JP5388833B2 - Cell stack, fuel cell module including the same, and fuel cell device - Google Patents

Description

  The present invention relates to a cell stack, a fuel cell module including the cell stack, and a fuel cell device.

  In recent years, various fuel cell modules in which a cell stack formed by electrically connecting a plurality of fuel cells is accommodated in a storage container have been proposed as next-generation energy.

  In the cell stack, a current collecting member is arranged between a plurality of fuel cells, and fuel cells adjacent to the current collecting member are joined by a conductive joining material, etc., thereby electrically connecting each fuel cell. Are connected in series.

  Here, when joining the current collecting member and the fuel battery cell, the conductive joining made of LaSrCoFe-based perovskite type oxides having different average particle diameters and having the same components of coarse powder and fine powder on the surface of the current collecting member A method of applying a material has been proposed (see, for example, Patent Document 1).

JP 2004-265742 A

  However, when the current collecting member and the fuel cell are joined using the conductive joining material made of LaSrCoFe-based perovskite type oxide having different average particle diameters and the same composition of coarse powder and fine powder, a cell stack is produced. At the time of operation of the fuel cell device or during the operation of the fuel cell device, stress is concentrated inside the conductive bonding material due to the difference in thermal expansion between the conductive bonding material and the interconnector or current collecting member. May occur. As a result, the long-term reliability of the cell stack may be reduced.

  Therefore, an object of the present invention is to provide a cell stack excellent in long-term reliability that can suppress the occurrence of cracks in the conductive bonding material even when the cell stack is manufactured or the fuel cell device is operated, and the cell stack includes the same. An object of the present invention is to provide a fuel cell module and a fuel cell device.

In the cell stack of the present invention, a fuel electrode layer, a solid electrolyte layer, and an air electrode layer made of a LaSrCoO ₃ -based perovskite oxide are stacked in this order on one of the opposing portions of the surface of the conductive support. And a plurality of fuel cells having an interconnector made of LaCrO ₃ perovskite oxide on the other side, the air electrode layer of one of the adjacent fuel cells, and the interconnector of the other fuel cell. Each of which is electrically connected in series by a current collecting member via a conductive bonding material, wherein the conductive bonding material is made of a LaSrCoO ₃ -based perovskite oxide having an average particle size of 1 μm or less. fines and the average particle diameter 3μm or more LaSrAO ₃ perovskite oxide (a is, Mn, Co, Al and F The coarse powder has a thermal expansion coefficient smaller than that of the fine powder, and the coarse powder contains more than the fine powder. It is characterized by.

In such a cell stack, the conductive bonding material has an average particle diameter of 1μm or less of the LaSrCoO ₃ perovskite of oxide fines and an average particle diameter 3μm or more LaSrAO ₃ perovskite oxide (A is, Mn, Co, Al, and Fe (including at least one of Co), coarse powder mixture, the thermal expansion coefficient of the coarse powder is smaller than that of the fine powder, and the coarse powder contains more than the fine powder Therefore, the thermal expansion coefficient of the conductive bonding material can be reduced.

  Thereby, the thermal expansion coefficients of the conductive bonding material, the interconnector and the current collecting member can be made closer, and the stress generated in the conductive bonding material can be relaxed.

  Thereby, the stress which arises inside an electroconductive joining material can be relieved, and it can suppress that a crack arises in an electroconductive joining material. Therefore, a cell stack having excellent long-term reliability can be obtained.

In the cell stack of the present invention, the coarse powder is preferably made of a LaSrMnO ₃ -based perovskite oxide.

In such a cell stack, since the coarse powder is made of a LaSrMnO ₃ -based perovskite oxide, the thermal expansion coefficient between the conductive bonding material and the interconnector or the current collecting member can be made closer and more conductive. The stress generated in the bonding material can be reduced. Thereby, it can suppress that a crack arises in an electroconductive joining material, and can improve the long-term reliability of a cell stack.

In the cell stack of the present invention, it is preferable that the coarse powder is composed of a LaSrCoO ₃ perovskite oxide and the composition ratio of Co constituting the fine powder is larger than the composition ratio of Co constituting the coarse powder.

  In such a cell stack, the coefficient of thermal expansion of the coarse powder is smaller than that of the fine powder, and the coarse powder is contained more than the fine powder, and the composition ratio of Co constituting the fine powder constitutes the coarse powder. Since it is larger than the composition ratio of Co, it is possible to suppress the generation of cracks in the conductive bonding material and to improve the conductivity of the conductive bonding material.

  Since the fuel cell module of the present invention is characterized in that the cell stack is stored in a storage container, the fuel cell module is excellent in long-term reliability.

  The fuel cell device of the present invention is a fuel cell device having excellent long-term reliability since the fuel module and the auxiliary machine for operating the fuel cell module are housed in an outer case. Can do.

