JP5873947B1 - Zygote - Google Patents

Abstract

A joined body of a current collecting member and a fuel battery cell, wherein “a configuration in which a plate-like portion of a metal current collecting member provided with an opening is embedded in a joining material film” is employed, “Providing an interface between the inner surface of the opening and the bonding material film that does not easily peel. The fixing portion 310 of the current collecting member is embedded in the bonding material film 80 to fix the fixing portion 310. The outer peripheral surface 310s of the peripheral portion and the inner side surface 312s of the opening 312 are covered with the bonding material film 80. The “fixed portion” with respect to the height (T) at which the inner side surface 312s of the opening is covered with the bonding material film 80. The ratio (S / T) of the line path (S) corresponding to the inner surface of the opening in the cross section of the opening along the “thickness direction” is 1.02 to 1.31. “Total of the lengths in the“ fixed portion thickness direction ”of a plurality of portions where the inner surface of the opening and the bonding material film are in contact with each other on the line corresponding to the inner surface of the opening in the cross section of the opening” , Is 21-95%. [Selection] Figure 27

Description

  The present invention relates to a joined body.

  Conventionally, “a fuel cell power generation unit including a fuel electrode, an electrolyte membrane, and an air electrode” and “a current collecting member having electron conductivity” are “a bonding material film made of a bonding material having electron conductivity”. There is known a joined body joined by the above (for example, see Patent Document 1).

  In the joined body described in the above document, the current collecting member has a plate-like portion. The bonding material film is “a conductive member having electronic conductivity electrically connected to any one of the fuel electrode and the air electrode of the power generation unit, or any one of the fuel electrode and the air electrode of the power generation unit” ( Hereinafter, it is referred to as a “base member”) and “a plate-like portion of the current collecting member”. The bonding material film is formed so that the plate-like portion of the current collecting member extends along the surface of the base member facing the plate-like portion, and the base member and the plate-like portion are electrically connected. The base member and the plate-like portion are joined.

  In the joined body described in the above document, a paste made of a joining material having electronic conductivity is used to join the base member and the plate-like portion of the current collecting member. That is, a paste film is formed on the joint surface of the base member by a technique such as coating. The plate-like portion of the current collecting member is bonded to the paste film. In this state, the paste film is baked. As a result, a joined body in which the base member and the plate-like portion of the current collecting member are electrically connected by the paste film fired body (bonding material film, fired film) is obtained.

  In such a joined body, it is preferable that electric resistance is small. For this reason, in the joined body described in the above document, “a configuration in which the plate-like portion of the current collecting member is embedded in the joining material film” is employed. This configuration is obtained by embedding the plate-like portion of the current collecting member in the paste film when the plate-like portion of the current collecting member is bonded to the paste film. In this configuration, the outer surface of the peripheral edge of the plate-like portion of the current collecting member is covered with the paste film (bonding material film). Therefore, the paste film (bonding material film) can contact not only the bottom surface of the plate-like portion of the current collecting member but also the outer surface of the peripheral portion of the plate-like portion of the current collecting member. Therefore, compared with the configuration in which only the bottom surface of the plate-shaped portion of the current collecting member is in contact with the surface of the bonding material film (that is, the configuration in which the plate-shaped portion of the current collecting member is not embedded in the bonding material film) The contact area with the material film is increased, and the electrical resistance at the junction between the current collecting member and the bonding material film can be reduced.

Japanese Patent No. 5356624

  In order to further reduce the electrical resistance of such a joined body, the present inventor provided an “opening that penetrates in the thickness direction” in the plate-like portion of the current collecting member, and “the current collector provided with the opening”. It is considered to adopt a configuration in which the plate-like portion of the member is embedded in the bonding material film (see FIGS. 20, 21 and the like described later). In this configuration, the inner surface of the opening is also covered with the paste film (bonding material film). Therefore, the paste film (bonding material film) can contact not only the bottom surface of the plate-shaped portion of the current collecting member and the outer surface of the peripheral portion of the plate-shaped portion of the current collecting member but also the inner surface of the opening. . Therefore, the contact area between the current collecting member and the bonding material film is further increased, and the electrical resistance at the bonding portion between the current collecting member and the bonding material film can be further reduced.

  The inventor repeated research, experiments, and the like on the above-described “configuration in which the plate-like portion of the current collecting member provided with the opening is embedded in the bonding material film”. As a result, it has been found that, depending on the form of the above-described configuration, peeling is likely to occur at the interface between the inner surface of the opening and the bonding material film when the paste is fired. The arrival of a bonded body in which such peeling does not easily occur has been desired.

  The present invention has been made in order to cope with the above-described problem, and the purpose thereof is a bonding in which “a configuration in which a plate-like portion of a current collecting member provided with an opening is embedded in a bonding material film” is employed. An object of the present invention is to provide a body that is difficult to cause peeling at the interface between the inner surface of the opening and the bonding material film.

  The feature of the joined body according to the present invention is that the current collecting member is made of metal and “the height of the inner surface of the opening covered with the joining material film (T)” Line path corresponding to the portion covered with the bonding material film on the inner side surface of the opening, obtained based on an image with a magnification of 30 times the cross section of the opening along the thickness direction. The ratio (S / T) is 1.02 to 1.31.

  The present inventor, when the ratio (S / T) is 1.02 to 1.31, compared to the case where the ratio is not so, the inner side surface of the opening provided in the plate-like portion of the current collecting member, and the bonding It has been found that peeling hardly occurs at the interface with the material film (this point will be described later).

It is a perspective view showing one cell used for a stack structure of a fuel cell including a joined body concerning an embodiment of the present invention. It is sectional drawing corresponding to the 2-2 line of the cell shown in FIG. It is the top view which showed the state of the fuel electrode and interconnector which were embed | buried under the recessed part of the support substrate shown in FIG. It is a figure for demonstrating the operation state of the cell shown in FIG. It is a figure for demonstrating the flow of the electric current in the operating state of the cell shown in FIG. It is a perspective view which shows the support substrate shown in FIG. FIG. 3 is a cross-sectional view corresponding to FIG. 2 in a first stage in the manufacturing process of the cell shown in FIG. 1. FIG. 3 is a cross-sectional view corresponding to FIG. 2 in a second stage in the manufacturing process of the cell shown in FIG. 1. FIG. 3 is a cross-sectional view corresponding to FIG. 2 in a third stage in the manufacturing process of the cell shown in FIG. 1. FIG. 4 is a cross-sectional view corresponding to FIG. 2 in a fourth stage in the manufacturing process of the cell shown in FIG. 1. FIG. 6 is a cross-sectional view corresponding to FIG. 2 in a fifth stage in the manufacturing process of the cell shown in FIG. 1. FIG. 6 is a cross-sectional view corresponding to FIG. 2 in a sixth stage in the manufacturing process of the cell shown in FIG. 1. FIG. 8 is a cross-sectional view corresponding to FIG. 2 in a seventh stage in the process of manufacturing the cell shown in FIG. 1. FIG. 8 is a cross-sectional view corresponding to FIG. 2 in an eighth stage in the manufacturing process of the cell shown in FIG. 1. 1 is an overall perspective view of a stack structure of a fuel cell including a joined body according to an embodiment of the present invention. FIG. 16 is an overall perspective view of the fuel manifold shown in FIG. 15. It is an enlarged view of the insertion hole formed in the support plate shown in FIG. It is the cross-sectional view which showed the mode of the junction part of an insertion hole and the one end part of a cell. It is the longitudinal cross-sectional view which showed the mode of the junction part of an insertion hole and the one end part of a cell. FIG. 20 is an overall perspective view of the current collecting member shown in FIG. 19. It is an expanded view of the current collection member shown in FIG. It is the figure which showed the mode of the elastic deformation of the current collection member when the relative rotational displacement seen from the x-axis direction generate | occur | produced between adjacent cells. It is the figure which showed the mode of the elastic deformation of the current collection member when the relative rotational displacement seen from the y-axis direction generate | occur | produced between adjacent cells. It is the figure which showed the mode of the elastic deformation of the current collection member in case the relative rotational displacement seen from the z-axis direction generate | occur | produced between adjacent cells. It is a perspective view corresponding to FIG. 20 about the modification of a current collection member. It is an expanded view corresponding to FIG. 21 about the modification of the current collection member shown in FIG. It is a figure which shows an example of the process of the process at the time of electrically connecting and fixing the plate-shaped part of a current collection member, and a base member via a bonding material paste (bonding material film | membrane). It is a figure for demonstrating the position of the cross section of the current collection member corresponding to sectional drawing shown in FIG. It is a 30-times partial enlarged view of the joined body shown in FIG. It is a 30-times partial enlarged view of the other example of the joined body shown in FIG. It is a 30-times partial enlarged view of the other example of the joined body shown in FIG.

