for the central portion of the barrier layer 13 to come into contact with the setter in the firing step of the barrier layer 13, so that it is easy to suppress the setter component from diffusing into the central portion of the solid electrolyte layer 12 that easily affects power generation performance. Become.

  When the surface 13S of the barrier layer 13 is viewed in plan, the first protrusion 131 is formed in a strip shape along one end of the surface 13S. However, the planar shape of the first convex portion 131 is not particularly limited, and may be, for example, a circular shape, a rectangular shape, a wavy shape, or the like.

  The first convex portion 131 is different from minute irregularities (so-called texture) formed on the surface 13S. For example, when the barrier layer 13 is formed by a screen printing method, unevenness of about 1 μm to 3 μm is formed on the surface 13S, but the height H1 of the first protrusion 131 is larger than the unevenness of the surface 13S.

  The second protrusion 132 protrudes toward the opposite side of the fuel electrode 11. The second convex portion 132 is formed on the surface 13S of the barrier layer 13. By forming not only the first convex portion 131 but also the second convex portion 132 on the barrier layer 13, the region where the barrier layer 13 contacts the setter in the firing process of the barrier layer 13 can be made narrower, so that the setter component is a solid electrolyte. Diffusion to the layer 12 can be further suppressed. As a result, it can suppress more that the electric power generation performance of the electric power generation part 10 falls.

  The position of the second convex portion 132 on the surface 13S is not particularly limited, but is preferably away from the center of the surface 13S, and more preferably away from the first convex portion 131. Thereby, in the baking process of the barrier layer 13, since the center part of the barrier layer 13 becomes more difficult to contact with a setter, it can further suppress that the electric power generation performance of the electric power generation part 10 falls.

  When the surface 13S of the barrier layer 13 is viewed in plan, the second convex portion 132 is formed in a strip shape along the other end of the surface 13S. The second convex portion 132 is disposed on the opposite side to the first convex portion 131. However, the planar shape of the second convex portion 132 is not particularly limited, and may be, for example, a circular shape, a rectangular shape, a wavy shape, or the like. The 2nd convex part 132 is different from the micro unevenness | corrugation formed in the surface 13S.

  Here, the ratio (W1 / H1) of the width W1 to the height H1 of the first protrusion 131 is preferably 1 or more. Similarly, the ratio (W2 / H2) of the width W2 to the height H2 of the second convex portion 132 is not particularly limited, but is preferably 1 or more. Thereby, it can suppress that a crack arises in each convex part 131,132 at the time of baking.

  Further, the heights H1 and H2 of the convex portions 131 and 132 are preferably 80 μm or less. Thereby, it can suppress more that a crack arises in each convex part 131,132 at the time of baking. The heights H1 and H2 of the convex portions 131 and 132 are preferably 8 μm or more. Thereby, it can suppress more that a setter component diffuses to the inside of the barrier layer 13 at the time of baking.

  Further, the width W1 of the first protrusion 131 is preferably less than 20% of the width A1 of the barrier layer 13. Similarly, the width W2 of the second protrusion 132 is preferably less than 20% of the width A1 of the barrier layer 13. Thereby, the functionality (oxygen ion conductivity) of the barrier layer 13 can be ensured.

  The heights H1 and H2 of the convex portions 131 and 132 may be different from each other, and the widths W1 and W2 of the convex portions 131 and 132 may be different from each other.

  In this embodiment, each convex part 131,132 is coat | covered with the air electrode 14, However, It is not restricted to this. At least a part of each of the convex portions 131 and 132 may be exposed from the air electrode 14.

5. Air electrode 14
The air electrode 14 includes an air electrode active layer 14a and an air electrode current collecting layer 14b.

The air electrode active layer 14 a is disposed on the barrier layer 13. The air electrode active layer 14a is made of a porous material having mixed conductivity. The air electrode active layer 14a includes, for example, (La, Sr) (Co, Fe) O ₃ (LSCF, lanthanum strontium cobalt ferrite), (La, Sr) FeO ₃ (LSF, lanthanum strontium ferrite), La (Ni, Fe) ) O ₃ (LNF, lanthanum nickel ferrite), (La, Sr) CoO ₃ (LSC, lanthanum strontium cobaltite), and the like.

  The porosity of the air electrode active layer 14a can be 20% or more, and preferably 30% or more. The thickness of the air electrode active layer 14a is not particularly limited, but can be 10 to 100 μm.

  The air electrode current collecting layer 14b is disposed on the air electrode active layer 14a. The air electrode current collecting layer 14b is made of a porous material having electronic conductivity. The air electrode current collecting layer 14b can be made of, for example, LSCF, LSC, Ag (silver), Ag—Pd (silver palladium alloy), or the like. The thickness of the air electrode current collecting layer 14b is not particularly limited, but may be 50 μm to 500 μm.

(Manufacturing method of the power generation unit 10)
Next, an example of a method for manufacturing the power generation unit 10 will be described.

  First, a molded body of the anode current collecting layer 11a is formed by molding a powder of the anode current collecting layer material by a die press molding method. Next, the anode active layer material is formed into a paste and screen-printed on the anode current collecting layer 11a to form the anode active layer 11b molded body.

  Next, the solid electrolyte material is made into a paste and screen-printed on the molded body of the fuel electrode active layer 11b to form the molded body of the solid electrolyte layer 12.

  Next, the barrier layer material is formed into a paste and screen-printed on the solid electrolyte layer 12 compact to form the barrier layer 13 compact. At this time, the molded body of the first convex portion 131 and the second convex portion 132 is integrally formed by increasing the number of times of printing at both ends. As a result, a laminated body is formed in which the molded bodies of the fuel electrode current collecting layer 11a, the fuel electrode active layer 11b, the solid electrolyte layer 12 and the barrier layer 13 are laminated.