The cell stack of the present invention, the conductive bonding material has an average particle diameter of 1μm or less of the LaSrCoO ₃ perovskite of oxide fines and an average particle diameter 3μm or more LaSrAO ₃ perovskite oxide (A is, Mn, Co , Comprising at least one of Al and Fe), the thermal expansion coefficient of the coarse powder is smaller than the thermal expansion coefficient of the fine powder, and the coarse powder is contained more than the fine powder. Therefore, the thermal expansion coefficients of the conductive bonding material, the interconnector, and the current collecting member can be made closer, and the stress generated in the conductive bonding material can be reduced. Thereby, the stress which arises inside an electroconductive joining material can be relieved, and it can suppress that a crack arises in an electroconductive joining material. Therefore, a cell stack having excellent long-term reliability can be obtained.

  In addition, the fuel cell module of the present invention can be a fuel cell module having excellent long-term reliability because the cell stack described above is housed in the housing container. The fuel cell device of the present invention is a fuel cell having excellent long-term reliability since the fuel cell module described above and an auxiliary machine for operating the fuel cell module are housed in an outer case. It can be a device.

An example of the cell stack apparatus which comprises the cell stack of this invention is shown, (a) is a side view which shows a cell stack apparatus schematically, (b) is a top view which expands and shows a part of (a) It is. It is sectional drawing which shows roughly joining of the current collection member and fuel cell in the cell stack of this invention. It is an external appearance perspective view which shows an example of the fuel cell module which accommodates the cell stack apparatus which comprises the cell stack of this invention in a storage container. It is a disassembled perspective view which shows an example of the fuel cell apparatus of this invention.

  FIG. 1 shows an example of a cell stack apparatus comprising the cell stack of the present invention, (a) is a side view schematically showing the cell stack apparatus, and (b) is an enlarged view of part of (a). The figure is an excerpted portion surrounded by a dotted frame shown in FIG. In the following drawings, the same numbers are assigned to the same members.

  Here, the cell stack 2 constituting the cell stack apparatus 1 is an elliptical columnar conductive support body 11 (hereinafter sometimes abbreviated as the support body 11) composed of a pair of opposed flat portions and arc-shaped portions at both ends. A porous fuel electrode layer 8 is provided so as to cover one flat portion and the arc-shaped portion, and a dense solid electrolyte layer 9 is laminated so as to cover the fuel electrode layer 8. An air electrode layer 10 is provided on the solid electrolyte layer 9 so as to face the fuel electrode layer 8. That is, the fuel electrode layer 8, the solid electrolyte layer 9, and the air electrode layer 10 are laminated in this order on one flat portion of the support 11. An interconnector 13 is laminated on the other flat portion of the support 11 on which the fuel electrode layer 8 and the solid electrolyte layer 9 are not formed. With such a configuration, the columnar fuel cell 3 is formed. As is apparent from FIG. 1B, the fuel electrode layer 8 and the solid electrolyte layer 9 are extended to both sides of the interconnector 13 via the arc-shaped portions at both ends, and the surface of the support 11 Is configured not to be exposed to the outside.

  A plurality of the fuel cells 3 are electrically connected in series with the current collecting member 4 interposed between the adjacent fuel cells 3 to constitute the cell stack 2. The current collecting member 4 interposed between the adjacent fuel cells 3 is connected to the air electrode layer 10 or the interconnector 13 via the conductive bonding material 14, respectively. Are electrically connected in series.

  And the lower end part of each fuel battery cell 3 which comprises the cell stack 2 mentioned above is fixed to the manifold 7 for supplying fuel gas (hydrogen containing gas) to the fuel battery cell 3, and a lower end part is to the manifold 7. The conductive member 5 is arranged so as to sandwich the cell stack from both ends of the fuel cell 3 in the arrangement direction of the fuel cell 3 via the current collecting member 4, thereby configuring the cell stack device 1.

  Here, in the conductive member 5 shown in FIG. 1, a current extraction portion 6 is provided for extending outward along the arrangement direction of the fuel cells 3 and for extracting a current generated by the power generation of the fuel cells 3. It has been.

  A plurality of fuel gas passages 12 penetrating in the longitudinal direction are provided inside the support 11 constituting the fuel cell 3, and the fuel gas supplied from the manifold 7 is supplied to the fuel gas passage 12. Is supplied to the fuel electrode layer 8 while flowing upward.

  Further, the support 11 may also serve as the fuel side electrode (fuel electrode layer 8), and the fuel cell 3 can be configured by sequentially laminating the solid electrolyte layer 9 and the air electrode layer 10 on the surface thereof.

  Various types of fuel cells are known as the fuel cells 3. However, in order to reduce the size and increase the efficiency of the fuel cell device that houses the fuel cells 3, the solid oxide that operates at high temperatures is used. It can be set as a physical fuel cell. Thereby, the fuel cell device can be reduced in size and increased in efficiency, and a load following operation can be performed to follow a fluctuating load required for a household fuel cell. Furthermore, an efficient solid oxide fuel cell system can be configured by combining heat generated by power generation with a hot water supply system.

  Below, each member which comprises the fuel cell 3 shown in FIG. 1 is demonstrated.

