JP6213614B2 - Solid oxide fuel cell and method for producing solid oxide fuel cell - Google Patents

Description

  The present invention relates to a solid oxide fuel cell that generates power by reacting with a fuel gas and an oxidant gas, and a method for manufacturing the same.

  A fuel cell is a cell that can directly convert chemical energy generated when fuel is oxidized into electric energy while continuously supplying fuel from the outside and exhausting combustion products. The types of fuel cells are classified according to the electrolyte, and those using a solid oxide having ionic conductivity for the electrolyte are called solid oxide fuel cells. As this solid oxide fuel cell, for example, the one described in Patent Document 1 is conventionally known.

  FIG. 8 is a cross-sectional view of a conventional solid oxide fuel cell. As shown in FIG. 8, a conventional solid oxide fuel cell 100 (hereinafter referred to as “fuel cell 100”) includes a metal substrate 101, a fuel electrode 102 disposed on one surface of the metal substrate 101, and a fuel electrode. An electrolyte 103 disposed on one surface of 102 and an air electrode 104 disposed on one surface of the electrolyte 103 are provided. A plurality of through holes 105 penetrating in the thickness direction are formed in the metal substrate 101, and these through holes 105 are formed by performing chemical etching on the metal substrate 101. When power is generated by the fuel cell 100, power is generated by supplying fuel gas to the fuel electrode 102 and supplying oxidant gas to the air electrode 104.

Japanese Patent No. 3940946

However, in the fuel cell 100 described above, since the metal substrate 101 is chemically etched, there are problems that the material and thickness of the metal substrate 101 are limited and that the cost is high.
Furthermore, if the number of through-holes 105 is increased in order to improve gas diffusibility, the contact area between the metal substrate 101 and the fuel electrode 102, that is, the current collection area becomes smaller, so that the performance deteriorates and the strength decreases. There was a problem.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a solid oxide fuel cell capable of improving strength and battery performance and a method for manufacturing the same.

  One aspect of the present invention is a solid oxide fuel cell for solving the above-described problem, wherein the fuel is disposed on at least one porous metal substrate and one surface of the at least one metal substrate. An electrode disposed on one surface of the fuel electrode, and an air electrode disposed on one surface of the electrolyte, and the metal substrate has a plurality of through-holes penetrating in the thickness direction. It is characterized by being.

  Alternatively, the present invention is not limited to the above, and is at least one porous metal substrate, an electrolyte disposed on one surface of the at least one metal substrate, and air disposed on one surface of the electrolyte. A solid oxide fuel cell in which the metal substrate has a fuel electrode activity, and the metal substrate has a plurality of through holes penetrating in the thickness direction. .

  The above-mentioned activity of the fuel electrode means that an oxidation reaction of a fuel gas such as hydrogen occurs on the surface of the fuel electrode.

  In the solid oxide fuel cell, the metal substrate is porous by forming a plurality of through holes penetrating in the thickness direction in the substrate green sheet and sintering the substrate green sheet having the through holes. It is preferable to be formed.

  According to such a structure, gas can be diffused in the metal substrate together with the through holes by using the porous metal substrate. Therefore, since it is not necessary to provide many through holes in order to improve gas diffusivity, the strength can be maintained. Further, since a sufficient current collecting area can be ensured while improving gas diffusivity, battery performance can be improved. Further, since chemical etching is not used when forming the through hole in the metal substrate, the material and thickness of the metal substrate are not limited, and the through hole can be formed at low cost. Therefore, according to the present invention, the strength can be improved and the battery performance can be improved.

  The solid oxide fuel cell of the present invention includes a plurality of the stacked metal substrates, and the through holes in the metal substrates constituting the plurality of metal substrates are in the metal substrate adjacent in the stacking direction. It is preferable that the hole diameter of the through hole in the metal substrate on the upper layer side in the stacking direction is smaller than the hole diameter of the through hole in the metal substrate on the lower layer side adjacent thereto.

  According to such a configuration, the through hole in the uppermost metal substrate in contact with the fuel electrode has the smallest diameter, and the contact area between the fuel electrode and the metal substrate can be increased. Therefore, by gradually reducing the diameter of the through hole, the current collection area can be increased while maintaining the gas diffusivity (arrival time) to the fuel electrode.