(Example of cell structure used for a stack structure including a joined body)
First, a cell 100 used in a stack structure of a fuel cell (SOFC) including a joined body according to an embodiment of the present invention will be described. As shown in FIG. 1, this cell 100 is electrically connected in series to the upper and lower surfaces (main surfaces (planes) on both sides parallel to each other) of a flat plate-like support substrate 10 having a longitudinal direction (x-axis direction). A plurality (four in this example) of the same power generation element portions A connected to each other are arranged at a predetermined interval in the longitudinal direction, so-called “horizontal stripe type”.

  The shape of the entire cell 100 viewed from above is, for example, a rectangle with a side length L1 in the longitudinal direction of 50 to 500 mm and a length L2 in the width direction (y-axis direction) perpendicular to the longitudinal direction of 10 to 100 mm. Yes (L1> L2). The total thickness L3 of the cell 100 is 1 to 5 mm (L2> L3). The entire cell 100 has a vertically symmetrical shape with respect to a plane passing through the center in the thickness direction and parallel to the main surface of the support substrate 10. Hereinafter, in addition to FIG. 1, details of the cell 100 will be described with reference to FIG. 2, which is a partial cross-sectional view of the cell 100 corresponding to line 2-2 shown in FIG. 1. FIG. 2 is a partial cross-sectional view showing a configuration (part of) each of a typical pair of adjacent power generation element portions A and A and a configuration between the power generation element portions A and A. The configuration between the other power generation element portions A and A in other sets is the same as the configuration shown in FIG.

  The support substrate 10 is a flat plate-like fired body made of a porous material having no electronic conductivity. As shown in FIG. 6 to be described later, a plurality of (six in this example) fuel gas passages 11 (through holes) extending in the longitudinal direction are provided in the support substrate 10 at predetermined intervals in the width direction. Is formed. In this example, each recess 12 includes a bottom wall made of the material of the support substrate 10 and side walls closed in the circumferential direction made of the material of the support substrate 10 over the entire circumference (two side walls along the longitudinal direction and the width direction). A rectangular parallelepiped depression defined by two side walls).

The support substrate 10 can be made of, for example, CSZ (calcia stabilized zirconia). Alternatively, it may be composed of NiO (nickel oxide) and YSZ (8YSZ) (yttria stabilized zirconia), NiO (nickel oxide) and Y ₂ O ₃ (yttria), or MgO. (Magnesium oxide) and MgAl ₂ O ₄ (magnesia alumina spinel) may be used.

  The support substrate 10 may be configured to include “transition metal oxide or transition metal” and insulating ceramics. As the “transition metal oxide or transition metal”, NiO (nickel oxide) or Ni (nickel) is suitable. The transition metal can function as a catalyst for promoting a reforming reaction of the fuel gas (hydrocarbon-based gas reforming catalyst).

Further, as the insulating ceramic, MgO (magnesium oxide) or “mixture of MgAl 2 O 4 (magnesia alumina spinel) and MgO (magnesium oxide)” is preferable. Further, CSZ (calcia stabilized zirconia), YSZ (8YSZ) (yttria stabilized zirconia), Y ₂ O ₃ (yttria) may be used as the insulating ceramic.

  As described above, since the support substrate 10 contains “transition metal oxide or transition metal”, the gas containing the residual gas component before the reforming is supplied to the fuel through the numerous pores inside the porous support substrate 10. In the process of being supplied from the gas flow path 11 to the fuel electrode, the catalytic action can promote the reforming of the residual gas component before the reforming. In addition, the insulating property of the support substrate 10 can be ensured by the support substrate 10 containing insulating ceramics. As a result, insulation between adjacent fuel electrodes can be ensured.

  The thickness of the support substrate 10 is 1 to 5 mm. Hereinafter, only the configuration on the upper surface side of the support substrate 10 will be described in consideration of the fact that the shape of the structure is vertically symmetrical. The same applies to the configuration of the lower surface side of the support substrate 10.

  As shown in FIGS. 2 and 3, the entire fuel electrode current collector 21 is embedded (filled) in each recess 12 formed in the upper surface (upper main surface) of the support substrate 10. Therefore, each fuel electrode current collector 21 has a rectangular parallelepiped shape. A recess 21 a is formed on the upper surface (outer surface) of each fuel electrode current collector 21. Each recess 21a has a rectangular parallelepiped shape defined by a bottom wall made of the material of the fuel electrode current collector 21 and side walls closed in the circumferential direction (two side walls along the longitudinal direction and two side walls along the width direction). It is a depression. Of the side walls closed in the circumferential direction, two side walls along the longitudinal direction are made of the material of the support substrate 10, and two side walls along the width direction are made of the material of the fuel electrode current collector 21.

  The entire anode active portion 22 is embedded (filled) in each recess 21a. Accordingly, each fuel electrode active portion 22 has a rectangular parallelepiped shape. A fuel electrode 20 is configured by the fuel electrode current collector 21 and the fuel electrode active unit 22. The fuel electrode 20 (fuel electrode current collector 21 + fuel electrode active part 22) is a fired body made of a porous material having electron conductivity. The two side surfaces and the bottom surface along the width direction of each anode active portion 22 are in contact with the anode current collecting portion 21 in the recess 21a.

  A recess 21b is formed in a portion of the upper surface (outer surface) of each fuel electrode current collector 21 excluding the recess 21a. Each recess 21b has a rectangular parallelepiped shape defined by a bottom wall made of the material of the fuel electrode current collector 21 and side walls closed in the circumferential direction (two side walls along the longitudinal direction and two side walls along the width direction). It is a depression. Of the side walls closed in the circumferential direction, two side walls along the longitudinal direction are made of the material of the support substrate 10, and two side walls along the width direction are made of the material of the fuel electrode current collector 21.

  An interconnector 30 is embedded (filled) in each recess 21b. Accordingly, each interconnector 30 has a rectangular parallelepiped shape. The interconnector 30 is a fired body made of a dense material having electronic conductivity. The two side surfaces and the bottom surface along the width direction of each interconnector 30 are in contact with the fuel electrode current collector 21 in the recess 21b.

  The upper surface (outer surface) of the fuel electrode 20 (the fuel electrode current collector 21 and the fuel electrode active unit 22), the upper surface (outer surface) of the interconnector 30, and the main surface of the support substrate 10 form one plane (recessed portion). The same plane as the main surface of the support substrate 10 when 12 is not formed) is formed. That is, no step is formed between the upper surface of the fuel electrode 20, the upper surface of the interconnector 30, and the main surface of the support substrate 10.

The fuel electrode active part 22 may be composed of, for example, NiO (nickel oxide) and YSZ (8YSZ) (yttria stabilized zirconia). Or you may comprise from NiO (nickel oxide) and GDC (gadolinium dope ceria). The fuel electrode current collector 21 can be composed of, for example, NiO (nickel oxide) and YSZ (8YSZ) (yttria stabilized zirconia). Alternatively, it may be composed of NiO (nickel oxide) and Y ₂ O ₃ (yttria), or may be composed of NiO (nickel oxide) and CSZ (calcia stabilized zirconia). The thickness of the anode active portion 22 is 5 to 30 μm, and the thickness of the anode current collecting portion 21 (that is, the depth of the recess 12) is 50 to 500 μm.

  As described above, the fuel electrode current collector 21 includes a substance having electronic conductivity. The fuel electrode active part 22 includes a substance having electron conductivity and a substance having oxygen ion conductivity. The “volume ratio of the substance having oxygen ion conductivity with respect to the entire volume excluding the pore portion” in the anode active portion 22 is the “oxidative ion conductivity relative to the entire volume excluding the pore portion” in the anode current collecting portion 21. It is larger than the “volume ratio of the substance having”.

The interconnector 30 can be composed of, for example, LaCrO ₃ (lanthanum chromite). Alternatively, it may be composed of (Sr, La) TiO ₃ (strontium titanate). The thickness of the interconnector 30 is 10 to 100 μm.