  Since the support 11 is required to be gas permeable in order to permeate the fuel gas to the fuel electrode layer 8 and to be conductive in order to collect current via the interconnector 13, for example, It is preferably formed of an iron group metal component and a specific rare earth oxide.

  Examples of the iron group metal component include an iron group metal element, an iron group metal oxide, an iron group metal alloy or an alloy oxide, and the like. More specifically, for example, iron group metals include Fe, Ni (nickel), and Co. Since they are particularly inexpensive and stable in fuel gas, Ni and / or NiO are used as iron group components. It is preferable to contain.

The specific rare earth oxide is used to bring the thermal expansion coefficient of the support 11 close to the thermal expansion coefficient of the solid electrolyte layer 9 to be described later. Y, Lu (lutetium), Yb, Tm ( A rare earth oxide containing at least one element selected from the group consisting of thulium), Er (erbium), Ho (holmium), Dy (dysprosium), Gd, Sm, Pr (praseodymium), Used in combination. Specific examples of such rare earth oxides include Y ₂ O ₃ , Lu ₂ O ₃ , Yb ₂ O ₃ , Tm ₂ O ₃ , Er ₂ O ₃ , Ho ₂ O ₃ , Dy ₂ O ₃ , Gd ₂ O. ₃ , Sm ₂ O ₃ , Pr ₂ O ₃ can be exemplified, and there is almost no solid solution or reaction with the iron group metal oxide, and the thermal expansion coefficient is almost the same as that of the solid electrolyte layer 9. And Y ₂ O ₃ and Yb ₂ O ₃ are preferable because they are inexpensive.

In the present invention, the volume ratio after firing-reduction is Ni: rare earth element oxide in terms of maintaining good conductivity of the support 11 and approximating the thermal expansion coefficient to that of the solid electrolyte layer 9. (For example, Ni: Y ₂ O ₃ ) is preferably in the range of 35:65 to 65:35 (Ni / (Ni + Y) is 65 to 86 mol% in molar ratio). The support 11 may contain other metal components and oxide components as long as required characteristics are not impaired.

  Further, since the support 11 needs to have fuel gas permeability, it is usually preferable that the open porosity is in the range of 30% or more, particularly 35 to 50%. The conductivity of the support 11 is 50 S / cm or more, preferably 300 S / cm or more, and particularly preferably 440 S / cm or more.

  In addition, the length of the flat part of the support 11 (length in the width direction of the support 11) is usually 15 to 35 mm, and the length of the arc-shaped part (arc length) is 2 to 8 mm. The thickness of the body 11 (thickness between both flat portions) is preferably 1.5 to 5 mm.

The fuel electrode layer 8 causes an electrode reaction, and can be formed from at least one of Ni and NiO, which are iron group metals, and ZrO _{2 in} which a rare earth element is dissolved. In addition, as a rare earth element, the rare earth elements (Y etc.) illustrated in the electroconductive support body 2 can be used.

In the fuel electrode layer 8, and at least one of Ni and NiO, ZrO ₂ content of the rare earth element is solid-solved is fired - volume ratio after reduction, Ni: ZrO ₂ (e.g. a rare earth element in solid solution, NiO: YSZ) is preferably in the range of 35:65 to 65:35. Further, the porosity of the fuel electrode layer 8 is preferably 15% or more, particularly preferably in the range of 20 to 40%, and the thickness thereof is preferably 1 to 30 μm. For example, if the thickness of the fuel electrode layer 8 is too thin, the performance may be deteriorated. If the thickness is too thick, peeling due to a difference in thermal expansion coefficient between the solid electrolyte layer 9 and the fuel electrode layer 8 described later may occur. May cause cracks.

The solid electrolyte layer 9 uses a dense ceramic made of partially stabilized or stabilized ZrO ₂ containing rare earth elements such as 3 to 15 mol% of Y (yttrium), Sc (scandium), Yb (ytterbium). Is preferred. As the rare earth element, Y is preferable because it is inexpensive. Further, the solid electrolyte layer 9 is desirably a dense material having a relative density (according to Archimedes method) of 93% or more, particularly 95% or more in terms of preventing gas permeation, and a thickness of 5 to 50 μm. Preferably there is.

  In addition, the solid electrolyte layer 9 and the air electrode layer 10 are firmly joined between the solid electrolyte layer 9 and the air electrode layer 10 described later, and the components of the solid electrolyte layer 9 and the components of the air electrode layer 10 are An intermediate layer (not shown) can also be provided for the purpose of suppressing the formation of a reaction layer having a high electrical resistance by reaction.

Here, the intermediate layer can be formed with a composition containing Ce (cerium) and another rare earth element. For example, (CeO ₂ ) _1-x (REO _1.5 ) _x (RE is Sm, It is preferably at least one of Y, Yb, and Gd, and x has a composition represented by the following formula: 0 <x ≦ 0.3. Furthermore, from the viewpoint of reducing electrical resistance, it is preferable to use Sm or Gd as RE, for example, it is preferably made of CeO ₂ in which 10 to 20 mol% of SmO _1.5 or GdO _1.5 is dissolved. . The intermediate layer may be composed of, for example, two layers. In this case, after the first layer is provided by simultaneous firing with the solid electrolyte layer 9, the second layer is separately fired at a temperature lower by 200 ° C. or more than the simultaneous firing. It is preferable to do.