  Next, as shown in FIG. 10, the laminated body is placed on the setter 30 with the molded body of the barrier layer 13 facing down and fired (1300 to 1600 ° C., 2 to 20 hours). At this time, only the first convex portion 131 and the second convex portion 132 in the barrier layer 13 are in contact with the setter 30, and the central portion of the barrier layer 13 is separated from the setter 30. Therefore, the constituent components of the setter 30 diffuse only in the first convex portion 131 and the second convex portion 132 and do not diffuse in the central portion of the barrier layer 13. In addition, since the barrier layer 13 is thick in the first convex portion 131 and the second convex portion 132, the constituent components of the setter 30 diffused in the first convex portion 131 and the second convex portion 132 are up to the solid electrolyte layer 12. Hard to reach. Therefore, it is possible to suppress the constituent components of the setter 30 from diffusing into the solid electrolyte layer 12. The setter 30 can be a plate member made of alumina, zirconia, yttria, or the like.

  Next, the air electrode material is made into a paste and screen-printed on the barrier layer 13 to form a molded body of the air electrode 14. Next, the molded body of the air electrode 14 is fired (900 to 1100 ° C. for 1 to 20 hours).

(Application example to interconnector part of fuel cell)
The case where the functional ceramic body 100 described above is applied to an interconnector portion of a fuel cell will be described with reference to the drawings. In the interconnector unit 20 described below, the “intermediate layer 21” corresponds to the “first layer 101” and the “interconnector 22” corresponds to the “second layer 102”.

  FIG. 11 is a cross-sectional view of the interconnector portion 20.

  The interconnector unit 20 includes the above-described anode current collecting layer 11a, intermediate layer 21, and interconnector 22. The interconnector unit 20 can be applied to various fuel cells such as a horizontal stripe type, a vertical stripe type, a fuel electrode support type, an electrolyte flat plate type, and a cylindrical type together with the power generation unit 10.

1. Intermediate layer 21
The intermediate layer 21 is disposed on the anode current collecting layer 11a. The intermediate layer 21 is interposed between the anode current collecting layer 11 a and the interconnector 22. The intermediate layer 21 is formed in the entire region between the anode current collecting layer 11 a and the interconnector 22, but may be formed only in a partial region between the anode current collecting layer 11 a and the interconnector 22. Good. The intermediate layer 21 has electronic conductivity and denseness. As a material constituting the intermediate layer 21, Y ₂ O ₃ , GDC, chromite material, or the like can be used.

  The porosity of the intermediate layer 21 can be 20% or less, and is preferably 10% or less. The thickness of the intermediate layer 21 is not particularly limited, but can be 2 μm to 20 μm.

2. Interconnector 22
The interconnector 22 is disposed on the intermediate layer 21. The interconnector 22 has electronic conductivity and denseness. As a material constituting the interconnector 22, for example, LaCrO ₃ (lanthanum chromite), (Sr, La) TiO ₃ (strontium titanate), or the like can be used. The interconnector 22 may contain at least one element selected from Ca, Mg, Al, and Sr.

  The porosity of the interconnector 22 can be 20% or less, and is preferably 10% or less. The thickness of the interconnector 22 is not particularly limited, but can be 10 μm to 100 μm.

3. The convex part of the interconnector 22 The interconnector 22 has a first convex part 221 and a second convex part 222.

  The 1st convex part 221 protrudes toward the opposite side to the fuel electrode current collection part 11a. The 1st convex part 221 is formed in the surface 22S on the opposite side to the fuel electrode current collection layer 11a of the interconnector 22. FIG. By forming the 1st convex part 221 in the interconnector 22, since the interconnector 22 becomes difficult to contact a setter in the baking process of the interconnector 22 mentioned later, while being able to suppress that a setter component diffuses into the interconnector 22. It is possible to suppress the compositional deviation in the interconnector 22 due to the interconnector component diffusing into the setter. As a result, it can suppress that the power generation performance of the electric power generation part 10 falls.

  The position of the first convex portion 221 on the surface 22S is not particularly limited, but is preferably separated from the center of the surface 22S. The 1st convex part 221 is formed in the one end part of the surface 22S. This prevents the center portion of the interconnector 22 from coming into contact with the setter in the firing process of the interconnector 22, thereby suppressing the setter component from diffusing into the center portion of the anode current collecting layer 11 a that easily affects the power generation performance. It becomes easy to do.

  When the surface 22S of the interconnector 22 is viewed in plan, the first convex portion 221 is formed in an elongated shape along one end side of the surface 22S. However, the planar shape of the first convex portion 221 is not particularly limited, and may be, for example, a circular shape, a rectangular shape, a wavy shape, or the like.

  The first convex portion 221 is different from minute irregularities (so-called texture) formed on the surface 22S. For example, when the interconnector 22 is formed by a screen printing method, unevenness of about 1 μm to 3 μm is formed on the surface 22S, but the height H3 of the first protrusion 221 is larger than the unevenness of the surface 22S.

  The 2nd convex part 222 protrudes toward the fuel electrode current collection layer 11a and the other side. The second convex portion 222 is formed on the surface 22S of the interconnector 22. By forming not only the first convex portion 221 but also the second convex portion 222 on the interconnector 22, the area where the interconnector 22 contacts the setter in the firing process of the interconnector 22 can be made narrower. The diffusion to 22 can be further suppressed. As a result, it can suppress more that the electric power generation performance of the electric power generation part 10 falls.

  The position of the second convex portion 222 on the surface 22S is not particularly limited, but is preferably away from the center of the surface 22S, and more preferably away from the first convex portion 221. Thereby, since it becomes difficult to contact the center part of the interconnector 22 with a setter in the baking process of the interconnector 22, it can further suppress that the electric power generation performance of the electric power generation part 10 falls.

  In the present embodiment, when the surface 22S of the interconnector 22 is viewed in plan, the second convex portion 222 is formed in a strip shape along the other end of the surface 22S. The second convex portion 222 is disposed on the opposite side to the first convex portion 221. However, the planar shape of the second convex portion 222 is not particularly limited, and may be, for example, a circular shape, a rectangular shape, a wavy shape, or the like. The second convex portion 222 is different from the minute irregularities formed on the surface 22S.

  Here, the ratio (W3 / H3) of the width W3 to the height H3 of the first convex portion 221 is preferably 1 or more. Similarly, the ratio (W4 / H4) of the width W4 to the height H4 of the second convex portion 222 is not particularly limited, but is preferably 1 or more. Thereby, it can suppress that a crack arises in each convex part 221,222 at the time of baking.