  Further, the present invention may have the following configuration in order to solve the above problems. That is, at least one porous metal substrate, a fuel electrode disposed on one surface of the at least one metal substrate, an electrolyte disposed on one surface of the fuel electrode, and one surface of the electrolyte A solid oxide fuel cell manufacturing method comprising a substrate forming step of forming the metal substrate, wherein the substrate forming step penetrates through the substrate green sheet in the thickness direction. It may be a method for manufacturing a solid oxide fuel cell comprising a through step for forming a plurality of through holes and a sintering step for sintering a green sheet for a substrate having the through holes.

  In addition, the present invention is not limited to this. At least one porous metal substrate, an electrolyte disposed on one surface of the at least one metal substrate, and an air electrode disposed on one surface of the electrolyte. And a substrate forming step for forming the metal substrate, wherein the substrate forming step forms a plurality of through-holes penetrating in the thickness direction in the green sheet for the substrate. And a sintering step of sintering the substrate green sheet having the through hole, wherein the substrate green sheet includes a material having a fuel electrode activity. It may be a method.

  According to the solid oxide fuel cell and the manufacturing method of the solid oxide fuel cell of the present invention, the strength can be improved and the power generation performance can be improved.

1 is a cross-sectional view of a solid oxide fuel cell according to an embodiment of the present invention. 1 is a bottom view of a solid oxide fuel cell according to an embodiment of the present invention. It is a figure explaining the manufacturing method of a solid oxide fuel cell. It is a flowchart of the manufacturing method of a solid oxide fuel cell. It is sectional drawing of the solid oxide fuel cell which concerns on other one Embodiment. It is sectional drawing of the solid oxide fuel cell which concerns on another one Embodiment. It is sectional drawing of the solid oxide fuel cell which concerns on another one Embodiment. It is sectional drawing of the conventional solid oxide fuel cell.

  Embodiments of the present invention will be described below with reference to the accompanying drawings. FIG. 1 is a cross-sectional view of a solid oxide fuel cell according to an embodiment of the present invention, and FIG. 2 is a bottom view of the solid oxide fuel cell. As shown in FIGS. 1 and 2, this solid oxide fuel cell 1 (hereinafter referred to as “fuel cell 1”) is disposed on a flat metal substrate 2 and one surface (front surface) of the metal substrate 2. A thin-film fuel electrode 3, a thin-film electrolyte 4 disposed on one surface (front surface) of the fuel electrode 3, and a thin-film air electrode 5 disposed on one surface (surface) of the electrolyte 4. ing.

  The metal substrate 2 is formed from a porous metal. Here, the term “porous” refers to a configuration having a large number of pores inside the metal substrate 2 and allows gas to pass through the plurality of pores. The metal substrate 2 has a plurality of through holes 6, 6... Which extend from the other surface (back surface) of the metal substrate 2 toward the fuel electrode 3. The fuel gas can be introduced into the fuel electrode 3. Further, the plurality of through holes 6, 6,... Are different in concept from the porous material. Further, the thickness of the metal substrate 2 is preferably 5 μm to 1000 μm, and more preferably 100 μm to 500 μm from the viewpoint of strength. Moreover, the hole diameter of the through hole 6 is preferably 0.1 μm to 250 μm, and more preferably 5 μm to 50 μm.

  The volume of the pores inside the porous metal substrate 2 is preferably 5 to 50% of the total volume of the metal substrate 2, and the occupied volume of the through holes 6 in the porous metal substrate 2 is the porous metal substrate 2. 2 to 10 to 70% of the total volume is preferred.

  The thicknesses of the fuel electrode 3 and the air electrode 5 can be 1 to 100 μm, preferably 5 to 50 μm, respectively.

  Moreover, the thickness of electrolyte can be 0.1 micrometer-100 micrometers, for example, Preferably it can be 1-50 micrometers.

  Next, the material of each component of the fuel cell 1 described above will be described.