  The air electrode layer 10 needs to have gas permeability. Therefore, the conductive ceramic (perovskite oxide) forming the air electrode layer 10 has a porosity of 20% or more, particularly 30 to 50%. Preferably there is. Furthermore, the thickness of the air electrode layer 10 is preferably 30 to 100 μm from the viewpoint of current collection.

  An interconnector 13 is laminated on the surface (one flat surface) opposite to the air electrode layer 10 side of the support 11 via an adhesion layer (not shown).

The interconnector 13 is preferably formed of conductive ceramics, but is in contact with a fuel gas (hydrogen-containing gas) and an oxygen-containing gas (air), and therefore has interconnected resistance and oxidation resistance. is necessary. For this reason, lanthanum chromite-based perovskite oxides (LaCrO ₃ -based oxides) are generally used as conductive ceramics having reduction resistance and oxidation resistance, and in particular, the support 11 and the solid electrolyte layer 9 For the purpose of bringing the thermal expansion coefficient closer, LaCrO ₃ -based oxide is used.

  Further, the thickness of the interconnector 13 is preferably 10 to 50 μm from the viewpoint of preventing gas leakage and electric resistance. If the thickness is smaller than this range, gas leakage is liable to occur. If the thickness is larger than this range, the electric resistance is large, and the current collecting function may be lowered due to a potential drop.

The adhesion layer can be formed of, for example, at least one of rare earth element oxide, ZrO _{2 in which} a rare earth element is dissolved, and CeO ₂ in which a rare earth element is dissolved, and at least one of Ni and NiO. More specifically, for example, a composition comprising at least one of Y ₂ O ₃ and Ni and NiO, a composition comprising at least one of ZrO ₂ (YSZ) in which Y is solid-solved, Ni and NiO, Y, Sm, It can be formed from a composition comprising CeO ₂ in which Gd or the like is dissolved, and at least one of Ni and NiO. Note that the rare earth element oxide or rare earth element ZrO ₂ (CeO ₂ ) and at least one of Ni and NiO have a volume ratio in the range of 40:60 to 60:40 after firing and reduction. It is preferable to form as follows.

  The current collecting member 4 is preferably configured to have heat resistance and oxidation resistance, and is composed of, for example, a metal containing Cr. As such a current collecting member 4, a pair of plate-like contact portions for making contact with adjacent fuel cells 3 provided at a predetermined interval, and one contact portion of the pair of contact portions. It is possible to use the current collecting member 4 having a configuration in which a plurality of conductive pieces having a connection portion that connects one end of the other contact portion and one end of the other contact portion are continuously formed in the longitudinal direction of the fuel cell 3.

  Further, since the interconnector 13 and the current collecting member 4 are electrically connected via the conductive bonding material 14, the contact between the two becomes an ohmic contact, the potential drop can be reduced, and the current collecting performance is reduced. It can be effectively avoided.

  By the way, the cell stack 2 is configured by connecting a plurality of the fuel battery cells 3 manufactured as described above to the current collecting member 4 through the conductive bonding material 14. Cracks are generated in the conductive bonding material 14 due to the thermal stress caused by the difference in thermal expansion coefficient between the conductive bonding material 14 and the interconnector 13 or the current collecting member 4 at the time of production or operation of the fuel cell device. The long-term reliability of the cell stack 2 may be reduced.

  FIG. 2 is a cross-sectional view schematically showing the joining of the current collecting member 4 and the fuel cell 3 in the cell stack 2 of the present invention, and the air electrode layer 10 formed on the upper surface of the solid electrolyte layer 9 and the current collector. It shows that the member 4 is connected via the conductive bonding material 14. Here, as shown in FIG. 2, the current collecting member 4 is preferably covered with the conductive bonding material 14 on the entire surface (outer surface), and is directly connected to the air electrode layer 10. Preferably not. Accordingly, the contact area between the current collecting member 4 and the conductive bonding material 14 can be increased, and the current collecting member 4 can be easily fixed.

The conductive bonding material 14 includes a coarse powder made of LaSrAO ₃ perovskite oxide (preferably in a range of _{3 to} 10 μm) having an average particle diameter of 3 μm or more, and a LaSrCoO ₃ perovskite oxide (average particle diameter of 1 μm or less). LaSrAO ₃ -based perovskite oxide that constitutes the coarse powder has a thermal expansion coefficient of LaSrCoO ₃ -based perovskite that constitutes the fine powder. The thermal expansion coefficient is smaller than that of the type oxide, and the coarse powder is contained more than the fine powder. A indicates that at least one of Mn, Co, Al, and Fe is included, and the same applies hereinafter.

  Here, the coarse powder and the fine powder constituting the conductive bonding material 14 will be described.