  Further, the heights H3 and H4 of the convex portions 221 and 222 are preferably 80 μm or less. Thereby, it can suppress more that a crack arises in each convex part 221,222 at the time of baking. Further, the heights H1 and H2 of the convex portions 221 and 222 are preferably 8 μm or more. Thereby, it can suppress more that a setter component diffuses to the inside of the interconnector 22 at the time of baking.

  Further, the width W3 of the first convex portion 221 is preferably less than 20% of the width A2 of the interconnector 22. Similarly, the width W2 of the second protrusion 132 is preferably less than 20% of the width A2 of the interconnector 22. Thereby, the functionality (electric conductivity) of the interconnector 22 can be ensured.

  The heights H3 and H4 of the convex portions 221 and 222 may be different from each other. Further, the widths W3 and W4 of the convex portions 221 and 222 may be different from each other.

(Manufacturing method of the interconnector part 20)
Next, an example of the manufacturing method of the interconnector part 20 is demonstrated.

  First, a molded body of the anode current collecting layer 11a is formed by molding a powder of the anode current collecting layer material by a die press molding method.

  Next, the intermediate layer material is formed into a paste and screen-printed on the formed body of the anode current collecting layer 11a, thereby forming the formed body of the intermediate layer 21.

  Next, the interconnector material is formed into a paste and screen-printed on the intermediate body 21 formed body to form the interconnector 22 formed body. At this time, by increasing the number of times of printing at both end portions, the molded body of the first convex portion 221 and the second convex portion 222 is integrally formed. As described above, a laminated body is formed in which the molded bodies of the fuel electrode current collecting layer 11a, the intermediate layer 21, and the interconnector 22 are laminated.

  Next, as shown in FIG. 12, the laminated body is fired (1300 to 1600 ° C., 2 to 20 hours) with the molded body of the interconnector 22 facing downward and placed on the setter 30. At this time, only the first convex portion 221 and the second convex portion 222 of the interconnector 22 are in contact with the setter 30, and the central portion of the interconnector 22 is separated from the setter 30. Therefore, the constituent components of the setter 30 diffuse only in the first convex portion 221 and the second convex portion 222 and do not diffuse in the central portion of the interconnector 22. In addition, since the interconnector 22 is thick in the first convex portion 221 and the second convex portion 222, the component of the setter 30 diffused in the first convex portion 221 and the second convex portion 222 is the fuel electrode current collecting layer. It is difficult to reach 11a. Therefore, it can suppress that the component of the setter 30 diffuses into the anode current collecting layer 11a.

(Application example 1 for horizontal stripe fuel cell)
Next, an application example 1 in which the power generation unit 10 and the interconnector unit 20 to which the functional ceramic body 100 is applied is applied to a horizontal stripe type fuel cell will be described with reference to the drawings.

  FIG. 13 is a cross-sectional view of the horizontal stripe fuel cell 1. The horizontal stripe fuel cell 1 is a solid oxide fuel cell (SOFC). The horizontal stripe fuel cell 1 includes a support substrate 2, a plurality of power generation units 10, and a plurality of interconnectors 20.

The support substrate 2 is formed in a flat plate shape that is long in one direction. The support substrate 2 contains an electrically insulating porous material as a main component. As a material constituting the support substrate 2, MgO (magnesium oxide), a mixture of MgAl ₂ O ₄ (magnesia alumina spinel) and MgO (magnesium oxide), CSZ (calcia stabilized zirconia), 8YSZ (yttria stabilized zirconia), Insulating ceramics such as Y ₂ O ₃ (yttria) and CZO (calcium zirconate) can be used.

  The support substrate 2 may contain a transition metal or an oxide of the transition metal that functions as a catalyst for promoting a reforming reaction of the fuel gas. Ni (nickel) is preferred as the transition metal. The thickness of the support substrate 2 is not particularly limited, but can be 1 mm to 5 mm. The porosity of the support substrate 2 is not particularly limited, but can be 20% to 60% in a reducing atmosphere.

  A gas flow path 2 a is formed inside the support substrate 2. The gas flow path 2 a extends along the longitudinal direction of the support substrate 2. During power generation, the fuel gas flowing through the gas flow path 2 a passes through the inside of the support substrate 2 and is supplied to the fuel electrode current collecting layer 11 a and the fuel electrode active layer 11 b of the power generation unit 10. The number of gas flow paths 2a can be set as appropriate.

  On the first main surface 2S and the second main surface 2T of the support substrate 2, the power generation units 10 and the interconnectors 20 are alternately arranged in the longitudinal direction. A pair of adjacent power generation units 10 and interconnector units 20 share the anode current collecting layer 11a.

  Both end portions of the solid electrolyte layer 12 of each power generation unit 10 are connected to the respective interconnectors 22 of the two interconnector units 20 disposed on both sides of each power generation unit 10. As described above, the solid electrolyte layer 12 and the interconnector 22 are connected to form a seal film that prevents leakage of the fuel gas and the oxygen-containing gas. The interconnector 22 is located on the same side as the solid electrolyte layer 12 and the barrier layer 13 with respect to the anode current collecting layer 11a.

  The air electrode current collecting layer 14b of each power generation unit 10 is connected to the interconnector 22 of the interconnector unit 20 that does not share the fuel electrode current collecting layer 11a. The barrier layer 13 of each power generation unit 10 is disposed on the solid electrolyte layer 12. The barrier layer 13 of each power generation unit 10 includes a first protrusion 131 and a second protrusion 132.

  The first convex portion 131 and the second convex portion 132 are farthest from the support substrate 2 among the constituent members of the horizontal stripe fuel cell 1 excluding the air electrode 14. That is, the first convex portion 131 and the second convex portion 132 are disposed at the highest position from the support substrate 2. Accordingly, when the barrier layer 13 is baked, only the first convex portion 131 and the second convex portion 132 are in contact with the setter 30 (see FIG. 10), so that the constituent components of the setter 30 diffuse into the interconnector 22. Can be suppressed.

