JP2015128024A - Method of manufacturing solid electrolyte type fuel battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a solid electrolyte type fuel battery preventing variation in pressure loss at an oxidant gas flow path and a fuel gas flow path, being hard to cause degradation.SOLUTION: A method of manufacturing a solid electrolyte type fuel battery includes a lamination press-bonding step for press-bonding components of a solid electrolyte type fuel battery 100 by lamination, and a sintering step in which the components are co-sintered for integration. In the lamination press-bonding step, a flow path formation disappearance material 70 that does not substantially change in thickness at the time of press-bonding is disposed between materials 12, 52 forming side wall parts of an oxidant gas flow path 12a and a fuel gas flow path 52a. As the flow path formation disappearance material 70, a material that disappears under heating at the time of co-sintering in the sintering step is used.

Description

  The present invention relates to a method for manufacturing a solid oxide fuel cell, and more particularly to a method for manufacturing a solid oxide fuel cell having a gas flow path.

A solid electrolyte fuel cell (also referred to as a solid oxide fuel cell (SOFC)) has a fuel electrode (anode): H ₂ + O ²⁻ → H ₂ O + 2e ⁻ , an air electrode (cathode): (1 / 2) A device that extracts electrical energy by the reaction of O ₂ + 2e ⁻ → O ²⁻ . In order to continuously extract electric energy, it is necessary to perform the reaction continuously. Therefore, oxidation of fuel gas (for example, H ₂ ) as an anode gas and air (O ₂ ) as a cathode gas supplied to the cathode is performed. The agent gas is continuously supplied.

  In such a fuel cell, a gas flow path for supplying gas to both electrodes is necessary. As a method for forming a gas flow path, when a solid electrolyte fuel cell is manufactured by integrally sintering a laminate in which each member forming a fuel battery cell is laminated, carbon powder is formed at a position where the gas flow path is formed. It has been proposed to form an oxidant gas flow path and a fuel gas flow path by disposing a sheet to be eliminated by firing (see, for example, Patent Document 1).

  In addition, it has been proposed to increase the mechanical strength of a fuel cell by forming a flow path with a porous body having communicating pores (see, for example, Patent Document 2).

JP 2009-252474 A JP 2000-294267 A

  In a fuel cell, it is known that the reaction rate has a dependency that the higher the temperature, the faster the reaction rate, and the reaction is an exothermic reaction. Accordingly, if the supply amount of the fuel gas or the oxidant gas varies depending on the position in the fuel cell, temperature variation occurs in the fuel cell. If there is temperature variation, the higher the temperature, the faster the material will deteriorate. As a result, the non-deteriorated portion compensates for the deteriorated portion to accelerate the reaction, so that a deterioration chain occurs in which the non-deteriorated portion is likely to deteriorate due to the temperature rise. In order not to generate this chain, it is important to reduce the variation in the gas supply amount, that is, the variation in the pressure loss in the flow path.

  However, in the technique of Patent Document 1, the laminate is formed by press-bonding by a method such as press molding. However, a sheet made of carbon powder may be deformed by press pressure. Further, if the solid electrolyte layer is made thin in order to reduce the internal resistance of the solid oxide fuel cell, the laminate is likely to warp. When the shape variation or deformation occurs in the flow path in this way, the pressure loss also varies. Further, in the technique of Patent Document 2, since a porous body is present in the flow path, the gas contact efficiency at the fuel electrode and the air electrode is reduced, and pressure loss occurs. Here, if the pore diameter of the porous body varies, the pressure loss varies.

  An object of the present invention is to solve the above-described problems, and to provide a method for manufacturing a solid oxide fuel cell that prevents variation in pressure loss in an oxidant gas flow channel and a fuel gas flow channel and is unlikely to cause deterioration. To do.

  In order to achieve the above object, a method for manufacturing a solid oxide fuel cell according to the present invention includes an air electrode layer, a solid electrolyte layer, and a stack of fuel electrode layers that are sequentially stacked, and the air electrode. A plurality of oxidant gas flow paths arranged to extend in a first direction for supplying oxidant gas to the surface of the layer; and for supplying fuel gas to the surface of the fuel electrode layer, A solid oxide fuel cell manufacturing method comprising a plurality of fuel gas passages arranged to extend in a second direction intersecting with a first direction, wherein the constituent members of the solid oxide fuel cell are A laminating material for forming a flow path, which includes a laminating and crimping step of laminating and crimping, and a firing step of integrating the constituent members by co-sintering, wherein the thickness does not substantially change during crimping in the laminating and crimping step. The oxidant gas flow path and Wherein arranged between the material forming the side wall portion of the fuel gas channel, as the channel formation loss material, characterized by using a material that disappears by heating during co-sintering in the firing step.