The coarse powder is composed of a LaSrAO ₃ perovskite oxide in order to bring the coefficient of thermal expansion close to that of the LaCrO ₃ perovskite oxide constituting the interconnector 13. The LaSrAO ₃ perovskite-type oxide, LaSrCoFeO ₃ type perovskite oxide (e.g., LaSrCoFeO _3), LaSrMnO ₃ perovskite oxide (e.g., LaSrMnO _3), LaSrFeO ₃ perovskite oxide (e.g. LaSrFeO _3), LaSrCoO _{At least one of a three-} based perovskite oxide (for example, LaSrCoO ₃ ) and a LaSrAlO ₃ -based perovskite oxide (for example, LaSrAlO ₃ ) is preferable, and the thermal expansion coefficient with the LaCrO ₃ -based perovskite oxide constituting the interconnector 13 From the point of approaching, a LaSrMnO ₃ -based perovskite oxide that does not contain Co having a high thermal expansion coefficient is particularly preferable. In the case where a LaSrCoFeO ₃ perovskite oxide is used, La _0.8 Sr _{0.2 with} a low Co content in that the thermal expansion coefficient is close to that of the LaCrO ₃ perovskite oxide constituting the interconnector 13. It is preferable to use Co _0.2 Fe _0.8 O ₃ or La _0.9 Sr _0.1 Co _0.1 Fe _0.9 O ₃ .

Fines, larger thermal expansion coefficient than LaSrAO ₃ perovskite oxide constituting the coarse powder consists of LaSrCoO ₃ perovskite oxide containing high conductivity Co. As the LaSrCoO ₃ -based perovskite oxide, at least one of LaSrCoFeO ₃ -based perovskite oxide (for example, LaSrCoFeO ₃ ) and LaSrCoO ₃ -based perovskite oxide (for example, LaSrCoO ₃ ) is preferable.

Specifically, for example, a coarse powder and LaSrMnO _3, when the fine powder and LaSrCoFeO _3, by coarse powder consists of LaSrMnO _3, LaCrO ₃ perovskite oxide constituting the interconnector 13 thermal expansion coefficient It can be brought close to an object, and the occurrence of cracks in the conductive bonding material 14 can be suppressed. Further, by using LaSrCoFeO ₃ as the fine powder, the conductivity of the conductive bonding material 14 can be improved.

In the case where both the coarse powder and the fine powder are composed of LaSrCoO ₃ -based perovskite oxide, the coefficient of thermal expansion of the conductive bonding material 14 can be reduced by reducing the Co content in the coarse powder. At the same time, the conductivity of the conductive bonding material 14 may be reduced. Therefore, when both the coarse powder and the fine powder are composed of LaSrCoO ₃ -based perovskite oxides, they are combined so that the composition ratio of Co constituting the fine powder is larger than the composition ratio of Co constituting the coarse powder. It is preferable.

Specifically, when both coarse powder and fine powder are LaSrCoO ₃ -based perovskite oxide LaSrCoFeO ₃ , the coarse powder is La _0.9 Sr _0.1 Co _0.1 Fe _0.9 O _3. Since the fine powder is La _0.6 Sr _0.4 Co _0.4 Fe _0.6 O ₃ , the amount of Co contained in the coarse powder is small. The conductivity of the conductive bonding material 14 can be improved because it can be made closer to a LaCrO ₃ -based perovskite oxide and the Co content of the fine powder is large.

  Moreover, in order to make the thermal expansion coefficient of the conductive bonding material 14 close to the interconnector 13 and the current collecting member 4, the conductive bonding material 14 contains more coarse powder than fine powder. By containing more coarse powder having a small thermal expansion coefficient than fine powder, the thermal expansion coefficient of the conductive bonding material 14 can be made closer to the interconnector 13 and the current collecting member 4 more easily. The crack which arises in can be suppressed.

  By setting the average particle size of the coarse powder to 3 μm or more, preferably 3 to 10 μm, firing shrinkage of the conductive bonding material 14 itself can be suppressed, and cracks generated in the conductive bonding material 14 are further suppressed. be able to. Moreover, when the average particle diameter of the fine powder is 0.1 μm or more, preferably 0.1 to 1 μm, more preferably 0.1 to 0.7 μm, the fine powder It can disperse | distribute uniformly, while being able to improve the sinterability of the molded object of the conductive joining material 14, it can improve joining strength. Thereby, it can suppress that the electroconductive joining material 14, the fuel cell 3 and the current collection member 4 peel, and can suppress that the electrical resistance of the electroconductive joining material 14 increases.

  The coarse powder and fine powder preferably have a raw material ratio in the range of 7: 3 to 9: 1 by mass ratio. By setting it as 7: 3 or more, the thermal expansion coefficient of the conductive bonding material 14 can be brought close to the interconnector 13 and the current collecting member 4, and by setting it as 9: 1 or less, the conductive bonding material 14 is molded. The sinterability of the body can be improved and the bonding strength can be improved.