  As a material of the metal substrate 2, for example, Fe, Ti, Cr, Cu, Ni, Ag can be used, one kind may be used alone, or two or more kinds of alloys may be used. As the alloy, for example, a stainless steel heat-resistant material can be used, and specifically, an austenitic stainless steel, a ferritic stainless steel, a nickel alloy such as Inconel or Hastelloy, or the like can be used.

  As the material of the fuel electrode 3, known materials can be used as the material of the fuel electrode of the solid oxide fuel cell. For example, a mixture of a metal catalyst and a ceramic powder material made of an oxide ion conductor is used. Can be used. As the metal catalyst used at this time, a material that is stable in a reducing atmosphere, such as nickel, iron, cobalt, or a noble metal (platinum, ruthenium, palladium, etc.) and has hydrogen oxidation activity can be used. In addition, as the oxide ion conductor, one having a fluorite structure or a perovskite structure can be preferably used. Examples of those having a fluorite structure include ceria-based oxides doped with samarium, gadolinium, and the like, and zirconia-based oxides containing scandium and yttrium. In addition, examples of those having a perovskite structure include lanthanum galide oxides doped with strontium and magnesium. Among the above materials, it is preferable to form the fuel electrode with a mixture of an oxide ion conductor and nickel. The mixed form of the ceramic material made of the oxide ion conductor and nickel may be a physical mixed form or a form of powder modification to nickel. Moreover, the ceramic material mentioned above can be used individually by 1 type or in mixture of 2 or more types. Moreover, the fuel electrode 3 can also be comprised using a metal catalyst alone.

  As the material of the electrolyte 4, those known as electrolytes for solid oxide fuel cells can be used. For example, ceria oxide (GDC) doped with samarium or gadolinium, lanthanum doped with strontium or magnesium An oxygen ion conductive ceramic material such as a galide oxide, zirconia oxide (YSZ) containing scandium or yttrium can be used.

As the material of the air electrode 5, known materials can be used as the material of the air electrode of the solid oxide fuel cell. Metal oxides can be used. Specifically, (Sm, Sr) CoO ₃ , (La, Sr) MnO ₃ , (La, Sr) CoO ₃ , (La, Sr) (Fe, Co) O ₃ , (La, Sr) (Fe, Co , Ni) O _{3 and the} like, and (La, Sr) (Fe, Co) O ₃ is preferable. The above-mentioned materials can be used alone or in combination of two or more.

  Next, a method for manufacturing a solid oxide fuel cell will be described. FIG. 3 is a diagram for explaining a method of manufacturing a solid oxide fuel cell. FIG. 4 is a flowchart of a method for manufacturing a solid oxide fuel cell.

  As shown in FIGS. 3 and 4, the fuel cell 1 can be manufactured by using a substrate green sheet 10, a fuel electrode green sheet 13, an electrolyte green sheet 14, and an air electrode paste 15. Each of these green sheets is a known green sheet for producing a solid oxide fuel cell, and a raw material powder, a binder, a dispersant, a plasticizer, a solvent, etc. are mixed to produce a slurry, and this slurry is formed into a thin film. It is a sheet in a state where it is extended into a shape and the solvent is removed.

  Here, an example of a method for manufacturing each of the green sheets will be described. For example, when manufacturing by the doctor blade method, the substrate green sheet 10 and the fuel electrode green sheet 13 can be manufactured by the following method. First, a pore-forming agent is added to the powder of the material for the metal substrate 2 or the fuel electrode 3 described above, a binder, a dispersant and a plasticizer are added, and the mixture is dispersed in a dispersion medium composed of an alcohol solvent such as ethanol or 2-propanol. A slurry is prepared. As for the addition amount of a pore making material, 5-20 w% is preferable. Since the added pore former burns and vaporizes during sintering, pores are formed at the locations where the pore former was present. Examples of the pore-forming agent include carbon-based powder and resin-based powder, but other materials may be used as long as they can be vaporized during sintering to form pores.

  Moreover, there is no restriction | limiting in the kind of binder used when producing the said slurry composition or kneading | mixing composition, A well-known organic or inorganic binder can be used. Organic binders include ethylene copolymers, styrene copolymers, acrylate and methacrylate copolymers, vinyl acetate copolymers, maleic acid copolymers, vinyl acetal resins, vinyl formal resins, polyvinyl Examples include butyral resins, vinyl alcohol resins, celluloses such as ethyl cellulose, and waxes.