  In addition, although the 1st convex part 221 and the 2nd convex part 222 are not formed in the interconnector 22 of the interconnector part 20 of the horizontal stripe type fuel cell 1, at least of the 1st convex part 221 and the 2nd convex part 222 One may be formed.

(Application example 2 for horizontal stripe fuel cell)
Next, an application example 2 in which the power generation unit 10 and the interconnector unit 20 to which the functional ceramic body 100 is applied is applied to a horizontal stripe fuel cell will be described with reference to the drawings.

  FIG. 14 is a cross-sectional view showing the configuration of the horizontal stripe fuel cell 1a. The horizontal stripe fuel cell 1a is a solid oxide fuel cell (SOFC). The horizontal stripe fuel cell 1 a includes a support substrate 2, a plurality of power generation units 10, and a plurality of interconnectors 20.

1. Support substrate 2
The support substrate 2 is formed in a flat plate shape that is long in one direction. The support substrate 2 contains an electrically insulating porous material as a main component. As a material constituting the support substrate 2, MgO (magnesium oxide), a mixture of MgAl ₂ O ₄ (magnesia alumina spinel) and MgO (magnesium oxide), CSZ (calcia stabilized zirconia), 8YSZ (yttria stabilized zirconia), Insulating ceramics such as Y ₂ O ₃ (yttria) and CZO (calcium zirconate) can be used.

  The support substrate 2 may contain a transition metal or an oxide of the transition metal that functions as a catalyst for promoting a reforming reaction of the fuel gas. Ni (nickel) is preferred as the transition metal. The thickness of the support substrate 2 is not particularly limited, but can be 1 mm to 5 mm. The porosity of the support substrate 2 is not particularly limited, but can be 20% to 60% in a reducing atmosphere.

  A gas flow path 2 a is formed inside the support substrate 2. The gas flow path 2 a extends along the longitudinal direction of the support substrate 2. During power generation, the fuel gas flowing through the gas flow path 2 a passes through the inside of the support substrate 2 and is supplied to the fuel electrode current collecting layer 11 a and the fuel electrode active layer 11 b of the power generation unit 10. The number of gas flow paths 2a can be set as appropriate.

  On the first main surface 2S and the second main surface 2T of the support substrate 2, the power generation units 10 and the interconnectors 20 are alternately arranged in the longitudinal direction. A pair of adjacent power generation units 10 and interconnector units 20 share the anode current collecting layer 11a.

2. Power generation unit 10
Next, the power generation unit 10 of the horizontal stripe fuel cell 1a will be described. The power generation unit 10 includes a fuel electrode 11, a solid electrolyte layer 12, a barrier layer 13, and an air electrode 14.

  The fuel electrode current collecting layer 11 a of the fuel electrode 11 is disposed in a recess 2 b formed on the main surface of the support substrate 2. The anode current collecting layer 11a is embedded in the recess 2b. The anode current collecting layer 11a has the same outer shape as the recess 2b. The outer surface of the anode current collecting layer 11 a is continuous with the main surface of the support substrate 2. The outer surface of the anode current collecting layer 11 a forms a plane with the main surface of the support substrate 2. Note that a step of about 50 μm or less may exist between the outer surface of the anode current collecting layer 11 a and the main surface of the support substrate 2.

  However, the anode current collecting layer 11a may not be embedded in the recess 2b. The anode current collecting layer 11 a may be disposed on the main surface of the support substrate 2.

  The fuel electrode active layer 11 b of the fuel electrode 11 is disposed outside the support substrate 2. Most of the anode active layer 11b is disposed on the anode current collecting layer 11a. One end of the anode active layer 11b is disposed on a seal layer 23 described later.

  The anode active layer 11 b has a first convex portion 111 and a second convex portion 112. Each of the first convex portion 111 and the second convex portion 112 protrudes toward the opposite side of the anode current collecting layer 11a in the stacking direction. Each of the first protrusions 111 and the second protrusions 112 protrudes toward the barrier layer 13 in the stacking direction. The thickness of the fuel electrode active layer 11 b is partially thicker at the first and second convex portions 111 and 112.

  The 1st convex part 111 and the 2nd convex part 112 of the anode active layer 11b are located in the outer edge of the anode active layer 11b. The first convex portion 111 of the anode active layer 11 b is located on the anode current collecting layer 11 a side of the first convex portion 131 of the barrier layer 13. The second convex portion 112 of the anode active layer 11 b is located on the anode current collecting layer 11 a side of the second convex portion 132 of the barrier layer 13. Therefore, even if the constituent components of the setter 30 diffuse from the first convex portion 131 and the second convex portion 132 of the barrier layer 13 during firing, the first convex portion 111 and the second convex portion 112 of the anode active layer 11b. Therefore, it is possible to suppress the diffusion component from reaching the anode current collecting layer 11a. In addition, due to the anchor effect of the first convex portion 111 and the second convex portion 112, the adhesion between the fuel electrode active layer 11b and the solid electrolyte layer 12 can be improved.

  The solid electrolyte layer 12 is disposed between the two sealing layers 23. The solid electrolyte layer 12 covers the anode active layer 11b. The solid electrolyte layer 12 has a first protrusion 121 and a second protrusion 122. Each of the first convex portion 121 and the second convex portion 122 projects toward the opposite side of the fuel electrode 11 in the stacking direction. Each of the first protrusion 121 and the second protrusion 122 protrudes toward the barrier layer 13 in the stacking direction. The solid electrolyte layer 12 is formed with a substantially uniform thickness as a whole.

  The first convex portion 121 of the solid electrolyte layer 12 is located on the anode current collecting layer 11 a side of the first convex portion 131 of the barrier layer 13. The first convex portion 121 of the solid electrolyte layer 12 is disposed between the first convex portion 131 of the barrier layer 13 and the first convex portion 111 of the anode active layer 11b in the stacking direction. The second convex portion 122 of the solid electrolyte layer 12 is located on the anode current collecting layer 11 a side of the second convex portion 132 of the barrier layer 13. The second convex portion 122 of the solid electrolyte layer 12 is disposed between the second convex portion 132 of the barrier layer 13 and the second convex portion 112 of the anode active layer 11b in the stacking direction. Therefore, even if the constituent components of the setter 30 are diffused from the first convex portion 131 and the second convex portion 132 of the barrier layer 13 during the firing, the first convex portion 121 and the second convex portion 122 of the solid electrolyte layer 12 Since the diffusion component can be accumulated, the diffusion component can be prevented from reaching the anode current collecting layer 11a. In addition, the adhesion between the solid electrolyte layer 12 and the barrier layer 13 can be improved by the anchor effect of the first convex portion 121 and the second convex portion 122.