  The thickness of the conductive bonding material 14 is preferably in the range of 30 to 300 μm. By setting the thickness to 30 μm or more, the bonding strength between the conductive bonding material 14 and the current collecting member 4 or the fuel cell 3 can be increased, and by setting the thickness to 100 μm or more, the current collecting member 4 and the conductive bonding material 14. The contact area can be increased, and the bonding strength can be further increased. Moreover, it can suppress that a crack arises by baking shrinkage of electroconductive joining material 14 itself by setting it as 300 micrometers or less.

  Further, detection of cracks in the conductive bonding material 14 and separation of the conductive bonding material 14 from the current collecting member 4 and the fuel cell 3 will be described. Cracks generated on the surface of the conductive bonding material 14 and peeling of the conductive bonding material 14 from the current collecting member 4 and the fuel cell 3 can be detected by observation using a loupe or the like. Further, the fuel cell 3 is cut so that the interface between the fuel cell 3 and the conductive bonding material 14 or the interface between the current collecting member 4 and the conductive bonding material 14 can be confirmed, and the cut section is photographed with a scanning line electron microscope (SEM). By doing so, it is possible to detect cracks and peeling occurring inside the conductive bonding material 14.

  The members constituting the fuel cell 3 according to the present invention have been described above. Next, a method for producing the fuel cell 3 (cell stack 2) according to the present invention will be described.

First, a clay is prepared by mixing an iron group metal such as Ni or its oxide powder, a rare earth oxide powder such as Y ₂ O ₃ , an organic binder, and a solvent, and using this clay A support molded body is prepared by extrusion molding and dried. In addition, you may use the calcined body which calcined the support body molded object at 900-1000 degreeC for 2 to 6 hours as a support body molded object.

Next, for example, ZrO ₂ (YSZ) raw material in which NiO and Y ₂ O ₃ are dissolved is weighed and mixed according to a predetermined composition. Then, an organic binder and a solvent are mixed with the mixed powder to prepare a fuel electrode layer slurry.

Further, a slurry obtained by adding toluene, a binder, a commercially available dispersant, etc. to a ZrO ₂ powder in which a rare earth element is solid-solubilized is molded to a thickness of 7 to 75 μm by a method such as a doctor blade. A solid electrolyte layer molded body is produced. The fuel electrode layer slurry is applied on the obtained sheet-shaped solid electrolyte layer molded body to form a fuel electrode layer molded body, and the surface on the fuel electrode layer molded body side is laminated on the support molded body. Alternatively, the fuel electrode layer slurry may be applied to a predetermined position of the support body molded body and dried, and the solid electrolyte layer molded body coated with the fuel electrode layer slurry may be laminated on the conductive support body molded body.

Subsequently, an interconnector material (for example, LaCrO ₃ oxide powder), an organic binder, and a solvent are mixed to prepare a slurry, an interconnector sheet is prepared, and a solid electrolyte layer molded body is not formed. Laminate on the exposed surface of the body compact.

  Next, the above-mentioned laminated molded body is subjected to binder removal treatment and co-fired at 1400 to 1600 ° C. for 2 to 6 hours in an oxygen-containing atmosphere.

Subsequently, a slurry for an air electrode layer containing LaSrCoFeO ₃ oxide powder and a solvent is applied onto the solid electrolyte layer 9 by screen printing, dried, and then fired at 1100 to 1200 ° C. for 1 to 3 hours. . The fuel cell 3 can be manufactured through the above steps.

Subsequently, a LaSrMnO ₃ powder having an average particle diameter of 3 [mu] m, an average particle diameter of 0.5μm and a LaSrCoFeO ₃ powder mixing ratio in weight ratio of 8: mixing 2 become as to prepare a powder for conductive bonding material . Next, the conductive bonding material powder, an organic binder, and a solvent are mixed to produce a conductive bonding material slurry, which is applied onto the air electrode layer 10 and the interconnector 13 by screen printing.

  Immediately after coating by the screen printing method, the current collecting member 4 is bonded, dried, and baked. Thereby, the cell stack formed by interposing the current collecting member 4 between the fuel battery cells 3 can be formed.

  In addition, it is preferable that the fuel cell 3 thereafter circulates a hydrogen-containing gas (fuel gas) therein to perform the reduction treatment of the support 11 and the fuel electrode layer 8. In that case, it is preferable to perform a reduction process at 750-1000 degreeC for 5 to 20 hours, for example.

  Moreover, although the example in which the conductive bonding material 14 is formed on the air electrode 10 and the interconnector 13 by screen printing has been described, the conductive bonding material 14 may be formed using other methods. For example, the current collecting member 4 is dipped in the above-described slurry for conductive bonding material, and the air electrode 10 of one fuel cell 3 and the interconnector 13 of the other fuel cell 3 are electrically connected between the fuel cells 3. The cell stack can be easily manufactured by interposing, bonding, drying, and firing.

  FIG. 3 is an external perspective view showing an example of a fuel cell module 17 in which the cell stack device 1 of the present invention is housed in a housing container. The cell shown in FIG. The stack apparatus 1 is accommodated.