  In the method for producing a solid oxide fuel cell of the present invention, it is preferable to use a resin film as the flow path forming disappearing material.

  Moreover, it is preferable to use a material that disappears at a temperature lower than 800 ° C. as the flow path forming disappearance material.

  According to the method for manufacturing a solid oxide fuel cell of the present invention, it is possible to prevent variations in pressure loss in the oxidant gas flow channel and the fuel gas flow channel, and as a result, to provide a solid electrolyte fuel cell that is unlikely to deteriorate. can do.

  The above object, other objects, features and advantages of the present invention will become more apparent from the following detailed description of embodiments with reference to the drawings.

FIG. 1 is an example of a solid electrolyte fuel cell obtained by the method for manufacturing a solid oxide fuel cell according to the present invention, and is an exploded perspective view showing an exploded state of members constituting the solid electrolyte fuel cell. FIG. FIG. 2 is an exploded perspective view illustrating a method for forming a gas flow path. FIG. 3 is a plan view for explaining an arrangement position of the flow path forming vanishing material when the gas flow path is formed.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited or limited to the following examples. The drawings referred to below are schematically described, and the ratio of the dimensions of objects drawn in the drawings may be different from the ratio of dimensions of actual objects. The dimensional ratio of the object may be different between the drawings.

  FIG. 1 is an example of a solid electrolyte fuel cell obtained by the method for manufacturing a solid oxide fuel cell according to the present invention, and is an exploded perspective view showing an exploded state of members constituting the solid electrolyte fuel cell. FIG.

  The solid oxide fuel cell 100 includes, for example, a first separator 10, a power generation element 30, and a second separator 50. The power generation element 30 includes a laminated body of an air electrode layer 32, a solid electrolyte layer 31, and a fuel electrode layer 33 that are sequentially stacked. The air electrode layer 32 has an air electrode 32a, and the fuel electrode layer 33 has a fuel electrode 33a. The first separator 10 is formed with a plurality of oxidant gas flow paths 12a for supplying an oxidant gas to the air electrode 32a. The second separator 50 is formed with a plurality of fuel gas passages 52a for supplying fuel gas to the fuel electrode 33a. In the solid oxide fuel cell 100, the first separator 10, the power generation element 30, and the second separator 50 are stacked in this order.

  Note that the solid oxide fuel cell 100 of this embodiment has only one power generation element 30. However, the present invention is not limited to this configuration. The fuel cell of the present invention may have, for example, a plurality of power generation elements. In that case, adjacent power generation elements are separated by a separator.

  The method for producing a solid oxide fuel cell according to the present invention includes a lamination pressure bonding step of laminating and pressing the constituent members of the solid electrolyte fuel cell, and a firing step of integrating the constituent members by co-sintering including. And in the said lamination | stacking crimping | compression-bonding process, the loss | disappearance material for flow path formation in which thickness does not change substantially at the time of crimping | bonding is arrange | positioned between the materials which form the side wall part of the oxidizing gas flow path 12a and the fuel gas flow path 52a. At this time, the oxidant gas flow path 12a and the fuel gas flow path 52a are formed by using a material that disappears due to heating during co-sintering in the firing step as the flow path forming disappearance material.

  FIG. 2 is an exploded perspective view for explaining a method for forming a gas flow path, and FIG. 3 is a plan view for explaining an arrangement position of the flow path forming vanishing material when the gas flow path is formed. 2 and 3 exemplify a method of forming the fuel gas flow path 52a of the second flow path forming member 52 in the solid oxide fuel cell 100 of FIG. 1, the first flow path forming member 12 is illustrated. The method of forming the fuel gas channel 12a is the same.