  The barrier layer 13 is disposed between the two sealing layers 23. The barrier layer 13 covers the solid electrolyte layer 12. The barrier layer 13 has a first protrusion 131 and a second protrusion 132. The first convex portion 131 of the barrier layer 13 is located on the opposite side of the anode current collecting layer 11a with respect to the first convex portion 111 of the anode active layer 11b. The second convex portion 132 of the barrier layer 13 is located on the opposite side of the anode current collecting layer 11a with respect to the second convex portion 112 of the anode active layer 11b.

  The air electrode active layer 14 a of the air electrode 14 is formed on the barrier layer 13. The air electrode active layer 14 a has a first convex portion 141 and a second convex portion 142. Each of the first convex portion 141 and the second convex portion 142 of the air electrode active layer 14a protrudes toward the opposite side of the barrier layer 13 in the stacking direction.

  The air electrode current collecting layer 14b of the air electrode 14 is formed on the air electrode active layer 14a. The air electrode current collecting layer 14 b includes a first convex portion 143 and a second convex portion 144. Each of the first convex portion 143 and the second convex portion 144 protrudes toward the side opposite to the air electrode active layer 14a. The second convex portion 144 is disposed on the second convex portion 142 of the air electrode active layer 14a in the stacking direction.

  Further, the air electrode current collecting layer 14 b has a third convex portion 145 and a fourth convex portion 146. Each of the third convex portion 145 and the fourth convex portion 146 of the air electrode current collecting layer 14 b protrudes toward the side opposite to the interconnector 22. The 3rd convex part 145 is arrange | positioned on the 1st convex part 221 of the interconnector 22 in the lamination direction. The 4th convex part 146 is arrange | positioned on the 2nd convex part 222 of the interconnector 22 in the lamination direction.

3. Interconnector section 20
Next, the interconnector portion 20 of the horizontal stripe fuel cell 1a will be described. The interconnector portion 20 of the horizontal stripe fuel cell 1 a includes an intermediate layer 21, an interconnector 22, and a seal layer 23.

  The intermediate layer 21 is disposed outside the support substrate 2. The intermediate layer 21 is disposed on the anode current collecting layer 11a. The intermediate layer 21 is disposed inside the seal layer 23. The intermediate layer 21 has a first convex portion 211 and a second convex portion 212. Each of the first convex portion 211 and the second convex portion 212 projects toward the side opposite to the anode current collecting layer 11a in the stacking direction. Each of the first convex portion 211 and the second convex portion 212 protrudes toward the interconnector 22 in the stacking direction. The intermediate layer 21 is partially thick at the first convex portion 211 and the second convex portion 212.

  The first convex portion 211 and the second convex portion 212 of the intermediate layer 21 are located on the outer edge of the intermediate layer 21. The first convex portion 211 of the intermediate layer 21 is located on the anode current collecting layer 11a side of the first convex portion 221 of the interconnector 22 in the stacking direction. The second convex portion 212 of the intermediate layer 21 is located on the anode current collecting layer 11a side of the second convex portion 222 of the interconnector 22 in the stacking direction. Therefore, even if the components of the setter 30 diffuse from the first convex portion 221 and the second convex portion 222 of the interconnector 22 during firing, they diffuse to the first convex portion 211 and the second convex portion 212 of the intermediate layer 21. Since components can be accumulated, diffusion components can be prevented from reaching the anode current collecting layer 11a. In addition, the adhesion between the intermediate layer 21 and the interconnector 22 can be improved by the anchor effect of the first convex portion 211 and the second convex portion 212.

  The intermediate layer 21 has a concave surface 21 </ b> S connected to the interconnector 22. The concave surface 21S is formed between the first convex portion 211 and the second convex portion 212. A substantially central portion of the concave surface 21S is recessed toward the anode current collecting layer 11a. As a result, the contact area between the intermediate layer 21 and the interconnector 22 can be increased as compared with the case where the intermediate layer 21 and the interconnector 22 contact each other between flat surfaces. The electrical resistance at the interface can be reduced.

  The seal layer 23 is disposed on the anode current collecting layer 11a. The seal layer 23 surrounds the intermediate layer 21. In the present embodiment, the seal layer 23 also surrounds a portion of the interconnector 22 on the anode current collecting layer 11a side. The seal layer 23 is connected to one end of each of the fuel electrode active layer 11b, the solid electrolyte layer 12, and the barrier layer 13.

The seal layer 23 has electrical insulation. That is, the seal layer 23 does not have electronic conductivity. The seal layer 23 can be made of, for example, MgO (magnesia), CaZrO ₃ (calcium zirconate), Y ₂ O ₃ (yttria), MgAl ₂ O ₄ (magnesia alumina spinel), or the like.

  The seal layer 23 has a first protrusion 231 and a second protrusion 232. Each of the first convex portion 231 and the second convex portion 232 protrudes toward the side opposite to the fuel electrode 11 in the stacking direction. Each of the first convex portion 231 and the second convex portion 232 protrudes toward the interconnector 22 in the stacking direction. In the present embodiment, the seal layer 23 is partially thick at the first convex portion 231 and the second convex portion 232.