  Next, the produced slurry is formed by a known doctor blade method to form a slurry layer on a film of polyethylene terephthalate or the like, and the dispersion medium is removed from the slurry layer to dry it. Alternatively, the fuel electrode green sheet 13 is formed. The dispersion medium is not limited to alcohol solvents, and other organic solvents such as toluene, xylene, and ketones may be used. In addition to the organic solvent, a slurry in which the mixed powder is dispersed in water may be used. For example, by using a predetermined dispersant, the mixed powder can be dispersed in water.

  The electrolyte green sheet 14 is produced by the following method. A binder, a dispersant, and a plasticizer are added to the powder of the material of the electrolyte 4 described above to prepare a slurry that is dispersed in a dispersion medium made of an organic solvent. The produced slurry forms a slurry layer on a film such as polyethylene terephthalate by a doctor blade method in the same manner as the fuel electrode and the like. The dispersion medium is removed from the slurry layer to dry the electrolyte, and the electrolyte green sheet 14 is formed.

  The air electrode paste 15 is a known paste for producing a solid oxide fuel cell, and can be produced by kneading a raw material powder of the material of the air electrode 5 with a binder, an organic solvent, or the like.

  Next, a method for manufacturing the fuel cell 1 will be described.

  When the fuel cell 1 is manufactured, first, as shown in FIGS. 3A, 3B, and 4, one substrate green sheet 10 is prepared, and the thickness direction with respect to the substrate green sheet 10 is prepared. A plurality of through-holes 12, 12,... Penetrating through are formed (penetration step S1). Specifically, the through holes 12 are formed in the substrate green sheet 10 using a known punching jig or the like. The number, the hole diameter, the formation position, and the like of the through holes 12 are not particularly limited and can be changed as appropriate.

  Next, as shown in FIG. 3C, the fuel electrode green sheet 13 is stacked on one surface (front surface) of the substrate green sheet 10 in which the through-holes 12 are formed (fuel electrode stacking step S2).

  Next, as shown in FIG. 3D, the electrolyte green sheet 14 is laminated on one surface (front surface) of the fuel electrode green sheet 13 (electrolyte lamination step S3). Thereby, it will be in the state by which each green sheet 10,13,14 was laminated | stacked.

Next, the laminate of the substrate green sheet 10, the fuel electrode green sheet 13, and the electrolyte green sheet 14 is co-sintered (first sintering step S4). The sintering temperature at this time is preferably 1100 ° C to 1500 ° C. As shown in FIG. 3E, the green sheet for substrate 10, the green sheet for fuel electrode 13, and the green sheet for electrolyte 14 become the metal substrate 2, the fuel electrode 3, and the electrolyte 4 by the sintering, respectively. At this time, when the metal substrate 2 is made of a metal material such as ferritic stainless steel or Ni, for example, in an inert atmosphere or reducing atmosphere such as N ₂ or Ar gas in order to prevent oxidation. Sintering is preferred. On the other hand, when the metal substrate 2 is made of a metal oxide material such as NiO, it can be sintered in an oxidizing atmosphere.

  Subsequently, as shown in FIG. 3F, the air electrode paste 15 is applied to one surface (surface) of the electrolyte 4 formed by sintering (application step S5). The air electrode paste 15 can be applied by, for example, a known screen printing method, doctor blade method, spray coating method, sputtering method, or the like.

Thereafter, the air electrode 5 is formed by sintering the air electrode paste 15, whereby the fuel cell 1 shown in FIG. 1 is manufactured (second sintering step S 6). The sintering temperature at this time is preferably 1100 ° C to 1500 ° C. Sintering is preferably performed in an inert atmosphere such as N ₂ or Ar gas or in a reducing atmosphere. However, sintering can be performed in an oxidizing atmosphere as long as the temperature can prevent oxidation of the metal substrate 2. . Further, when sintering is performed in an oxidizing atmosphere in the first sintering step S4, the air electrode is sintered by the above method after the reduction treatment of the metal substrate 2 before the second sintering step S6. However, the metal substrate 2 can be reduced after the second sintering step S6.