  2 and 3, (a) shows a flow path forming disappearing material 70, and (b) and (c) show a second flow path forming member 52. FIG. 2 is a perspective view, FIG. 3 is a plan view, and (a) to (c) of each figure show corresponding members. The flow path forming disappearing material 70 has a shape corresponding to the fuel gas flow path 52 a so as to surround the linear convex portion 52 c constituting the second flow path forming member 52. FIG. 2D shows a perspective view of a state in which the flow path forming disappearing material 70 and the second flow path forming member 52 are combined into a single sheet. The green sheet of the second flow path forming member 52 including the flow path forming disappearing material 70 in the form of one sheet is interposed between the green sheet of the power generation element 30 and the green sheet of the second separator body 51. In addition, the green sheet of the first flow path forming member 12 including the flow path forming disappearing material 70 that is similarly formed into a single sheet is used as the green sheet of the power generation element 30 and the first sheet. Each member is laminated and pressure-bonded in the order shown in FIG. 1 so as to be between the green sheets of the separator body 11. The laminated body after pressure bonding is fired and co-sintered to integrate. Since the flow path forming disappearance material 70 uses a material that disappears by heating during co-sintering, the sheet of FIG. 2D is formed with a flow path as shown in FIG. 2E after firing. Only the member 52 remains. Similarly, the green sheet of the first flow path forming member 12 including the flow path forming disappearing material 70 is also in a state where only the flow path forming member 52 remains.

  It is important for the flow path forming disappearing material 70 that the thickness does not substantially change during pressure bonding. When a material that does not substantially change in thickness due to the press pressure at the time of pressure bonding is used, distortion and undulation are unlikely to occur in the shape of the flow path at the stage before firing. By firing in such a state where no distortion or the like is seen, the gas flow path formed after firing can be made homogeneous. Therefore, the pressure loss variation when the gas is flowed can be reduced, and the fuel cell can be hardly deteriorated. Here, “substantially” that the thickness does not change during pressure bonding means that the change in thickness due to the pressing pressure is within ± 1%.

  As the flow path forming disappearing material 70, it is preferable to use a resin film. As the resin film, films such as PET (polyethylene terephthalate), polyethylene naphthalate, polyphenylene sulfide, and polyimide can be used.

  Moreover, as the flow path forming disappearing material 70, it is preferable to use a material that disappears at a temperature of less than 800 ° C. More preferably, the material disappears at less than 600 ° C. The ceramic material constituting the solid oxide fuel cell starts to shrink around 800 ° C. during firing. Therefore, it is preferable that the flow path forming disappearing material 70 disappears at around 800 ° C., since unevenness is less likely to occur in the shrinkage.

In addition, the press pressure of the crimping | compression-bonding in the said lamination | stacking crimping | compression-bonding process is performed in the range of 1200-1800 kgf / cm < ² >, for example, and the calcination temperature in the said baking process is performed in the range of 1100-1400 degreeC, for example.

  The following can be used for the constituent members of the solid oxide fuel cell 100. Each component is prepared as a green sheet having a predetermined shape by mixing and molding the following materials with a binder and a solvent. A solid electrolyte fuel cell can be obtained through a lamination pressure bonding process in which these green sheets are laminated and pressure-bonded, and a firing process in which the obtained laminated body is integrated by co-sintering.

[Power generation element 30]
In the power generation element 30, the oxidant gas supplied from the oxidant gas flow path (oxidant gas manifold) 61 and the fuel gas supplied from the fuel gas flow path (fuel gas manifold) 62 react to generate power. Is the part where Here, the oxidant gas can be composed of, for example, an aerobic gas such as air or oxygen gas. The fuel gas may be a gas containing hydrogen gas or hydrocarbon gas such as carbon monoxide gas.

[Solid electrolyte layer 31]
The power generation element 30 includes a solid electrolyte layer 31. It is preferable that the solid electrolyte layer 31 has high ionic conductivity. The solid electrolyte layer 31 can be formed of, for example, stabilized zirconia or partially stabilized zirconia. Specific examples of the stabilized zirconia include 10 mol% yttria stabilized zirconia (10YSZ), 11 mol% scandia stabilized zirconia (11ScSZ), and the like. Specific examples of the partially stabilized zirconia include 3 mol% yttria partially stabilized zirconia (3YSZ). In addition, the solid electrolyte layer 31 is, for example, a ceria-based oxide doped with Sm, Gd, or the like, or La _0.8 Sr in which LaGaO ₃ is used as a base and a part of La and Ga is substituted with Sr and Mg, respectively. It can also be formed of a perovskite oxide such as _0.2 Ga _0.8 Mg _0.2 O _(3-δ) .