  The first convex portion 231 of the seal layer 23 is located on the anode current collecting layer 11 a side of the first convex portion 221 of the interconnector 22. The first convex portion 231 of the seal layer 23 is disposed between the first convex portion 221 of the interconnector 22 and the first convex portion 211 of the intermediate layer 21 in the stacking direction. The second convex portion 232 of the seal layer 23 is located on the anode current collecting layer 11 a side of the second convex portion 222 of the interconnector 22. The second convex portion 232 of the seal layer 23 is disposed between the second convex portion 222 of the interconnector 22 and the second convex portion 222 of the intermediate layer 21 in the stacking direction. Therefore, even if the components of the setter 30 diffuse from the first convex portion 221 and the second convex portion 222 of the interconnector 22 during firing, they diffuse to the first convex portion 231 and the second convex portion 232 of the seal layer 23. Since components can be accumulated, diffusion components can be prevented from reaching the anode current collecting layer 11a. In addition, due to the anchor effect of the first convex portion 231 and the second convex portion 232, the adhesion between the seal layer 23 and the interconnector 22 can be improved.

  The interconnector 22 is disposed on the intermediate layer 21. The interconnector 22 has a first convex part 221 and a second convex part 222. Each of the first convex portion 221 and the second convex portion 222 protrudes toward the side opposite to the anode current collecting layer 11a in the stacking direction. Each of the first convex portion 221 and the second convex portion 222 protrudes toward the air electrode 14 in the stacking direction. In the present embodiment, the interconnector 22 is thick at the central portion that contacts the concave surface 21 </ b> S of the intermediate layer 21. Therefore, it is possible to suppress the occurrence of gas leak between the fuel electrode side and the air electrode side.

  The first convex portion 221 and the second convex portion 222 of the interconnector 22 are located on the outer edge of the interconnector 22. The first convex portion 221 of the interconnector 22 is located on the opposite side of the anode current collecting layer 11a with respect to the first convex portion 211 of the intermediate layer 21. The second convex portion 222 of the interconnector 22 is located on the opposite side of the anode current collecting layer 11a with respect to the second convex portion 212 of the intermediate layer 21. Therefore, even if the constituent components of the setter 30 diffuse into the first convex portion 221 and the second convex portion 222 of the interconnector 22 during firing, it is possible to suppress the diffusion component from reaching the anode current collecting layer 11a. In addition, due to the anchor effect of the first convex portion 221 and the second convex portion 222, the adhesion between the interconnector 22 and the air electrode 14 can be improved.

  In the present embodiment, the first convex portion 221 and the second convex portion 222 of the interconnector 22 are higher than the first convex portion 131 and the second convex portion 132 of the barrier layer 13, but the first convex portion of the barrier layer 13. It may be the same height as the portion 131 and the second convex portion 132, or may be lower than the first convex portion 131 and the second convex portion 132 of the barrier layer 13.

(Vertical stripe fuel cell 3)
Next, an application example in which the power generation unit 10 and the interconnector unit 20 to which the functional ceramic body 100 is applied is applied to a vertical stripe type fuel cell will be described with reference to the drawings.

  FIG. 15 is a cross-sectional view of the vertical stripe fuel cell 3. The vertical stripe fuel cell 3 is a solid oxide fuel cell. The vertical stripe fuel cell 3 includes a pair of power generation unit 10 and interconnector unit 20. The pair of power generation units 10 and the interconnector unit 20 share one anode current collecting layer 11a. The anode current collecting layer 11 a functions as a support substrate for the vertical stripe fuel cell 3.

  The anode current collecting layer 11a is formed in a flat plate shape. A gas flow path 2a is formed inside the anode current collecting layer 11a. During power generation, the fuel gas flowing through the gas flow path 2a passes through the anode current collecting layer 11a and is supplied to the anode active layer 11b of the power generation unit 10. The number of gas flow paths 2a can be set as appropriate.

  The power generation unit 10 is disposed on the first main surface 11S of the anode current collecting layer 11a. An interconnector portion 20 is disposed on the second main surface 11T of the anode current collecting layer 11a. Both ends of the solid electrolyte layer 12 of the power generation unit 10 cover the side surfaces of the anode current collecting layer 11 a and are connected to both ends of the interconnector 22 of the interconnector unit 20. As described above, the solid electrolyte layer 12 and the interconnector 22 are connected to form a seal film that prevents leakage of the fuel gas and the oxygen-containing gas. The interconnector 22 is located on the opposite side of the solid electrolyte layer 12 and the barrier layer 13 with respect to the anode current collecting layer 11a.

  The interconnector 22 has a first convex part 221 and a second convex part 222. Accordingly, when the interconnector 22 is fired, only the first convex portion 221 and the second convex portion 222 are in contact with the setter 30 (see FIG. 12), so the setter 30 is connected to the interconnector 22 and the anode current collecting layer 11a. Can be prevented from diffusing.

  In addition, although the 1st convex part 131 and the 2nd convex part 132 are not formed in the barrier layer 13 of the electric power generation part 10 of the vertical stripe type fuel cell 3, at least one of the 1st convex part 131 and the 2nd convex part 132 is formed. May be formed.

(Other embodiments)
The present invention is not limited to the embodiment described above, and various modifications or changes can be made without departing from the scope of the present invention.

  In the above embodiment, the case where the functional ceramic body 100 according to the present invention is applied to a horizontal stripe fuel cell has been described as an example. However, the functional ceramic body 100 according to the present invention is a vertical stripe type, fuel electrode support type. The present invention can be applied to various fuel cells such as an electrolyte flat plate type and a cylindrical type. The functional ceramic body 100 according to the present invention can be applied to a solid oxide electrochemical cell including a solid oxide electrolytic cell in addition to a solid oxide fuel cell.

  In the following, examples of “power generation part of fuel cell” will be described as an example of “functional ceramic body” according to the present invention, but the present invention is not limited to the examples described below.

(Production of sample Nos. 1 to 17)
Sample no. The power generation part of the fuel cell concerning 1-17 was produced. Sample No. As shown in FIGS. 16 and 17, the power generation units 1 to 17 include a fuel electrode, an electrolyte, and an air electrode. Sample No. In 1 to 17, convex portions are provided on the electrolyte and the air electrode, respectively, but in this embodiment, the effect of the convex portions of the electrolyte is confirmed.

First, a mixed body of NiO and Y ₂ O ₃ was die press molded to form a fuel electrode molded body.