  The entire surface excluding the central portion in the longitudinal direction of each portion where the plurality of interconnectors 30 are formed on the outer peripheral surface extending in the longitudinal direction of the support substrate 10 in a state where the fuel electrode 20 and the interconnector 30 are embedded in the respective recesses 12. Is covered with a solid electrolyte membrane 40. The solid electrolyte membrane 40 is a fired body made of a dense material having ionic conductivity and not electron conductivity. The solid electrolyte membrane 40 can be made of, for example, YSZ (8YSZ) (yttria stabilized zirconia). Or you may comprise from LSGM (lantern gallate). The thickness of the solid electrolyte membrane 40 is 3 to 50 μm.

  That is, the entire outer peripheral surface extending in the longitudinal direction of the support substrate 10 in a state where the fuel electrode 20 is embedded in each recess 12 is covered with a dense layer composed of the interconnector 30 and the solid electrolyte membrane 40. This dense layer exhibits a gas sealing function that prevents mixing of the fuel gas flowing in the space inside the dense layer and the air flowing in the space outside the dense layer.

  As shown in FIG. 2, in this example, the solid electrolyte membrane 40 covers the upper surface of the fuel electrode 20, both end portions in the longitudinal direction on the upper surface of the interconnector 30, and the main surface of the support substrate 10. Here, as described above, no step is formed between the upper surface of the fuel electrode 20, the upper surface of the interconnector 30, and the main surface of the support substrate 10. Therefore, the solid electrolyte membrane 40 is flattened. As a result, compared with the case where a step is formed in the solid electrolyte membrane 40, the generation of cracks in the solid electrolyte membrane 40 due to stress concentration can be suppressed, and the gas sealing function of the solid electrolyte membrane 40 is reduced. Can be suppressed.

  An air electrode 60 is formed on the upper surface of a portion in contact with each fuel electrode active part 22 in the solid electrolyte membrane 40 via a reaction preventing film 50. The reaction preventing film 50 is a fired body made of a dense material, and the air electrode 60 is a fired body made of a porous material having electron conductivity. The shape of the reaction preventing film 50 and the air electrode 60 viewed from above is substantially the same rectangle as the fuel electrode active part 22.

The reaction preventing film 50 can be made of, for example, GDC = (Ce, Gd) O ₂ (gadolinium-doped ceria). The thickness of the reaction preventing film 50 is 3 to 50 μm. The air electrode 60 can be made of, for example, LSCF = (La, Sr) (Co, Fe) O ₃ (lanthanum strontium cobalt ferrite). Alternatively, from LSF = (La, Sr) FeO ₃ (lanthanum strontium ferrite), LNF = La (Ni, Fe) O ₃ (lanthanum nickel ferrite), LSC = (La, Sr) CoO ₃ (lanthanum strontium cobaltite), etc. It may be configured. Further, the air electrode 60 may be configured by two layers of a first layer (inner layer) made of LSCF and a second layer (outer layer) made of LSC. The thickness of the air electrode 60 is 10 to 100 μm.

  The reaction preventing film 50 is interposed because the YSZ in the solid electrolyte film 40 and the Sr in the air electrode 60 react with each other in the SOFC during the production or operation of the SOFC, and the solid electrolyte film 40 and the air electrode. This is to suppress the occurrence of a phenomenon in which a reaction layer having a large electric resistance is formed at the interface with the substrate 60.

  Here, the laminated body formed by laminating the fuel electrode 20, the solid electrolyte membrane 40, the reaction preventing membrane 50, and the air electrode 60 corresponds to the “power generation element portion A” (see FIG. 2). In other words, a plurality (four in this example) of power generating element portions A are arranged on the upper surface of the support substrate 10 at a predetermined interval in the longitudinal direction.

  For each pair of adjacent power generation element portions A and A, the air electrode 60 of one power generation element portion A (on the left side in FIG. 2) and the interconnector of the other power generation element portion A (on the right side in FIG. 2). The air electrode current collecting film 70 is formed on the upper surfaces of the air electrode 60, the solid electrolyte film 40, and the interconnector 30. The air electrode current collector film 70 is a fired body made of a porous material having electron conductivity. The shape of the air electrode current collector film 70 as viewed from above is a rectangle.

The air electrode current collector film 70 can be made of, for example, LSCF = (La, Sr) (Co, Fe) O ₃ (lanthanum strontium cobalt ferrite). Alternatively, LSC = (La, Sr) CoO ₃ (lanthanum strontium cobaltite) may be used. Or you may comprise from Ag (silver) and Ag-Pd (silver palladium alloy). The thickness of the air electrode current collector film 70 is 50 to 500 μm.

  By forming each air electrode current collecting film 70 in this way, for each pair of adjacent power generation element portions A and A, the air electrode 60 of one power generation element portion A (on the left side in FIG. 2), The other fuel electrode 20 (particularly, the fuel electrode current collector 21) of the power generating element part A (on the right side in FIG. 2) passes through the “air electrode current collector film 70 and interconnector 30” having electronic conductivity. Are electrically connected. As a result, a plurality (four in this example) of power generation element portions A arranged on the upper surface of the support substrate 10 are electrically connected in series. Here, the “air electrode current collector film 70 and the interconnector 30” having electronic conductivity correspond to “electrical connection portions”.

  The interconnector 30 corresponds to the “first portion made of a dense material” in the “electrical connection portion” and has a porosity of 10% or less. The air electrode current collecting film 70 corresponds to the “second portion made of a porous material” in the “electrical connection portion”, and has a porosity of 20 to 60%.

  The porosity of the film was measured as follows. First, a so-called “resin filling” process was performed on the membrane so that the resin entered the pores of the membrane. The surface of the “resin-filled” film was mechanically polished. By performing image processing on the image obtained by observing the microstructure of the mechanically polished surface with a scanning electron microscope, the pore portion (the portion where the resin enters) and the non-pore portion ( The area of the portion where the resin did not enter was calculated. That ratio was taken as the porosity of the membrane.

As described above, as shown in FIG. 4, the fuel gas (hydrogen gas or the like) flows through the fuel gas flow path 11 of the support substrate 10 with respect to the “horizontal stripe type” cell 100 shown in FIG. 10 by exposing the upper and lower surfaces (in particular, each air electrode current collecting film 70) to “gas containing oxygen” (air or the like) (or flowing a gas containing oxygen along the upper and lower surfaces of the support substrate 10), An electromotive force is generated by an oxygen partial pressure difference generated between both side surfaces of the solid electrolyte membrane 40. Furthermore, when this structure is connected to an external load, chemical reactions shown in the following formulas (1) and (2) occur, and current flows (power generation state).
(1/2) · O ₂ + 2e ⁻ → O ₂ ⁻ (at the air electrode 60) (1)
H ₂ + O ₂ ⁻ → H ₂ O + 2e ⁻ (in the fuel electrode 20) (2)

  In the power generation state, as shown in FIG. 5, a current flows as indicated by an arrow in each pair of adjacent power generation element portions A and A. As a result, as shown in FIG. 4, from the entire cell 100 (specifically, in FIG. 4, the interconnector 30 of the power generating element part A on the foremost side and the air electrode 60 of the power generating element part A on the farthest side) The power is removed.

(Cell manufacturing method)
Next, an example of a manufacturing method of the “horizontal stripe type” cell 100 shown in FIG. 1 will be briefly described with reference to FIGS. In this specification, “g” at the end of the symbol of each member indicates that the member is “before firing”.

  First, a support substrate molded body 10g having the shape shown in FIG. 6 is produced. The molded body 10g of the support substrate is manufactured by using a method such as extrusion molding or cutting using a slurry obtained by adding a binder or the like to the material of the support substrate 10 (for example, CSZ). obtain. Hereinafter, the description will be continued with reference to FIGS. 7 to 14 showing partial cross sections corresponding to line 7-7 shown in FIG. 6.

  When the support substrate molded body 10g is manufactured as shown in FIG. 7, the fuel electrode current collector is then placed in each recess formed in the upper and lower surfaces of the support substrate molded body 10g as shown in FIG. Each of the molded parts 21g is embedded and formed. Next, as shown in FIG. 9, a molded body 22g of the fuel electrode active portion is embedded and formed in each recess formed in the outer surface of the molded body 21g of each fuel electrode current collector. The molded body 21g of each fuel electrode current collector and each of the fuel electrode active parts 22g use, for example, a slurry obtained by adding a binder or the like to the powder of the material of the fuel electrode 20 (for example, Ni and YSZ), It is embedded and formed using printing methods.