  The solid electrolyte layer 31 is sandwiched between the air electrode layer 32 and the fuel electrode layer 33. That is, the air electrode layer 32 is formed on one main surface of the solid electrolyte layer 31, and the fuel electrode layer 33 is formed on the other main surface.

[Air electrode layer 32]
The air electrode layer 32 has an air electrode 32a. The air electrode 32a is a cathode. In the air electrode 32a, oxygen takes in electrons and oxygen ions are formed. The air electrode 32a is preferably porous, has high conductivity, and is less likely to cause a solid-solid reaction with the solid electrolyte layer 31 and the like at high temperatures. The air electrode 32a can be formed of, for example, scandia-stabilized zirconia (ScSZ), Sn-doped indium oxide, PrCoO ₃ oxide, LaCoO ₃ oxide, LaMnO ₃ oxide, or the like. Specific examples of LaMnO ₃ -based oxides include, for example, La _0.8 Sr _0.2 MnO ₃ (common name: LSM), La _0.8 Sr _0.2 Co _0.2 Fe _0.8 O ₃ (common name: LSCF) and La _0.6 Ca _0.4 MnO ₃ (common name: LCM). The air electrode 32a may be made of a mixed material in which two or more of the above materials are mixed.

[Fuel electrode layer 33]
The fuel electrode layer 33 has a fuel electrode 33a. The fuel electrode 33a is an anode. In the fuel electrode 33a, oxygen ions and the fuel gas react to emit electrons. The fuel electrode 33a is preferably porous, has high electron conductivity, and does not easily cause a solid-solid reaction with the solid electrolyte layer 31 and the like at a high temperature. The fuel electrode 33a can be made of, for example, NiO, yttria stabilized zirconia (YSZ) / nickel metal porous cermet, scandia stabilized zirconia (ScSZ) / nickel metal porous cermet, or the like. The fuel electrode layer 33 may be made of a mixed material obtained by mixing two or more of the above materials.

[First separator 10]
On the air electrode layer 32 of the power generation element 30, the first separator 10 constituted by the first separator body 11 and the first flow path forming member 12 is disposed. The first separator 10 is formed with an oxidant gas passage 12a for supplying an oxidant gas to the air electrode 32a. The oxidant gas flow path 12a extends from the oxidant gas manifold 61 from the x1 side in the x direction toward the x2 side. The oxidant gas flow path 12a is partitioned into a plurality in the y direction, which is the width direction of the oxidant gas flow path 12a, by a plurality of linear protrusions 12c extending along the x direction.

  The materials of the first separator body 11 and the first flow path forming member 12 are not particularly limited. Each of the first separator body 11 and the first flow path forming member 12 can be formed of, for example, stabilized zirconia such as yttria stabilized zirconia, partially stabilized zirconia, or the like. Further, each of the first separator body 11 and the first flow path forming portion 12 is made of, for example, a conductive ceramic such as lanthanum chromite or strontium titanate to which a rare earth metal is added, or an insulating property such as alumina or zirconium silicate. It can also be formed from ceramics.

  A plurality of via-hole electrodes 12c1 are embedded in each of the plurality of linear protrusions 12c. The plurality of via-hole electrodes 12c1 are formed so as to penetrate the plurality of linear protrusions 12c in the z direction. The first separator body 11 has a plurality of via hole electrodes 11c corresponding to the positions of the plurality of via hole electrodes 12c1. The plurality of via-hole electrodes 11 c are formed so as to penetrate the first separator body 11. By the plurality of via-hole electrodes 11c and the plurality of via-hole electrodes 12c1, the surface on the opposite side of the linear separator 12c from the first separator body 11 is opposite to the linear protrusion 12c of the first separator body 11. A plurality of via-hole electrodes reaching the surface are formed.