  According to the fuel cell 1 and the manufacturing method thereof according to the above embodiment, the metal substrate 2 is formed from the substrate green sheet 10 in the substrate forming step of forming the metal substrate 2, so that the material and thickness of the metal substrate 2 are limited. Therefore, the strength of the metal substrate 2 can be improved. Further, since the chemical etching is not used when the through hole 6 is formed in the metal substrate 2, the through hole 6 can be formed at a low cost. Therefore, according to the present invention, the strength can be improved and the cost can be suppressed.

  Further, according to the fuel cell 1, when supplying the fuel gas to the fuel electrode 3, the fuel gas can be introduced through the through hole 6 and can be diffused by the porous metal substrate 2. . Accordingly, since the introduction and diffusion of the fuel gas can be performed simultaneously, the fuel gas can be efficiently supplied to the fuel electrode 3.

  As mentioned above, although one Embodiment of this invention was described, the specific aspect of this invention is not limited to the said embodiment. For example, the configuration of the through hole 6 of the metal substrate 2 is not particularly limited as long as the through hole 6 is formed so as to penetrate in the thickness direction of the metal substrate 2. As shown in FIG. May be inclined. When the inclined through hole 6 is formed, the inclined through hole 12 is formed in the substrate green sheet 10 in the above-described through step S2. Even with such a configuration, the fuel gas can be introduced into the fuel electrode 3.

  FIGS. 6A to 6E are cross-sectional views of solid oxide fuel cells according to still other embodiments. As shown in FIGS. 6A to 6E, the number of metal substrates 2 is not particularly limited, and a plurality of metal substrates 2, 2... May be stacked in the thickness direction.

  6A to 6E, the formation positions and the hole diameters of the plurality of through holes 6, 6,... Are not particularly limited and can be changed as appropriate. For example, the through holes 6, 6... Of the stacked metal substrates 2, 2... May be aligned with each other in the stacking direction, and the centers of the holes may be shifted from each other. . Further, as indicated by a dotted line X in FIG. 6, it is preferable that the through holes 6, 6... Of the stacked metal substrates 2,. Moreover, it does not necessarily have to communicate with the lamination direction. Further, as shown in FIGS. 6C and 6D, a plurality of through holes 6 having different hole diameters may be formed in the metal substrate 2 of each layer.

  Moreover, as shown in FIG.6 (e), the structure which the hole diameter of several through-holes 6,6 .. shrinks in steps in the lamination direction of the metal substrate 2 may be sufficient. In the configuration shown in FIG. 6 (e), each through hole 6 in each metal substrate 2 constituting the plurality of stacked metal substrates 2 communicates with any one of the through holes 6 in the metal substrate 2 adjacent in the stacking direction. ing. As described above, since the through holes 6 are connected in the stacking direction of the plurality of metal substrates 2, gas can be passed through the through holes 6 communicating from the lowermost layer to the uppermost layer of the stacked metal substrates 2. Moreover, in this embodiment, in the metal substrate 2 which overlaps adjacently, the hole diameter of the through hole 6 in the upper metal substrate 2 is smaller than the hole diameter of the through hole 6 in the lower metal substrate 2. That is, the hole diameter of the through hole 6 in the upper metal substrate 2 in the stacking direction is smaller than the hole diameter of the through hole 6 in the lower metal substrate 2 adjacent thereto. Therefore, the hole diameter of the through hole 6 is gradually reduced from the lowermost metal substrate 2 toward the uppermost metal substrate 2. According to such a configuration, since the through hole 6 in the uppermost metal substrate 2 that is in contact with the fuel electrode 3 has the smallest diameter, by gradually reducing the diameter of the through hole, The current collection area can be increased while maintaining the gas diffusivity (arrival time).

  When manufacturing the fuel cell 1 in which a plurality of metal substrates 2 are stacked, a plurality of substrate green sheets 10 are prepared in the above-described penetration step S1, and a plurality of green sheets 10 for each of the plurality of substrates are provided. Through-holes 12 are formed. And if the several green sheet 10 for substrates in which the through-hole 12 was formed is laminated | stacked and each subsequent step S3-S6 is performed, the fuel cell 1 which has the several laminated metal substrate 2 will be manufactured.