Subsequently, as shown in FIG. 10, in each concave portion formed in “the portion excluding the portion where the molded body 22 g of the fuel electrode active portion is embedded” on the outer surface of the molded body 21 g of each fuel electrode current collector. The interconnector molded bodies 30g are respectively embedded and formed. The molded body 30g of each interconnector is embedded and formed by using a slurry obtained by adding a binder or the like to the material of the interconnector 30 (for example, LaCrO ₃ ), using a printing method or the like. .

  Next, as shown in FIG. 11, the outer periphery extending in the longitudinal direction of the molded body 10g of the support substrate in a state in which the molded body (21g + 22g) of the plurality of fuel electrodes and the molded body 30g of the plurality of interconnectors are respectively embedded and formed. A solid electrolyte membrane molded film 40g is formed on the entire surface excluding the central portion in the longitudinal direction of each portion where the plurality of interconnector molded bodies 30g are formed. The molded membrane 40g of the solid electrolyte membrane is formed using, for example, a printing method, a dipping method, etc., using a slurry obtained by adding a binder or the like to the powder of the material of the solid electrolyte membrane 40 (for example, YSZ). The

  Next, as shown in FIG. 12, a reaction prevention film molding film 50g is formed on the outer surface of the solid electrolyte membrane molding body 40g in contact with the fuel electrode molding body 22g. The molded film 50g of each reaction preventing film is formed using a slurry obtained by adding a binder or the like to the powder of the material (for example, GDC) of the reaction preventing film 50, using a printing method or the like.

  Then, 10 g of the support substrate molded body in which various molded films are thus formed is fired in air at 1500 ° C. for 3 hours. Thereby, the structure of the state in which the air electrode 60 and the air electrode current collection film | membrane 70 are not formed in the cell 100 shown in FIG. 1 is obtained.

  Next, as shown in FIG. 13, an air electrode forming film 60 g is formed on the outer surface of each reaction preventing film 50. The molded film 60g of each air electrode is formed using a slurry obtained by adding a binder or the like to the powder of the material of the air electrode 60 (for example, LSCF), using a printing method or the like.

  Next, as shown in FIG. 14, for each pair of adjacent power generation element portions, air is formed so as to straddle the air electrode molding film 60 g of one power generation element portion and the interconnector 30 of the other power generation element portion. On the outer surface of the electrode forming film 60 g, the solid electrolyte film 40, and the interconnector 30, the air electrode current collecting film forming film 70 g is formed. The forming film 70g of each air electrode current collector film is obtained by using a slurry obtained by adding a binder or the like to the powder of the material of the air electrode current collector film 70 (for example, LSCF), using a printing method or the like. It is formed.

  Then, the support substrate 10 in which the molded films 60g and 70g are thus formed is baked in air at 1050 ° C. for 3 hours. Thereby, the cell 100 shown in FIG. 1 is obtained. In the above, an example of the manufacturing method of the cell 100 shown in FIG. 1 was demonstrated.

  At this time, the Ni component in the fuel electrode 20 is NiO by firing in an oxygen-containing atmosphere. Therefore, in order to acquire these electroconductivity, after that, reducing fuel gas is flowed from the support substrate 10 side, and NiO is reduced at 800 to 1000 ° C. for 1 to 10 hours. This reduction process may be performed during power generation.

(Example of overall structure of stack structure)
Next, a “solid oxide fuel cell (SOFC) stack structure including a joined body according to an embodiment of the present invention” using the cell 100 described above will be described. As shown in FIG. 15, this stack structure includes a large number of cells 100 and a fuel manifold 200 for supplying fuel gas to each of the large number of cells 100. The entire fuel manifold 200 is made of a material such as stainless steel. The fuel manifold 200 is a rectangular parallelepiped casing having an internal space (a rectangular parallelepiped space, corresponding to the first internal space) and having a longitudinal direction (z-axis direction).

  The upper wall (top plate, in other words, the top plate (flat plate) of the gas tank) of the fuel manifold 200 also serves as a support plate 210 for supporting a large number of cells 100. Further, the fuel manifold 200 has an introduction passage 220 for introducing fuel gas from the outside into the internal space of the fuel manifold 200 on one side of the longitudinal direction (z-axis direction) of the fuel manifold 200 on the support plate 210. It is provided at the end of the z-axis positive direction side. The introduction passage 220 and the internal space of the fuel manifold 200 communicate with each other.

  Each cell 100 protrudes upward (in the positive x-axis direction) from the support plate 210 (= the upper wall of the manifold 200) and when viewed from above, each cell 100 is in the y-axis direction (the first The longitudinal direction of each cell 100 (x-axis direction) so that each cell 100 extends along one direction) and the plurality of cells 100 are separated from each other along the z-axis direction (second direction) and stacked. The end of the fuel gas inflow side is joined and supported by the support plate 210. The internal space of the fuel manifold 200 communicates with each of the fuel gas flow paths 11 of the plurality of cells 100. The end portion on the fuel gas discharge side in the longitudinal direction (x-axis direction) of each cell 100 is a free end. Therefore, this stack structure can be expressed as a “cantilever stack structure”.

  As shown in FIG. 16, a large number of insertion holes 211 (through holes) communicating with the internal space of the fuel manifold 200 are formed on the surface of the support plate 210 (= the upper wall of the manifold 200). One end of the corresponding cell 100 on the fuel gas inflow side is inserted into each insertion hole 211.

  As shown in FIG. 17, in the present embodiment, the plurality of insertion holes 211 have the same shape. Each insertion hole 211 has an oval shape (L4> L5) extending in the y-axis direction having a length L4 and a width L5. The plurality of insertion holes 211 are arranged at the same position in the y-axis direction and at the same interval in the z-axis direction.

  The length L4 of each insertion hole 211 is 0.2 to 3 mm longer than the length L2 (see FIG. 1) of the side surface of one end of the cell 100. Similarly, the width L5 of each insertion hole 211 is 0.2 to 3 mm larger than the width L3 (see FIG. 1) of the side surface of one end of the cell 100. That is, as shown in FIGS. 18 and 19, when one end of the cell 100 is inserted into the insertion hole 211, a gap is formed between the inner wall of the insertion hole 211 and the outer wall of one end of the cell 100. In other words, one end of the cell 100 is loosely fitted in the insertion hole 211. In FIG. 18 and FIG. 19 (particularly FIG. 18), the gap is exaggerated.

  As shown in FIGS. 18 and 19, solidified bonding material 250 is provided so as to fill the gap in each of the bonding portions between the insertion hole 211 and one end of the cell 100. Thereby, each insertion hole 211 and the one end part of the corresponding cell 100 are joined and fixed, respectively. As shown in FIG. 19, one end of the gas flow path 11 of each cell 100 communicates with the internal space of the fuel manifold 200.

The bonding material 250 is made of crystallized glass such as MgO—CaO—SiO ₂ —B ₂ O ₃ or MgO—BaO—SiO ₂ —B ₂ O ₃ . In this specification, crystallized glass means that the ratio (crystallinity) of “volume occupied by crystal phase” to the total volume is 60% or more, and “volume occupied by amorphous phase and impurities relative to the total volume”. "Refers to glass (ceramics) having a ratio of less than 40%. The crystallinity of the crystallized glass is specifically determined by, for example, “the crystal phase and the composition after the crystal phase is identified by using XRD or the like and crystallized by using SEM and EDS or SEM and EPMA. The volume ratio of the crystal phase region is calculated based on the result of observing the distribution.

  Further, as shown in FIG. 19, in the space between adjacent cells 100, 100 (hereinafter also referred to as “inter-cell space”), the adjacent cells 100, 100 are electrically connected in series. Current collecting members 300 are interposed. In addition, a current collecting member 400 for electrically connecting the front side and the back side of each cell 100 in series is also provided. The width of each inter-cell space (distance in the z-axis direction) is the same.

  As can be understood from FIG. 19, the current collecting member 300 includes the power generating element portion A (hereinafter referred to as “the lowest power generation”) provided on the lowermost side in the vertical direction (x-axis direction) among the plurality of power generating element portions A. (Also referred to as “element portion AS”). In other words, the current collecting member 300 is connected to the base side (that is, the fuel gas inflow side) of the cell 100 protruding from the upper wall of the fuel manifold 200. This is because if the current collecting member 300 is provided on the tip side (that is, the fuel gas discharge side) of the cell 100 where the temperature is higher than the base side of the cell 100, peeling occurs at the junction between the current collecting member 300 and the cell 100. Because it is easy to do. When the surplus fuel gas discharged from the gas discharge port reacts (burns) with the surrounding air (oxygen), the temperature at the front end side of the cell 100 is locally increased by receiving heat from the combustion.