The material of the via hole electrode 11c and the via hole electrode 12c1 is not particularly limited. Each of the via-hole electrode 11c and the via-hole electrode 12c1 includes, for example, an Ag—Pd alloy, an Ag—Pt alloy, lanthanum chromite (LaCrO ₃ ) added with alkaline earth metal, lanthanum ferrate (LaFeO ₃ ), lanthanum strontium manganite. (LSM: Lanthanum Strontium Manganite) or the like.

[Second separator 50]
On the fuel electrode layer 33 of the power generation element 30, a second separator 50 configured by a second separator body 51 and a second flow path forming member 52 is disposed. The second separator 50 is formed with a fuel gas passage 52a for supplying fuel gas to the fuel electrode 33a. The fuel gas flow path 52a extends from the fuel gas manifold 62 from the y1 side in the y direction toward the y2 side. The fuel gas flow path 52a is divided into a plurality in the x direction, which is the width direction of the fuel gas flow path 52a, by a plurality of linear protrusions 52c extending along the y direction.

  The materials of the second separator body 51 and the second flow path forming member 52 are not particularly limited. Each of the second separator main body 51 and the second flow path forming member 52 can be formed of, for example, stabilized zirconia, partially stabilized zirconia, or the like. Each of the second separator main body 51 and the second flow path forming member 52 includes, for example, conductive ceramics such as lanthanum chromite and strontium titanate to which rare earth metals are added, and insulating properties such as alumina and zirconium silicate. It can also be formed from ceramics.

  A plurality of via-hole electrodes 52c1 are embedded in each of the plurality of linear protrusions 52c. The plurality of via-hole electrodes 52c1 are formed so as to penetrate the plurality of linear protrusions 52c in the z direction. The second separator main body 51 has a plurality of via hole electrodes 51c corresponding to the positions of the plurality of via hole electrodes 52c1. The plurality of via hole electrodes 51 c are formed so as to penetrate the second separator body 51. By the plurality of via hole electrodes 51c and the plurality of via hole electrodes 52c1, the surface of the linear convex portion 52c opposite to the second separator main body 51 from the surface opposite to the linear convex portion 52c of the second separator main body 51 is provided. A plurality of via-hole electrodes reaching the surface are formed.

  The material of the via hole electrode 51c and the via hole electrode 52c1 is not particularly limited. Each of the via-hole electrode 51c and the via-hole electrode 52c1 is made of, for example, Ag—Pd alloy, Ag—Pt alloy, nickel metal, yttria stabilized zirconia (YSZ) / nickel metal, scandia stabilized zirconia (ScSZ), nickel metal, or the like. Can be formed.

Example 1
In order to form the second flow path forming member 52 having the shape shown in FIG. 1, a PET film having a shape corresponding to the fuel gas flow path 52 a (see FIG. 2A) as the flow path forming disappearing material 70 (see FIG. 2A). A thickness of 50 μm) was prepared.

  In the solid oxide fuel cell support structure 100, the second separator 50 was formed using a green sheet using the following material powder.

10% by weight of zircon (ZrSiO ₄ ) added to zirconia (ZrO ₂ ) (ceria stabilized zirconia: CeSZ) stabilized with 12 mol% of ceria (CeO ₂ ) (electrical insulating material).

  Using the material powder, a green sheet was produced as follows for the flow path forming member 52 including the linear convex portion 52c formed by the members shown in FIGS. 2B and 2C.

  For the flow path forming member 52, the volume fraction of each of the material powder, the polyvinyl butyral binder, and a mixture of ethanol and toluene as the organic solvent (weight ratio is 1: 4) It mixed so that it might become 15 vol% of powder, 15 vol% of binders, and 70 vol% of organic solvents. After mixing, a green sheet was prepared by a doctor blade method. The thickness of the green sheet was 60 μm.

  In the green sheet on which the linear protrusions 52c are formed, through holes for forming a plurality of via hole electrodes 52c1 are formed as shown in FIG. 2 (b). The formed through hole was filled with a paste composed of 50% by weight of silver and 50% by weight of palladium, thereby preparing a conductive paste filling layer for forming the via-hole electrode 52c1. The green sheet which forms this linear convex part 52c was arrange | positioned in the space | gap part of the said PET film.