  A reformer 19 for reforming raw fuel such as natural gas or kerosene to generate fuel gas is disposed above the cell stack 2 in order to obtain fuel gas used in the fuel cell 3. ing. The fuel gas generated by the reformer 19 is supplied to the manifold 7 via the gas flow pipe 20 and supplied to the fuel gas flow path 12 provided inside the fuel battery cell 3 via the manifold 7. The

  FIG. 3 shows a state in which a part (front and rear surfaces) of the storage container 18 is removed, and the cell stack device 1 and the reformer 19 housed inside are taken out rearward. Here, in the fuel cell module 17 shown in FIG. 3, the cell stack device 1 can be slid and stored in the storage container 18. The cell stack device 1 may include a reformer 19.

  Further, in FIG. 3, the oxygen-containing gas introduction member 21 provided in the storage container 18 is disposed between the cell stacks 2 juxtaposed on the manifold 7 and the oxygen-containing gas is matched to the flow of the fuel gas. The oxygen-containing gas is supplied to the lower end of the fuel cell 3 so that the fuel cell 3 flows laterally from the lower end toward the upper end. Then, the fuel gas discharged from the fuel gas flow path of the fuel battery cell 3 and the oxygen-containing gas are combusted on the upper end side of the fuel battery cell 3 to increase or maintain the temperature of the fuel battery cell 3 at a high temperature. In addition to speeding up the activation of the cell stack device 1, the power generation efficiency can be improved. Further, the fuel gas discharged from the fuel gas flow path of the fuel battery cell 3 and the oxygen-containing gas are combusted on the upper end side of the fuel battery cell 3 so that the upper side of the fuel battery cell 3 (cell stack 1). It is possible to efficiently warm the reformer 19 disposed in the. Thereby, the reforming reaction can be efficiently performed in the reformer 19.

  Furthermore, in the fuel cell module 17 of the present invention, since the cell stack device 1 configured using the cell stack 2 with improved long-term reliability is stored in the storage container 18, the long-term reliability is improved. The fuel cell module 17 can be obtained.

  4 is an exploded perspective view showing an example of the fuel cell device of the present invention in which the fuel cell module 17 shown in FIG. 3 and an auxiliary machine for operating the fuel cell stack device 1 are housed in an outer case. FIG. In FIG. 4, a part of the configuration is omitted.

  The fuel cell device 22 shown in FIG. 4 divides the inside of an exterior case composed of a support column 23 and an exterior plate 24 into upper and lower portions by a partition plate 25, and a module storage chamber 26 for storing the above-described fuel cell module 17 on the upper side. The lower side is configured as an auxiliary equipment storage chamber 27 for storing auxiliary equipment for operating the fuel cell module 17. It should be noted that auxiliary equipment stored in the auxiliary equipment storage chamber 27 is omitted.

  Further, the partition plate 25 is provided with an air circulation port 28 for flowing the air in the auxiliary machine storage chamber 27 to the module storage chamber 26 side, and a part of the exterior plate 24 constituting the module storage chamber 26 An exhaust port 29 for exhausting the air in the module storage chamber 26 is provided.

  In such a fuel cell device 22, as described above, the fuel cell module 17 that can improve long-term reliability is housed in the module housing chamber 26, so that the fuel with improved long-term reliability can be obtained. The battery device 22 can be obtained.

  Although the present invention has been described in detail above, the present invention is not limited to the above-described embodiments, and various modifications and improvements can be made without departing from the paper of the present invention.

  For example, in the fuel battery cell 3 of the present invention, a hollow flat plate is shown, but the present invention can also be used in a cylindrical fuel battery cell. Further, in the fuel cell 3 of the present invention, the example in which the laminated body is provided in almost the entire region other than the region where the interconnector 13 is provided has been shown. However, a solid electrolyte is provided between the interconnector 13 and the fuel electrode layer 8. It is sufficient that the layer 9 is provided.

First, NiO powder having an average particle diameter of 0.5 μm and Y ₂ O ₃ powder having an average particle diameter of 0.9 μm are calcined and reduced, so that the volume ratio is 48% by volume for Ni and 52% by volume for Y ₂ O _3. The kneaded material prepared with an organic binder and a solvent was molded by extrusion molding, dried and degreased to prepare a conductive support molded body.

Next, a slurry for a fuel electrode layer in which a NiO powder having an average particle size of 0.5 μm, a ZrO ₂ powder in which Y ₂ O ₃ is solid-solved, an organic binder, and a solvent are mixed is prepared, and a screen printing method is performed on the support body. Was applied and dried to form a coating layer for the fuel electrode layer. Next, using a slurry obtained by mixing a ZrO ₂ powder (raw material powder for a solid electrolyte layer) having a particle diameter of 0.8 μm by a microtrack method in which 8 mol% of yttrium was dissolved, an organic binder, and a solvent, A sheet for a solid electrolyte layer having a thickness of 30 μm was prepared by a doctor blade method. The sheet for the solid electrolyte layer was attached on the coating layer for the fuel electrode layer and dried.