As shown in FIG. 19, each current collecting member 300 (more specifically, a pair of fixing portions 310 and 310 described later of the current collecting member 300) is adjacent to each other using a bonding material film 80 having electron conductivity. The base members B and B provided in the cells 100 and 100 are respectively joined. Here, the “base member B” means “any one of the fuel electrode 20 and the air electrode 60 of the lowermost power generation element part AS of the cell 100” or “the fuel electrode 20 of the lowermost power generation element part AS and This refers to a conductive member having electronic conductivity electrically connected to any one of the air electrodes 60. The conductive member is a fired body made of a porous conductive ceramic material such as lanthanum strontium cobalt ferrite LSCF = (La, Sr) (Co, Fe) O ₃ . The combination of the base members B and B of the adjacent cells 100 and 100 may be any one of a fuel electrode and a fuel electrode, a fuel electrode and an air electrode, an air electrode and an air electrode.

The current collecting member 300 is made of a dense metal material typified by a stainless steel material (SUS material) mainly composed of Fe and Cr, such as ZMG232L manufactured by Hitachi Metals, Ltd. The bonding material film 80 is a fired body made of a transition metal oxide (that is, a conductive ceramic material) having a spinel crystal structure such as MnCo ₂ O ₄ , CuMn ₂ O ₄ , or CuFe ₂ O ₄ .

(Shape of current collector)
Hereinafter, the three-dimensional shape of the current collecting member 300 will be described with reference to FIGS. As shown in FIG. 20, the current collecting member 300 includes a pair of fixing portions 310 and 310, and a connecting portion 320 that connects a pair of side end portions 311 and 311 that are part of the pair of fixing portions 310 and 310, Consists of Here, the current collecting member 300 corresponds to the “current collecting member” of the present invention, and the fixing portion 310 of the current collecting member 300 corresponds to the “plate portion of the current collecting member” of the present invention.

  The pair of fixing portions 310 and 310 are a pair of flat plate-like (thin rectangular parallelepiped) portions facing each other in parallel with a gap in the z-axis direction. Each fixing portion 310 is provided with a plurality (six in this example) of opening portions 312 (long holes penetrating in the thickness direction) spaced apart from each other in the x-axis direction and extending in parallel with each other in the y-axis direction. ing. In this example, each opening 312 has an elongated rectangular shape. That is, each opening 312 has a slit shape.

  The pair of fixing portions 310 and 310 are respectively joined to the joining surfaces (planes along the xy plane) of the corresponding base members B and B of the adjacent cells 100 and 100 via the joining material film 80 ( (See FIG. 19). The pair of side end portions 311 and 311 are regions extending in the x-axis direction at the end portion on the y-axis negative direction side of the pair of fixed portions 310 and 310, and are spaced apart from each other in the z-axis direction. It is a pair of strip-shaped parts facing each other in parallel.

  The connection part 320 has a first extension part and a second extension part 323. The first extending portion includes a pair of first portions 321 and 321 extending from the end on the x-axis positive direction side of the pair of side end portions 311 and 311 toward the y-axis negative direction side, and a pair of first portions. It is comprised from a pair of 2nd part 322,322 extended respectively toward a x-axis negative direction side from a pair of front-end | tip part in the front end side (y-axis negative direction side) of the part 321,321. The pair of first portions 321 and 321 and the pair of second portions 322 and 322 are both a pair of strip-shaped portions facing each other in parallel with a gap in the z-axis direction.

  The second extending portion 323 has a strip shape extending in the z-axis direction, and connects a pair of tip portions on the tip side (x-axis negative direction side) of the pair of second portions 322 and 322.

  A current collecting member 300 shown in FIG. 20 has a thin plate-like member produced in the shape shown in FIG. 21 by wire electric discharge machining or the like at the boundary line between the second extending portion 323 and the pair of second portions 322 and 322. It is completed by bending each along a right angle.

  In the thin plate-like member shown in FIG. 21, “a direction (paper surface) perpendicular to the extending direction (left and right direction of the paper surface) of the first portion 321 on the main surface (plane parallel to the paper surface) corresponding to the first portion 321. (Vertical direction) width A21 "," direction (right and left direction on the paper surface) orthogonal to the extending direction (up and down direction on the paper surface) of the main surface (plane parallel to the paper surface) corresponding to the second portion 322 " ) And a direction orthogonal to the extending direction of the second extending portion 323 (left and right direction on the drawing) in the main surface (a plane parallel to the drawing surface) corresponding to the second extending portion 323. The width A23 "(up and down direction in the drawing) is all greater than the plate thickness of the thin plate member shown in FIG.

  Hereinafter, actions and effects of the current collecting member 300 having the above three-dimensional shape will be briefly described with reference to FIGS. In the stack structure described above, three-dimensional relative displacement (relative position shift, relative position shift, etc.) inevitably occurs between adjacent cells 100 and 100 during SOFC operation. Can do. In addition, between the adjacent cells 100, 100, a pair of fixing portions 310, 310 are joined and fixed to the corresponding cells 100, respectively. This means that, in the current collecting member 300 shown in FIG. 20, a three-dimensional relative displacement (relative positional deviation, relative positional deviation, etc.) is unavoidable between the pair of fixed portions 310, 310. It also means that it can occur.

  Here, as shown in FIG. 22, the current collecting member 300 has low rigidity against “elastic deformation accompanied by relative rotational displacement as seen from the x-axis direction between the pair of fixing portions 310, 310”. This is because when the pair of fixing portions 310, 310 relatively receive a moment around the x-axis, the bending rigidity of the pair of first portions 321, 321 and the torsional rigidity of the pair of second portions 322, 322, And it is based on the bending rigidity of the 2nd extension part 323 being low.

  Further, as shown in FIG. 23, the current collecting member 300 has low rigidity against “elastic deformation accompanied by relative rotational displacement as seen from the y-axis direction between the pair of fixing portions 310 and 310”. This is because the torsional rigidity of the pair of first portions 321 and 321 and the bending of the pair of second portions 322 and 322 when the pair of fixing portions 310 and 310 receive a moment about the y-axis relatively. Based on low stiffness.

  Furthermore, as shown in FIG. 24, the current collecting member 300 has low rigidity against “elastic deformation accompanied by relative rotational displacement as seen from the z-axis direction between the pair of fixing portions 310 and 310”. This is based on the fact that the torsional rigidity of the second extending portion 323 is low when the pair of fixing portions 310 and 310 receive a moment around the z axis relatively.

  As described above, the current collecting member 300 has low rigidity with respect to all of “elastic deformation with relative rotation displacements between the pair of fixing portions 310 and 310 viewed from the three axial directions of the x axis, the y axis, and the z axis”. . Therefore, it can be said that the current collecting member 300 has low rigidity against “elastic deformation that causes a three-dimensional relative displacement between the pair of fixing portions 310, 310”. As a result, even if a three-dimensional relative displacement occurs between the adjacent cells 100, 100, “the pair of fixing portions 310, 310 of the current collecting member” and “the base member B of the adjacent cells 100, 100” The stress acting on the joint with “B” is reduced. As a result, the reliability at the joint is increased.

  Even if the current collecting member 300 having the shape shown in FIGS. 25 and 26 is adopted as the current collecting member 300, the same operation and effect as described above can be obtained. The current collecting member 300 shown in FIGS. 25 and 26 differs from the current collecting member 300 shown in FIGS. 20 and 21 only in the orientation of the plane of the second extending portion 323. In the current collecting member 300 shown in FIG. 25, a thin plate-like member produced in the shape shown in FIG. 26 by wire electric discharge machining or the like is used as a boundary line between the second extending portion 323 and the pair of second portions 322 and 322. It is completed by bending each along a right angle.