  As for other parts of the second flow path member 52, a green sheet having the shape shown in FIG. 2 (c) is used, and the members shown in FIGS. A sheet (green sheet for a flow path forming member) shown in (d) was produced. When the sheet of FIG. 2D is baked, the flow path forming disappearing material 70 (PET film) shown in FIG. 2A disappears, and the member of FIG. A path forming member 52 is produced. A green sheet for the first flow path forming member 12 was produced in the same manner. Here, the interval between the flow paths (the distance between the linear convex portion and the adjacent linear convex portion) was set to 1 mm.

  About each member which comprises the electric power generation element 30, material powder was prepared as follows.

Solid electrolyte layer 31: zirconia (ZrO ₂ ) (scandiaceria stabilized zirconia: ScCeSZ) stabilized with scandia (Sc ₂ O ₃ ) added in an amount of 10 mol% and ceria (CeO ₂ ) added in an amount of 1 mol%.

Air electrode layer 32: stabilized with 60% by weight of La _0.8 Sr _0.2 MnO ₃ , 10 mol% of scandia (Sc ₂ O ₃ ) and 1 mol% of ceria (CeO ₂ ). Mixture with 40% by weight of zirconia (ZrO ₂ ) (scandiaceria stabilized zirconia: ScCeSZ).

Fuel electrode layer 33: Zirconia (ZrO ₂ ) stabilized with 60% by weight of nickel oxide (NiO), scandia (Sc ₂ O ₃ ) with an addition amount of 10 mol% and ceria (CeO ₂ ) with an addition amount of 1 mol% (Scandiaceria stabilized zirconia: ScCeSZ) A mixture with 40% by weight.

  Green sheets of the solid electrolyte layer 31, the air electrode layer 32, and the fuel electrode layer 33 were produced as follows.

  20 to 40 parts by weight of carbon powder was added to 100 parts by weight of the material powder of each of the air electrode layer 32 and the fuel electrode layer 33 so that pores necessary for gas diffusion were sufficiently formed after firing. Each volume fraction of this mixed powder, a polyvinyl butyral binder, and a mixture of ethanol and toluene as an organic solvent (mixing ratio is 1: 4 by weight) has a material volume of 15 vol%, a binder of 15 vol%, It mixed so that it might become 70 vol% of organic solvents. After mixing, green sheets of the air electrode layer 32 and the fuel electrode layer 33 were produced by the doctor blade method.

  The volume fraction of each of the material powder of the solid electrolyte layer 31, the polyvinyl butyral binder, and a mixture of ethanol and toluene as an organic solvent (weight ratio is 1: 4) is 15 vol% of the material powder, It mixed so that it might become 15 vol% of binders and 70 vol% of organic solvents. After mixing, a green sheet of the solid electrolyte layer 31 was produced by a doctor blade method.

The green sheets constituting the solid oxide fuel cell 100 produced as described above were laminated in the order shown in FIG. This laminate was pressure bonded by cold isostatic pressing (CIP) at a pressure of 1500 kgf / cm ² and a temperature of 80 ° C. for 5 minutes. The pressure-bonded body was degreased within a temperature range of 400 to 500 ° C., and then fired by holding for 6 hours within a temperature range of 1100 to 1400 ° C. By this baking, the above PET film (flow-path forming lost material 70) disappeared. Thereby, the solid oxide fuel cell 100 of Example 1 having the oxidant gas channel 12a and the fuel gas channel 52a could be formed.

  In the solid oxide fuel cell 100 of Example 1, the thickness of the first separator body 11 of the first separator 10 after firing is 190 μm, and the thickness of the first flow path forming member 12 after firing (oxidation). The height of the agent gas passage 12a) was 120 μm. The thickness of the second separator body 51 of the second separator 50 after firing was 180 μm, and the thickness of the second flow path forming member 52 after firing (the height of the fuel gas flow path 52a) was 120 μm. It was. The power generation element 30 has a configuration of an air electrode layer 32 (thickness after firing: 300 μm) / solid electrolyte layer 31 (thickness after firing: 50 μm) / fuel electrode layer 33 (thickness after firing: 300 μm). .

(Comparative Example 1)
As Comparative Example 1, a solid electrolyte fuel cell was produced in the same manner as in Example 1 except that a sheet made of carbon powder and a binder was used instead of the PET film of Example 1. In this example, the carbon powder disappeared by firing, whereby the oxidant gas passage 12a and the fuel gas passage 52a could be formed. The sheet is prepared by mixing carbon powder, a polyvinyl butyral binder, and a mixture of ethanol and toluene as an organic solvent such that the respective volume fractions are 15 vol% of material powder, 15 vol% of binder, and 70 vol% of organic solvent. This is a manufactured sheet.