  When manufacturing the fuel cell 1 in which the through holes 6 are reduced in diameter along the stacking direction of the metal substrate 2, the through holes 12 are large when the plurality of substrate green sheets 10 are stacked. The substrate green sheet 10 is laminated on the lower layer, and the substrate green sheet 10 having the small through-holes 12 is laminated on the upper layer. Thus, when the substrate green sheet 10 is sintered, the hole diameter of the through hole 6 in the upper metal substrate 2 is smaller than the hole diameter of the through hole 6 in the lower metal substrate 2.

  Moreover, in the said embodiment, although the fuel electrode 3 was arrange | positioned at the one surface (surface) of the metal substrate 2, this fuel electrode 3 was abbreviate | omitted and as shown to FIG. 7 (a), (b), metal The structure which arrange | positions the electrolyte 4 to the one surface (surface) of the board | substrate 2 may be sufficient. 7A and 7B, the same components as those in FIG. 1 or FIG. When the electrolyte 4 is directly arranged on the metal substrate 2 as described above, it is preferable that the material of the metal substrate 2 has a fuel electrode activity. For example, a mixed material of nickel oxide and iron oxide can be used. Examples of the material having the fuel electrode activity include Cu, Ni, Pt, Ru, etc., which are used alone or in combination of two or more with Fe, Cr, Al, Mn, Mo, Nb, etc. can do. Even with such a configuration, it is possible to generate electric power when the metal substrate 2 having the activity of the fuel electrode functions as the fuel electrode.

  Moreover, when manufacturing the fuel cell 1 in which the electrolyte 4 is disposed on one surface (front surface) of the metal substrate 2, the electrolyte stacking step S3 is performed without performing the fuel electrode stacking step S2. And if each subsequent step (1st sintering step S4, application | coating step S5, 2nd sintering step S6) is performed, the fuel cell 1 by which the electrolyte 4 is arrange | positioned on the one surface of the metal substrate 2 will be manufactured. When a material having the activity of the fuel electrode is used, co-sintering may be performed in a reducing atmosphere, or sintering is performed in an oxidizing atmosphere, and then only the metal substrate 2 is reduced to thereby reduce the fuel cell. 1 can be formed.

  Moreover, in the said embodiment, when forming the metal substrate 2 in the board | substrate formation step, it formed from the one sheet | seat green sheet 10, However, It is not limited to this structure, At least 1 layer (one sheet) The metal substrate 2 can be formed with the substrate green sheet 10). Therefore, the metal substrate 2 may be formed using a plurality of substrate green sheets 10. In this case, in the substrate forming step, first, a plurality of substrate green sheets 10 are prepared, and the plurality of substrate green sheets 10 are stacked in the thickness direction (substrate stacking step). Subsequently, a plurality of through-holes 12 penetrating in the thickness direction are formed with respect to the plurality of laminated green sheets 10 for substrate (penetration step S1). And if each subsequent step S3-S6 is performed, the fuel cell 1 which has the metal substrate 2 formed from the some green sheet 10 for substrates will be manufactured. Moreover, when forming the laminated | stacked metal substrate 2, it can form by further laminating | stacking the several laminated | stacked green sheet 10 for substrates, and sintering.

  Moreover, in the said embodiment, although the fuel electrode 3 is arrange | positioned on the metal substrate 2, when using the metal substrate 2 which does not have fuel electrode activity, the air electrode 5 is formed and the electrolyte 4, The fuel electrode 3 may be arranged.

  Moreover, in the said embodiment, although the air electrode 5 was formed by the method using the air electrode paste 15, the formation method of the air electrode 5 is not limited to this, The above-mentioned fuel electrode 3 and electrolyte 4 are mentioned. Similarly to the above, it can be formed by a method using a green sheet.

  Moreover, in the said embodiment, although the fuel electrode 3 and the electrolyte 4 were formed by the method using a green sheet, the formation method of the fuel electrode 3 and the electrolyte 4 is not limited to this, The above-mentioned air electrode Similarly to 5, it can be formed by a method using a paste.