  Next, a slurry containing GDC (gadolinium-doped ceria) and YSZ (yttria-stabilized zirconia) was applied onto the fuel electrode molded body to form a molded body of the main body portion of the electrolyte layer. Subsequently, the same slurry was applied in a strip shape on the molded body of the main body, thereby forming a molded body of the convex portion. At this time, as shown in Table 1, the width W and height H of the convex portions were adjusted by adjusting the application width and application height of the slurry. Thereby, the molded object of the electrolyte which has a main-body part and a convex part was formed.

  Next, as shown in FIG. 18, the fuel electrode and the electrolyte are formed by firing (1400 ° C., 2 hours) in a state where one end portion and the convex portion of the electrolyte are in contact with the setter with the molded body of the electrolyte facing downward. Formed.

  Next, the air electrode compact was formed by applying a slurry containing LSCF (lanthanum strontium cobalt ferrite) on the electrolyte. At this time, a part of the air electrode was raised along the convex part of the electrolyte, so that the convex part was also formed on the air electrode.

  Next, as shown in FIG. 19, by firing (1000 ° C., 1 hour) with the air electrode molded body facing upward, one end of the air electrode and the convex portion are in contact with the setter, the air electrode Formed. The reason why the air electrode molded body is directed upward is to accurately evaluate the effect of suppressing the diffusion of the setter component by the convex portion of the electrolyte by suppressing the diffusion of the setter component from the air electrode to the electrolyte.

  Sample No. 1 to 17, the fuel electrode has a length of 20 mm, a width of 20 mm, and a thickness of 1 mm, the electrolyte has a length of 20 mm, a width of 20 mm (width A), and a thickness of 15 μm, and the air electrode has a length of 18 mm, a width of 18 mm, and a thickness of 50 μm. Met. The length of the convex portion of the electrolyte was 18 mm, and the width W and height H were as shown in Table 1.

(Production of sample No. 18)
Except that no protrusion was formed on the electrolyte, Sample No. Sample No. 1 to 17 in the same process. 18 power generation units were produced. Therefore, the electrolyte is baked in a state where the entire surface is in contact with the setter.

(Production of sample Nos. 19 to 35)
Sample no. The power generation part of the fuel cell according to 19 to 35 was produced. Sample No. As shown in FIGS. 20 and 21, the power generation units 19 to 35 include a fuel electrode, an electrolyte, and an air electrode, and a convex portion is provided on the air electrode.

First, a mixed body of NiO and Y ₂ O ₃ was die press molded to form a fuel electrode molded body.

  Next, a slurry containing GDC (gadolinium-doped ceria) and YSZ (yttria-stabilized zirconia) was applied onto the fuel electrode compact, thereby forming an electrolyte layer compact.

  Next, as shown in FIG. 22, the fuel electrode and the electrolyte were formed by firing (1400 ° C., 2 hours) in a state where the molded body of the fuel electrode faced down and placed on the setter.

  Next, a slurry containing LSCF (lanthanum strontium cobalt ferrite) was applied in a strip shape on the electrolyte to form a molded body of the air electrode body. Subsequently, the same slurry was applied in a strip shape on the molded body of the main body, thereby forming a molded body of the convex portion. At this time, by adjusting the application width and application height of the slurry, the width W and height H of the protrusions were adjusted as shown in Table 2. Thereby, the molded object of the air electrode which has a main-body part and a convex part was formed.

  Next, as shown in FIG. 23, by firing (1000 ° C., 1 hour) with the air electrode molded body facing downward, with the convex portion of the air electrode and one end of the electrolyte in contact with the setter. Formed an air electrode.

  Sample No. 19 to 35, the fuel electrode has a length of 100 mm, a width of 100 mm, and a thickness of 1 mm, the electrolyte has a length of 100 mm, a width of 100 mm, and a thickness of 15 μm, and the air electrode has a length of 90 mm, a width of 20 mm (width A), and a thickness of 50 μm. Met. Moreover, the length of the convex part of the air electrode was 90 mm, and the width W and the height H were as shown in Table 2.

(Production of sample No. 36)
Except that no projection was formed on the air electrode, Sample No. In the same process as in 19-35, sample no. 36 power generation units were produced. Therefore, the air electrode is fired in a state where the entire surface is in contact with the setter.

(Element diffusion from setter)
Sample No. About 1-18, the average density | concentration of the setter component (Al element) in the main-body part of an electrolyte was measured by conducting the elemental analysis of the cross section of the main-body part of an electrolyte by the EDS method using SEM. Specifically, the average density of three visual fields (each visual field is 10 μm × 10 μm) at the center in the thickness direction was measured.

  Sample No. For Samples 19-36, Sample No. Similarly to 1-18, the average concentration of the setter component (Al element) in the body part of the air electrode was measured by elemental analysis of the cross section of the body part of the air electrode by the EDS method using SEM.

  In Tables 1 and 2, a sample having an average Al element concentration of 10,000 ppm or more in the electrolyte or air electrode main body is evaluated as x, a sample having an average concentration of 1000 ppm or more and less than 10,000 ppm is evaluated as ○, and the average concentration is less than 1000 ppm. The samples were evaluated as ◎.

(Crack in convex part)
Sample No. About 1-17, the presence or absence of the crack in a convex part surface was confirmed by observing the cross section of the convex part of an electrolyte with SEM (scanning electron microscope). Specifically, three randomly selected SEM images were acquired, and the total number of cracks having a length of 3 μm or more was counted.

  Sample No. About 19-35, the presence or absence of the crack in the convex part surface was confirmed by observing the cross section of the convex part of an air electrode with SEM (scanning electron microscope). Specifically, three randomly selected SEM images were acquired, and the total number of cracks of 3 μm or more was counted.

  In Table 1, a sample having a total number of cracks of 3 or more was evaluated as △, a sample having a total number of cracks of 1 or more and less than 3 was evaluated as サ ン プ ル, and a sample in which no crack was confirmed was evaluated as ◎. did.

(Output generator output measurement)
Sample No. 1-17 and sample no. About 19-35, while supplying oxidant gas to an air electrode, while supplying nitrogen gas to a fuel electrode, it heated up to 750 degreeC, and when it reached 750 degreeC, it reduced by supplying hydrogen gas to an anode. For 3 hours. Subsequently, the initial output of the fuel cell at 750 ° C. was measured while the supply of the oxidant gas and the supply of hydrogen gas were continued.