(Comparative Example 2)
As Comparative Example 2, a solid oxide fuel cell was produced in the same manner as in Example 1 except that instead of the PET film of Example 1, a sheet made of acrylic resin beads, zirconia powder, and a binder was used. In this example, the acrylic resin beads disappeared by firing, whereby the oxidant gas channel 12a and the fuel gas channel 52a could be formed. The sheet comprises acrylic resin beads, zirconia powder, a polyvinyl butyral binder, and a mixture of ethanol and toluene as an organic solvent, each having a volume fraction of 15 vol% of material powder, 15 vol% of binder, and 70 vol% of organic solvent. It is the sheet | seat produced by mixing so that it may become.

Table 1 shows the results of evaluating the variation in pressure loss by flowing gas through the gas flow paths of the solid oxide fuel cells obtained in Examples and Comparative Examples. The variation in pressure loss is measured by measuring the amount of gas coming out of each flow path when 4 × 10 ⁻³ m ³ / min N ₂ gas is allowed to flow through the manifold. Defined.

  In Example 1 using a PET film as the flow path forming disappearance material, it can be seen that the variation in pressure loss is extremely small compared to the comparative example. This is presumably because the PET film was not deformed by the press pressure when the laminated green sheet was pressure-bonded, and the flow path shape was not deformed in the pre-firing stage. On the other hand, in the case of the sheet made of carbon powder and binder used in Comparative Example 1 and the sheet made of acrylic resin beads, zirconia powder and binder used in Comparative Example 2, It is considered that these sheets were deformed by the press pressure, and the pressure loss was greatly varied because the sheets were fired in a state where the flow path was deformed.

  Thus, by manufacturing a solid oxide fuel cell using a flow path disappearing material such as a PET film whose thickness does not substantially change during pressure bonding, pressure loss in the oxidant gas flow path and the fuel gas flow path is reduced. It can be seen that a solid electrolyte fuel cell with little variation can be obtained. By adopting such a manufacturing method, it is possible to obtain a solid oxide fuel cell that is unlikely to deteriorate.

DESCRIPTION OF SYMBOLS 100 Solid electrolyte fuel cell 10 1st separator 11 1st separator main body 11c Via-hole electrode 12 1st flow-path formation member 12a Oxidant gas flow path 12c Linear convex part 12c1 Via-hole electrode 30 Electric power generation element 31 Solid electrolyte layer 32 Air electrode layer 32a Air electrode 33 Fuel electrode layer 33a Fuel electrode 50 Second separator 51 Second separator body 51c Via hole electrode 52 Second flow path forming member 52a Fuel gas flow path 52c Linear protrusion 52c1 Via hole electrode 61 Oxidation Agent gas manifold 62 Fuel gas manifold 70 Flow path forming vanishing material

Claims (3)

A power generation element composed of a laminate of an air electrode layer, a solid electrolyte layer, and a fuel electrode layer, which are sequentially stacked;
A plurality of oxidant gas flow paths arranged to extend in a first direction to supply oxidant gas to the surface of the air electrode layer;
A solid oxide fuel cell comprising: a plurality of fuel gas flow paths arranged to extend in a second direction intersecting the first direction to supply fuel gas to the surface of the fuel electrode layer A manufacturing method comprising:
A lamination crimping step of laminating the components of the solid oxide fuel cell and crimping;
And a firing step in which the constituent members are integrated by co-sintering,
In the laminating pressure bonding step, a flow path forming disappearing material whose thickness does not substantially change at the time of pressure bonding is disposed between the materials forming the side walls of the oxidant gas flow path and the fuel gas flow path,
A method for producing a solid oxide fuel cell, wherein a material that disappears by heating during co-sintering in the firing step is used as the flow path forming disappearance material.   The method for producing a solid oxide fuel cell according to claim 1, wherein a resin film is used as the flow path forming disappearing material. The method for producing a solid oxide fuel cell according to claim 1, wherein a material that disappears at a temperature of less than 800 ° C. is used as the flow path forming disappearance material.

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