  Thus, the formation method of the fuel electrode 3, the electrolyte 4 and the air electrode 5 is not particularly limited, and is a spray coating method, a spin coating method, an electrophoresis method, an ink jet method, a CVD method (chemical vapor deposition method), It can be produced using a general printing method such as an EVD method (electrochemical vapor deposition method), a PLD method (pulse laser deposition method), an aerosol deposition method, an ion plating method, or a sputtering method.

Moreover, in the said embodiment, although the porous metal substrate 2 was produced by sintering the board | substrate green sheet 10 containing the pore making material, the method of producing the porous metal substrate 2 is the method of producing the porous metal substrate 2. It is not limited to this configuration. For example, the porous metal substrate 2 can be produced by adjusting the sintering temperature when the substrate green sheet 10 is sintered using the substrate green sheet 10 that does not contain a pore-forming agent. Specifically, NiO—Fe ₂ O ₃ (mass ratio 9: 1, nickel oxide: average particle diameter 1 μm, iron oxide: average particle diameter 3 μm), which is a mixed material of nickel oxide and iron oxide, is used for a substrate. When the green sheet 10 is sintered at 1500 ° C. to obtain a dense substrate 2, a large number of pores can be formed inside the substrate 2 by sintering at 1400 ° C. lower than this temperature.

  Moreover, in the case of the said material, although a board | substrate is reduce | restored, it can also be made porous by the volume contraction in that case.

DESCRIPTION OF SYMBOLS 1 Solid oxide fuel cell 2 Metal substrate 3 Fuel electrode 4 Electrolyte 5 Air electrode 6 Through-hole 10 Green sheet for substrates 11 Laminate for substrates 13 Green sheet for fuel electrodes 14 Green sheet for electrolytes 15 Air electrode green sheets

Claims (6)

A porous at least one layer of metal substrate having pores;
A fuel electrode disposed on one surface of the at least one metal substrate;
An electrolyte disposed on one side of the fuel electrode;
An air electrode disposed on one surface of the electrolyte,
The metal substrate has a plurality of through-holes penetrating in a thickness direction different from the pores,
The fuel electrode is a solid oxide fuel cell arranged so as to close the through hole. A porous at least one layer of metal substrate having pores;
An electrolyte disposed on one side of the at least one metal substrate;
An air electrode disposed on one surface of the electrolyte,
The metal substrate has a fuel electrode activity, and the metal substrate has a plurality of through holes penetrating in a thickness direction different from the pores,
The electrolyte is a solid oxide fuel cell arranged so as to close the through hole. A porous at least one metal substrate having pores, a fuel electrode disposed on one surface of the at least one metal substrate, an electrolyte disposed on one surface of the fuel electrode, A method of manufacturing a solid oxide fuel cell comprising an air electrode disposed on one surface of an electrolyte,
A substrate forming step of forming the metal substrate;
The substrate forming step includes a step of forming a plurality of through holes penetrating the substrate green sheet in the thickness direction, and sintering the substrate green sheet having the through holes to form pores different from the through holes. Forming a metal substrate having a sintering step,
The method of manufacturing a solid oxide fuel cell, wherein the fuel electrode is disposed so as to close the through hole. A porous at least one metal substrate having pores, an electrolyte disposed on one surface of the at least one metal substrate, and an air electrode disposed on one surface of the electrolyte. A method for producing a solid oxide fuel cell, comprising:
A substrate forming step of forming the metal substrate;
The substrate forming step includes a step of forming a plurality of through holes penetrating the substrate green sheet in the thickness direction, and sintering the substrate green sheet having the through holes to form pores different from the through holes. Forming a metal substrate having a sintering step,
The green sheet for a substrate includes a substance having an activity of a fuel electrode,
The method for manufacturing a solid oxide fuel cell, wherein the electrolyte is disposed so as to close the through hole.   The method for producing a solid oxide fuel cell according to claim 3 or 4, wherein the green sheet for a substrate contains a pore-forming agent. 6. The method for manufacturing a solid oxide fuel cell according to claim 3, wherein in the through step, the through hole is formed by punching.