  In the thin plate-like member shown in FIG. 26, “a direction (paper surface) perpendicular to the extending direction (paper sheet vertical direction) of the first portion 321 on the main surface (plane parallel to the paper surface) corresponding to the first portion 321. (Width A21 in the left-right direction) "," direction (vertical direction on the paper surface) perpendicular to the extending direction (left-right direction on the paper surface) of the main surface (plane parallel to the paper surface) of the portion corresponding to the second portion 322 " ) And a direction orthogonal to the extending direction of the second extending portion 323 (left and right direction on the drawing) in the main surface (a plane parallel to the drawing surface) corresponding to the second extending portion 323. The width A23 "(up and down direction in the drawing) is all greater than the plate thickness of the thin plate member shown in FIG.

  As described above, when operating the SOFC stack structure described above, as shown in FIGS. 15 and 19, high-temperature (for example, 600 to 800 ° C.) “fuel gas” (hydrogen, etc.) and “air” are used. Circulate. That is, as shown in FIG. 15, the fuel gas introduced from the introduction passage 220 moves to the internal space of the fuel manifold 200, and then enters the gas flow path 11 of the corresponding cell 100 via each insertion hole 211. Each is introduced. The fuel gas that has passed through each gas flow path 11 is then discharged from the other end (free end) of each gas flow path 11 to the outside. On the other hand, as shown in FIG. 19, air is supplied from an air manifold (not shown) so as to move mainly along the cell width direction (y-axis direction) in each inter-cell space.

(Assembly method of stack structure)
Next, the stack structure including the “joint” according to the embodiment of the present invention illustrated in FIG. 15 and the like is assembled, for example, by the following procedure. First, a required number of completed cells 100, a completed fuel manifold 200, a required number of completed current collecting members 300, and the like are prepared. Next, the plurality of cells 100 are aligned and fixed in a stack using a predetermined jig or the like. Next, one end of each of the plurality of cells 100 is inserted into the corresponding insertion hole 211 of the support plate 210 at a time while maintaining the state in which the plurality of cells 100 are aligned and fixed in a stack. Next, a paste for the bonding material 250 is filled in each gap of the bonding portion between the insertion hole 211 and one end of the cell 100.

  Next, heat treatment is applied to the paste filled as described above (the paste is fired). As a result, the paste is solidified to form the bonding material 300. That is, one end of each cell 100 is joined and supported on the support plate 210 using the joining material 300. Thereafter, the predetermined jig is removed from the plurality of cells 100.

  Next, in the plurality of cells 100 arranged in a stack, the base members B and B of the adjacent cells 100 and 100 are bonded to the pair of fixing portions 310 and 310 of the current collecting member 300 using the bonding material film 80. Each is joined and fixed (this process will be described later). Thereafter, the above-described cantilever stack structure is completed through a process such as assembling the current collecting member 400 at a predetermined position of each cell 100.

  In the example described above, after one end of each cell 100 is joined and supported by the support plate 210, the base members B and B of the adjacent cells 100 and 100 are the pair of fixing portions 310 of the current collecting member 300, 310, the base members B and B of the adjacent cells 100 and 100 are joined and fixed to the pair of fixing portions 310 and 310 of the current collecting member 300, respectively. The portions may be joined and supported by the support plate 210, respectively.

  Hereinafter, the joining of the fixing portion 310 of each current collecting member 300 and the base member B of the corresponding cell 100 will be described with reference to FIG. FIG. 27 shows a part of a cross section (a plane parallel to the xz plane) along one of the cutting lines shown in FIG. 28 in the joint portion between the fixing portion 310 and the base member B of the current collecting member 300.

  As shown in the upper diagram of FIG. 27, first, a paste film for the bonding material film 80 is applied to the surface of the base member B of the cell 100 (bonding surface; in this example, a flat surface). Etc. are used. The paste film for the bonding material film 80 may be formed at the bonding portion of the fixing portion 310 of the current collecting member 300, or the bonding portion on the surface of the base member B and the fixing portion 310 of the current collecting member 300. You may form in a junction location, respectively. The thickness (total) of this paste film is 20 to 500 μm. Instead of this paste film, a tape made of the same material as the paste film may be attached to the joint location.

  Next, the fixing portion 310 of the current collecting member 300 is pressed against the upper surface of the paste film with a predetermined load. As a result, as shown in the middle diagram of FIG. 27, the “respective portions corresponding to the opening 312” and the “portion corresponding to the peripheral portion of the fixing portion 310” on the surface of the paste film are upward (in the negative z-axis direction). ). As a result, in the example shown in FIG. 27, the entire fixing portion 310 of the current collecting member 300 is embedded in the paste film. In other words, the entire area of the bottom surface (in this example, a flat surface) of the fixing portion 310, the outer peripheral surface 310 s of the peripheral portion of the fixing portion 310, and the inner side surface 312 s of each opening 312 provided in the fixing portion 310. Is covered with a paste film. Note that only a part (lower part) in the thickness direction of the fixing portion 310 of the current collecting member 300 may be embedded in the paste film. In this case, the entire bottom surface (in this example, a flat surface) of the fixed portion 310, only the lower portion of the outer surface 310s of the peripheral portion of the fixed portion 310, and the inner surface of each opening 312 provided in the fixed portion 310. Only the lower part of 312s is covered with the paste film.

  27, the paste film in which the fixing portion 310 of the current collecting member 300 is embedded is baked (temperature: 800 to 1000 ° C. (preferably 850 ° C., time: 1 hr)) to obtain a bonding material. A film 80 is formed. As a result, the fixing portion 310 of each current collecting member 300 and the corresponding base member B are bonded and fixed via the bonding material film 80, and each of the adjacent cells 100, 100 is in the corresponding inter-cell space. The current collecting member 300 is electrically connected via the bonding material film 80.

  In this “joint”, the fixing portion 310 of the current collecting member 300 is embedded in the joined body film 80, whereby the bottom surface of the fixing portion 310, the outer peripheral surface 310 s of the peripheral portion of the fixing portion 310, and each opening 312. The entire inner surface 312 s is covered with the bonding material film 80. Therefore, compared with the configuration in which only the bottom surface of the fixing portion 310 is in contact with the surface of the bonding material film 80 (that is, the configuration in which the fixing portion 310 is not embedded in the bonding material film 80), the current collecting member 300 and the bonding material film 80 The contact area between them increases, and the electrical resistance at the junction between the current collecting member 300 and the bonding material film 80 can be reduced.

(Suppression of peeling at the interface between the inner surface of the opening and the bonding material film)
When the above-described “configuration in which the fixing portion of the current collecting member provided with the opening is embedded in the bonding material film” is employed, the fixing portion of the current collecting member 300 is used when the paste for the bonding material film 80 is fired. In some cases, peeling is likely to occur at the interface between the inner surface 312 s of the opening 312 provided in 310 and the bonding material film 80.

  Here, as shown in FIGS. 29 and 30 which are partially enlarged views of the lower diagram of FIG. 27, “the height at which the inner surface 312s of the opening 312 is covered with the bonding material film 80 (the thickness direction of the fixing portion 310). (Distance in (z-axis direction)) (mm) ”is“ T ”, and“ the bonding material of the inner side surface 312s of the opening 312 in the cross section of the opening 312 along the thickness direction (z-axis direction) of the fixed part 310 ” The path length (mm) corresponding to the portion covered by the film 80 is “S”.

  FIG. 29 shows an example where the entire fixing portion 310 of the current collecting member 300 is embedded in the bonding material film 80, and FIG. 30 shows only the lower portion of the fixing portion 310 of the current collecting member 300 in the bonding material film. An example in the case of being embedded in 80 is shown. As shown in FIG. 29, when the entire fixing portion 310 of the current collecting member 300 is embedded in the bonding material film 80, the entire area of the inner side surface 312 s of the opening 312 is covered with the bonding material film 80. In this case, the value T is equal to the thickness (plate thickness) of the fixing portion 310 of the current collecting member 300. As shown in FIG. 30, when only the lower portion of the fixing portion 310 of the current collecting member 300 is embedded in the bonding material film 80, only the lower portion of the inner side surface 312 s of the opening 312 is bonded to the bonding material film 80. Covered with. In this case, the value T is smaller than the thickness (plate thickness) of the fixing portion 310 of the current collecting member 300.

  In the cross-sectional views shown in FIGS. 29 and 30, the path S is a line corresponding to a portion of the inner surface 312 s of the opening 312 that is covered with the bonding material film 80 (in the line corresponding to the inner surface 312 s, it is high in the drawing). Is a length obtained in consideration of fine undulations (irregularities) in a range corresponding to the thickness T). The path S is a value that takes into account the fine waviness (unevenness) that can be confirmed in an image by performing image analysis on an image with a magnification of 30 times as shown in FIGS. 29 and 30, for example. It can be calculated as (path length).