In Table 1, samples having an initial output of 0.2 W / cm ² or more were evaluated as “◯”, and samples having an initial output of less than 0.2 W / cm ² were evaluated as “Δ”.

  As shown in Table 1, the sample No. 1 was fired by bringing the convex portion of the electrolyte into contact with the setter. In Nos. 1 to 17, sample Nos. 1 and 7 were fired by bringing the entire surface of the electrolyte into contact with a setter. Compared to 18, element diffusion from the setter to the main body of the electrolyte could be suppressed. This is because the setter component can be prevented from diffusing into the main body of the electrolyte by narrowing the contact area between the setter and the electrolyte.

  Similarly, as shown in Table 2, the sample No. 1 was fired by bringing the convex part of the air electrode into contact with the setter. In Nos. 19 to 35, sample No. 1 was fired by bringing the entire surface of the air electrode into contact with a setter. Compared to 35, element diffusion from the setter to the main body of the air electrode could be suppressed. This is because the setter component can be prevented from diffusing into the main body of the air electrode by narrowing the contact area between the setter and the air electrode.

  Further, as shown in Table 1, sample No. 1 in which the ratio (W / H) of the width W to the height H of the convex portion of the electrolyte was 1 or more. In 1-6,8,9,11-13,15-17, the crack in a convex part was able to be suppressed. This is because the strength of the convex portion can be secured by suppressing the shape of the convex portion from being excessively sharp.

  Similarly, as shown in Table 2, sample No. 1 in which the ratio (W / H) of the width W to the height H of the convex portion of the air electrode was 1 or more. In 19-24, 26, 27, 29-31, 33-35, the crack in a convex part was able to be controlled. This is because the shape of the convex portion can be suppressed from being excessively sharp.

  In addition, as shown in Table 1, the sample No. 1 in which the height H of the convex portion of the electrolyte was 80 μm or less was used. In 1-13, the crack in a convex part was able to be suppressed more. This is because the shape of the convex portion can be further suppressed from being excessively sharp.

  Similarly, as shown in Table 2, the sample No. 1 was adjusted so that the height H of the convex portion of the air electrode was 80 μm or less. In 19-31, the crack in a convex part could be suppressed more. This is because the shape of the convex portion can be further suppressed from being excessively sharp.

  In addition, as shown in Table 1, the sample No. 1 in which the height H of the convex portion of the electrolyte was 8 μm or more was used. In 3-17, element diffusion from the setter to the main body of the electrolyte could be further suppressed. This is because element diffusion from the convex portion of the electrolyte to the main body portion can be further suppressed by sufficiently securing the height of the electrolyte.

  Similarly, as shown in Table 2, a sample No. 1 having a height H of the convex portion of the air electrode of 8 μm or more was used. In 21-35, the element diffusion from the setter to the main body of the air electrode could be further suppressed. This is because element diffusion from the convex portion of the air electrode to the main body portion can be further suppressed by sufficiently securing the height of the air electrode.

  Further, as shown in Table 1, sample No. 1 was obtained in which the width W of the convex portion of the electrolyte was less than 20% of the total width A of the main body portion. In 1 to 5, 7 to 12, and 14 to 16, the initial output could be improved. This is because the functionality (oxygen ion conductivity) of the main body portion of the electrolyte can be secured by suppressing the area occupied by the convex portions on the surface of the electrolyte.

  Similarly, as shown in Table 2, a sample No. in which the width W of the convex portion of the air electrode was less than 20% of the total width A of the main body portion was obtained. In 19 to 23, 25 to 30, and 32 to 34, the initial output could be improved. This is because the functionality (electrocatalytic property) of the main body portion of the air electrode can be secured by suppressing the area occupied by the projections on the surface of the air electrode.

DESCRIPTION OF SYMBOLS 100 Functional ceramic body 101 1st layer 102 2nd layer 102a Main body part 102b-102f Convex part W Convex part width H Convex part height 1 Horizontal stripe type fuel cell 2 Support substrate 2b Concave part 3 Vertical stripe type fuel cell 10 Power generation part DESCRIPTION OF SYMBOLS 11 Fuel electrode 11a Fuel electrode current collection layer 11b Fuel electrode active layer 12 Solid electrolyte layer 13 Barrier layer 13S Surface 131 1st convex part 132 2nd convex part 14 Air electrode 14a Air electrode active layer 14b Air electrode current collection layer 20 Interconnector Part 21 Intermediate layer 22 Interconnector

Claims (8)

A first layer composed of ceramics and / or metal;
A second layer formed on the first layer and made of ceramic and / or metal;
With
The second layer has a protrusion protruding toward the opposite side of the first layer,
In the cross section parallel to the thickness direction of the second layer, the ratio of the width of the convex portion to the height of the convex portion is 1 or more,
The functional ceramic body in which a height of the convex portion is 80 μm or less in a cross section parallel to the thickness direction of the second layer. A first layer composed of ceramics and / or metal;
A second layer formed on the first layer and made of ceramic and / or metal;
With
The second layer has a protrusion protruding toward the opposite side of the first layer,
In the cross section parallel to the thickness direction of the second layer, the height of the convex portion is 8 μm or more,
In a cross section parallel to the thickness direction of the second layer, the width of the convex portion is less than 20% of the width of the second layer.
Functional ceramic body. In the plan view of the second layer, the convex portion extends along a predetermined direction.
The functional ceramic body according to claim 1 or 2. In the plan view of the second layer, the convex portion is formed in a continuous annular shape,
The functional ceramic body according to claim 1 or 2 . In the plan view of the second layer, the convex portion is formed in an intermittent ring shape,
The functional ceramic body according to claim 1 or 2 . In the plan view of the second layer, the convex portion has a rectangular ring shape,
The functional ceramic body according to claim 4 or 5. In the plan view of the second layer, the convex portion is an aggregate of a plurality of convex portions separated from each other.
The functional ceramic body according to claim 1 or 2 . In the plan view of the second layer, the convex portion is disposed on an outer edge of the second layer.
The functional ceramic body according to claim 3.