  The present inventor conducted various experiments and the like in order to cope with the above-mentioned problem of “peeling at the interface between the inner side surface 312 s of the opening and the bonding material film 80”. As a result, the present inventors have found that the occurrence of such peeling has a strong correlation with the value “S / T”. Hereinafter, test A in which this has been confirmed will be described.

(Test A)
In the test A, for the joined body equivalent to the “joined body of the fixed portion of the current collecting member and the base member” joined according to the procedure shown in FIG. A plurality of samples having different combinations of materials and values “S / T” were produced. Specifically, as shown in Table 1, 15 types (combinations) were prepared. Ten samples (N = 10) were made for each level.

For each sample, a rectangular parallelepiped member made of La (Ni, Fe, Cu) O ₃ was used as the base member. The porosity of the base member was 25 to 50%. As the shape of the fixing part of the current collecting member, a shape equivalent to the fixing part 310 (including six openings 312) shown in FIG. 21 was adopted. The shape (including the opening) of the fixed portion of the current collecting member was formed by wire electric discharge machining. The planar shape of the entire fixing part was a rectangle of 14 mm × 49 mm. The width H2 (mm) and length H3 (mm) of each opening, and the interval H1 (mm) between adjacent openings (see FIG. 21) were 1 mm, 43 mm, and 1 mm, respectively. The thickness of the fixed part of the current collecting member was 0.5 to 0.6 mm. In each sample, the entire fixing portion of the current collecting member was embedded in the bonding material film. Accordingly, the “height T” matches the “thickness” of the fixed portion of the current collecting member.

  For each sample, the “thickness” (= “height T”) of the fixing portion of the current collecting member is “each cross-section of the fixing portion along the 10 cutting lines shown in FIG. The “average value of each value (10 values) obtained at an arbitrary position on a parallel plane” was adopted. As the “path S” of the inner surface of the opening, “an arbitrary opening included in each cross section (a plane parallel to the xz plane) of the fixed portion along the 10 cutting lines shown in FIG. The average value of the respective values (10 values) obtained based on the image obtained by enlarging the cross-section 30 times at the position of is adopted. The adjustment of the path S with respect to the thickness T (adjustment of the value S / T) was made by adjusting the discharge energy in wire electric discharge machining. Specifically, the greater the discharge energy, the greater the value S (and hence the value “S / T”).

  Each sample (a joined body of the fixing portion of the current collecting member and the base member) was joined through the procedure shown in FIG. The thickness of the paste film for the bonding material film shown in the upper diagram of FIG. 27 was 30 to 300 μm. The paste was fired at 800 to 1000 ° C. (preferably 850 ° C.) for 1 hr. The porosity of the bonding material film after firing was 20 to 50%. For each sample, as shown in the lower diagram of FIG. 27, the entire area of the bottom surface (plane) of the fixed portion, the outer surface of the peripheral portion of the fixed portion, and the inner surface of each opening provided in the fixed portion, It was covered with a bonding material film (firing film). The distance between the bottom surface of the fixed part and the surface of the base member was 0.1 to 0.5 mm.

  As can be understood from Table 1, when the value “S / T” is smaller than 1.02 or larger than 1.31, “peeling at the interface between the inner surface of the opening and the bonding material film” occurs. If the value “S / T” is within the range of 1.02 to 1.31, it can be said that the peeling is difficult to occur. If the value “S / T” is less than 1.02, it is considered that the anchor effect at the bonding interface between the inner surface and the bonding material film cannot be sufficiently obtained, and thus peeling easily occurs. On the other hand, if the value “S / T” is larger than 1.31, it is considered that separation tends to occur because voids are likely to remain at the bonding interface between the inner surface and the bonding material film. Accordingly, the value “S / T” is preferably in the range of 1.02 to 1.31. The standard deviation of the value “S / T” in each sample is within 0.1.

  By the way, as shown in FIGS. 29 and 30, in actuality, fine waviness (unevenness) is inevitably generated on the inner surface of the opening. Specifically, in an image in which the cross section is enlarged 30 times, the diameter of the opening portion increases as the opening portion is separated from the base member in a portion covered with the bonding material film. Due to the presence of this undulation, at the interface between the inner surface of the opening and the bonding material film, a portion where the inner surface of the opening and the bonding material film do not contact each other is generated as shown in FIGS. obtain. Here, the “bonding rate” (%) of the interface between the inner surface of the opening and the bonding material film is covered with the bonding material film on the inner surface of the opening in the section of the opening with respect to the “height T”. The total length in the thickness direction of the fixed portions of the plurality of portions where the inner surface of the opening and the bonding material film are in contact with each other on the line corresponding to the portion (the range corresponding to the height T in the figure) ”Ratio. The “joining rate” can be confirmed, for example, by performing image analysis on an image having a cross-sectional enlargement ratio of 30 times as shown in FIGS. 29 and 30. It can be calculated based on the lengths of the “contact portion with the material film and the non-contact portion”.

  The present inventor has found that the occurrence of the “peeling at the interface between the inner surface of the opening and the bonding material film” has a strong correlation not only with the value “S / T” but also with the “bonding rate”. I found it. Hereinafter, test B in which this has been confirmed will be described.

(Test B)
In the test B, the combination of the material of the current collecting member (fixed part thereof), the material of the bonding material film, the value “S / T”, and the “bonding rate (%)” is different for the bonded body similar to the test A. Multiple samples were made. Specifically, as shown in Table 2, 15 types (combinations) were prepared. Ten samples (N = 10) were made for each level.

  The shape, material, etc. of each member used for each sample in Test B are the same as in Test A. In Test B, the value “S / T” was adjusted within the range of 1.02 to 1.31. As for “joining rate” for each sample, as in Test A, “arbitrary opening included in each cross section (plane parallel to the xz plane) of the fixed portion along the 10 cutting lines shown in FIG. The maximum value among the respective values (10 values) obtained based on an image obtained by enlarging the cross section 30 times at an arbitrary position of the part was adopted. The “bonding rate” is adjusted by adjusting the viscosity of the paste for the bonding material. Specifically, the “joining rate” increases as the viscosity of the paste decreases.

  In test B, a severe thermal cycle test (temperature range: normal temperature to 800 ° C., heating rate: 2 hours, cooling rate: 4 hours, 10 cycles) for each sample (fired body) produced. Was implemented.

  As can be understood from Table 2, when the value “S / T” is in the range of 1.02 to 1.31, when the “joining rate” is less than 21% or greater than 95%, "Peeling at the interface between the inner surface of the part and the bonding material film" is likely to occur, and if the "bonding rate" is in the range of 21 to 95 (%), it can be said that the peeling is difficult to occur. From the above, when the value “S / T” is in the range of 1.02 to 1.31, the separation is difficult to occur, and further, the “joining rate” is in the range of 21 to 95 (%). It can be said that peeling is less likely to occur. If the bonding rate is less than 21%, it is considered that sufficient strength cannot be obtained due to insufficient contact between the inner surface and the bonding material film, and peeling easily occurs. Further, if the “bonding rate” is greater than 95%, it is considered that peeling is likely to occur because the influence of the difference between the thermal expansion coefficient of the bonding material film and the thermal expansion coefficient of the current collecting member is strongly influenced. That is, it is considered that the unbonded portion exists at a certain rate as described above, so that distortion at the time of bonding can be eliminated, and as a result, peeling at the boundary between the inner surface and the bonding material film is less likely to occur. It is done.

  As described above, in the embodiment of the stack structure described above, in order to reduce the possibility that the separation occurs, the fixing portion 310 and the base member B of the current collecting member 300 for each of the adjacent cells 100 and 100 are separated. The value “S / T” is in the range of 1.02 to 1.31 (and the “joining rate” is in the range of 21 to 95 (%)) in at least one of the pair of joint portions. And the value “S / T” is in the range of 1.02 to 1.31 (and the “joining rate” is in the range of 21 to 95 (%) in both of the pair of joint portions. More preferred).

  The results of the tests A and B described above correspond to the case where the cell 100 is flat (the surface of the base member B is flat) and the fixing portion 310 of the current collecting member 300 is flat. The cell 100 has a cylindrical shape (therefore, the surface of the base member B is a part of the cylindrical surface), and the fixing portion 310 of the current collecting member 300 has a thin curved plate shape along the cylindrical surface. It has already been confirmed that similar results can be obtained. The results of the tests A and B described above correspond to the case where the entire fixing portion 310 of the current collecting member 300 is embedded in the bonding material film 80, but the lower side of the fixing portion 310 of the current collecting member 300. It has already been confirmed that the same result can be obtained even when only the portion is embedded in the bonding material film 80.

  The present invention is not limited to the above embodiment, and various modifications can be employed within the scope of the present invention. For example, in the above embodiment, a “horizontal stripe type” SOFC cell (a cell in which a plurality of power generation units are provided in one cell) is employed as the SOFC cell to be joined by the “joint”. As the SOFC cell to be joined by the “joined body”, a “vertical stripe type” SOFC cell may be adopted. The “vertical stripe type” SOFC cell has a stack structure in which a plurality of SOFC cells (cells each provided with one power generation unit) are stacked in the cell thickness direction.

  Moreover, in the said embodiment, although the connection part of the cell and current collection member in the stack structure of several SOFC cells is employ | adopted as a "joined body" concerning this invention, the "joined body" concerning this invention As an alternative, a connecting portion between the SOFC cell and the current collecting member existing alone may be employed.

Further, as shown in FIG. 31, the current collecting member 300 may have a coating film 310b. Specifically, the fixing portion 310 of the current collecting member 300 includes a fixing portion main body portion 310a and a coating film 310b. The coating film 310b covers both surfaces of the fixed portion main body portion 310a and covers the inner side surface 312a of the opening portion of the fixed portion main body portion 310a. The coating film 310 b covering the inner side surface 312 a defines the inner side surface 312 s of the opening 312 of the fixing unit 30. The coating film 310b can be formed from, for example, MnCo ₂ O ₄ , (La, Sr) MnO 3, or ZnO. The coating film 310b has a thickness of about 3 to 30 μm, for example.

  When the current collecting member 300 includes the coating film 310b, the height T is a height based on the boundary surface between the coating film 310b and the bonding material film 80. That is, in the thickness direction, the thickness of the coating film 310b positioned between the bonding material film 80 and the fixing portion 310 is included in the height T. In the case where the coating film 310b and the bonding material film 80 are made of the same material, for example, the coating film 310b and the bonding material film 80 are used by utilizing the fact that the porosity of the coating film 310b and the bonding material film 80 is different. Can be distinguished. In general, the porosity of the coating film 310 b is smaller than the porosity of the bonding material film 80. For this reason, the position where the porosity is different can be used as the boundary surface between the coating film 310b and the bonding material film 80. For example, a position where the porosity differs by 10% or more can be used as the boundary surface.

  When the current collecting member 300 includes the coating film 310b, the path S corresponds to a line corresponding to a portion covered with the bonding material film 80 on the coating film 310b covering the inner side surface 312a of the opening of the fixed main body 310a. This is the path.

DESCRIPTION OF SYMBOLS 10 ... Support substrate, 11 ... Fuel gas flow path, 20 ... Fuel electrode, 30 ... Interconnector, 40 ... Solid electrolyte membrane, 50 ... Reaction prevention membrane, 60 ... Air electrode, 70 ... Air electrode current collection membrane, 80 ... Joining Material film, 300 ... current collecting member, 310 ... fixing part, 312 ... opening, 312s ... inner surface, A ... power generation element part, B ... base member

Claims (4)

A fuel cell power generation unit including a fuel electrode, an electrolyte membrane, and an air electrode;
A current collecting member having a plate-like portion and made of metal;
The base member and the plate-like portion which are any one of the fuel electrode and the air electrode, or a conductive member having electronic conductivity electrically connected to any one of the fuel electrode and the air electrode A bonding material film made of a bonding material having electronic conductivity, interposed between
With
In the bonding material film, the base member and the plate-like portion are electrically connected so that the plate-like portion extends along a surface of the base member facing the plate-like portion. And joining the base member and the plate-like part,
The plate-like portion has an opening penetrating in the thickness direction of the plate-like portion,
When the plate-like portion is embedded in the bonding material film, the outer peripheral surface of the plate-like portion and the inner side surface of the opening are covered with the bonding material film,
The magnification of the cross section of the opening along the thickness direction of the plate-like portion with respect to the height (T) at which the inner surface of the opening is covered with the bonding material film is obtained based on an image of 30 times. The ratio (S / T) of the line path (S) corresponding to the portion covered with the bonding material film on the inner surface of the opening is 1.02 to 1.31.
Joined body.
The joined body according to claim 1,
The bonding material on the inner surface of the opening is obtained based on an image in which the enlargement ratio of the cross section of the opening is 30 times the height (T) at which the inner surface of the opening is covered with the bonding material film. It is the ratio of the total length in the thickness direction of the plate-like portion of a plurality of portions where the inner surface of the opening and the bonding material film are in contact with each other on a line corresponding to the portion covered with the film A joined body having a joining rate of 21 to 95%.
A first power generation unit of a fuel cell including a fuel electrode, an electrolyte membrane, and an air electrode;
A second power generation unit of a fuel cell including a fuel electrode, an electrolyte membrane, and an air electrode;
A first plate-like portion, a second plate-like portion, and a connecting portion for connecting the first and second plate-like portions, and a current collecting member made of metal,
Electronic conductivity electrically connected to any one of the fuel electrode and the air electrode of the first power generation unit, or one of the fuel electrode and the air electrode of the first power generation unit. A first bonding material film made of a bonding material having electronic conductivity and interposed between a first base member which is a conductive member and a first plate-like portion of the current collecting member;
Electronic conductivity electrically connected to any one of the fuel electrode and the air electrode of the second power generation unit, or any one of the fuel electrode and the air electrode of the second power generation unit. A second bonding material film made of a bonding material having electronic conductivity, interposed between the second base member, which is a conductive member, and the second plate-shaped portion of the current collecting member;
With
The first bonding material film includes the first base member and the first base member so that the first plate-like portion extends along a surface of the first base member facing the first plate-like portion. Joining the first base member and the first plate-like portion so that the one plate-like portion is electrically connected;
The second bonding material film is formed so that the second plate-shaped portion extends along a surface of the second base member facing the second plate-shaped portion, and the second base member and the second base member Joining the second base member and the second plate-like portion so that the two plate-like portions are electrically connected;
The first plate-like portion has a first opening that penetrates in the thickness direction of the first plate-like portion,
By embedding the first plate-like portion in the first bonding material film, the outer surface of the peripheral portion of the first plate-like portion and the inner surface of the first opening portion are the first bonding material. Covered with a membrane,
The magnification of the cross section of the first opening along the thickness direction of the first plate-like portion is 30 times the height (T) at which the inner surface of the first opening is covered with the first bonding material film. The ratio (S / T) of the line path (S) corresponding to the portion covered with the first bonding material film on the inner side surface of the first opening obtained based on the image of 1.02 is 1.02. ~ 1.31
The second plate-like portion has a second opening that penetrates in the thickness direction of the second plate-like portion,
Since the second plate-like portion is embedded in the second bonding material film, the outer surface of the peripheral portion of the second plate-like portion and the inner surface of the second opening portion are the second bonding material. Covered with a membrane,
The magnification of the cross section of the second opening along the thickness direction of the second plate-shaped portion is 30 times the height (T) at which the inner surface of the second opening is covered with the second bonding material film. The ratio (S / T) of the line path (S) corresponding to the portion covered with the second bonding material film on the inner surface of the second opening obtained based on the image of 1.02 is 1.02. ~ 1.31
Joined body.
The joined body according to claim 3,
The first opening, which is obtained based on an image in which the magnification of the cross section of the first opening is 30 times the height (T) at which the inner surface of the first opening is covered with the first bonding material film. The first plate of a plurality of portions where the inner surface of the first opening and the first bonding material film are in contact with each other on the line corresponding to the portion covered with the first bonding material film on the inner surface of the portion The first joining rate, which is a ratio of the total length in the thickness direction of the shaped part, is 21 to 95%,
The second opening, which is obtained based on an image in which the magnification of the cross section of the second opening is 30 times the height (T) at which the inner surface of the second opening is covered with the second bonding material film. The second plate of a plurality of portions where the inner surface of the second opening and the second bonding material film are in contact with each other on the line corresponding to the portion covered with the second bonding material film on the inner surface of the portion 2nd joining rate which is the ratio of the sum total of the length of the thickness direction of a shape part is 21-95%, and is a joined body.