  Subsequently, the laminated molded body in which the molded bodies were laminated as described above was calcined at 1000 ° C. for 3 hours.

Subsequently, a slurry for an interconnector in which a LaCrO ₃ oxide, an organic binder, and a solvent are mixed is prepared, and this is laminated on the exposed support calcined body where the solid electrolyte layer calcined body is not formed. And co-firing at 1510 ° C. in the atmosphere for 3 hours.

Next, a mixed liquid composed of LaSrCoFeO ₃ powder having an average particle diameter of 2 μm and isopropyl alcohol was prepared and spray-coated on the surface of the intermediate layer of the laminated sintered body to form an air electrode layer molded body. Was baked in 4 hours to form an air electrode layer, and a fuel cell was produced.

  Next, the coarse powder and fine powder of each raw material described in Table 1 are mixed at respective mixing ratios to prepare a conductive bonding material powder, which is composed of a conductive bonding material powder, isopropyl alcohol, and a pore former. The mixed solution was applied on the air electrode layer and the interconnector by screen printing.

  Next, after applying the conductive bonding material, a pair of plate-like contact portions for contacting with adjacent fuel cells provided at a predetermined interval, and one contact portion of the pair of contact portions A current collecting member (for example, in the longitudinal direction of the fuel cell) formed by continuously forming a plurality of conductive pieces having a connection portion connecting one end of the other contact portion and one end of the other contact portion in the longitudinal direction of the fuel cell A current collecting member consisting of a pair of connecting portions along the contact portion and a contact portion provided so as to bridge each connecting portion was bonded and dried, and then fired at 1150 ° C. for 2 hours. In addition, the fuel gas was distribute | circulated to the fuel cell after baking at 850 degreeC for 10 hours, and the reduction process was performed.

  A current stacking member was connected between the five fuel cells thus formed via a conductive bonding material to prepare a cell stack.

  Next, the presence or absence of cracks in the produced cell stack was observed using a loupe or the like. The subsequent test was also performed on the cell stack in which cracks had occurred.

Subsequently, the fuel gas is circulated through the fuel gas flow path of the obtained fuel battery cell, the oxygen-containing gas is circulated outside the fuel battery cell, and the fuel battery cell is heated to 750 ° C. using an electric furnace, A power generation test was performed under the condition of a current density of 0.3 A / cm ² .

  After the power generation test, the presence or absence of cracks in the cell stack was confirmed by the same method as described above.

As shown in Table 1, the average particle diameter of 1μm or less of the LaSrCoO ₃ type perovskite oxide fines and an average particle diameter 3μm or more LaSrAO ₃ perovskite oxide consisting (A is, Mn, Co, Al and Fe Sample No. 1 comprising a mixture of coarse powders comprising at least one of them, the thermal expansion coefficient of the coarse powder being smaller than the thermal expansion coefficient of the fine powder, and containing the coarse powder more than the fine powder. In Nos. 4-7, 10-14, and 17-21, cracks did not occur even when the cell stack was fabricated and after the power generation test was completed.

  On the other hand, Sample No. with a coefficient of thermal expansion greater than or equal to that of coarse powder than fine powder. Nos. 1, 2 and 24 had cracks after the end of the power generation test. Sample No. containing no fine powder. 3. Sample No. containing no coarse powder No. 9 and Sample No. with the same coarse powder content as fine powder. In No. 8, cracks occurred even when the cell stack was produced and after the power generation test was completed.

  Sample No. with an average particle diameter of coarse powder of 11 μm Sample No. 15 having an average particle size of 10 μm. Compared to 14, the bonding strength was low, and cracks were generated in the conductive bonding material. Sample No. with an average particle size of coarse powder of 2.5 μm In No. 23, the shrinkage of the conductive bonding material itself was large, and cracks were generated at the time of cell stack preparation and after the end of the power generation test.

  In addition, Sample No. with an average particle size of fine powder of 0.05 μm was used. No. 16 was unable to apply the slurry due to poor dispersion of the fine powder when the slurry for conductive bonding material was produced. Sample No. with an average particle size of 1.2 μm of fine powder. In No. 23, cracks occurred in the conductive bonding material, and the bonding strength of the conductive bonding material was low, and peeling occurred between the conductive bonding material and the current collecting member.

1: Cell stack device 2: Cell stack 3: Fuel cell 4: Current collecting member 8: Fuel electrode layer 9: Solid electrolyte layer 10: Air electrode layer 11: Conductive support 13: Interconnector 14: Conductive bonding material 17: Fuel cell module 22: Fuel cell device

Claims (5)

A fuel electrode layer, a solid electrolyte layer, and an air electrode layer made of a LaSrCoO ₃ -based perovskite oxide are stacked in this order on one of the opposing portions of the surface of the conductive support, and the LaCrO ₃ -based perovskite type is stacked on the other side. A plurality of fuel cells each provided with an interconnector made of oxide are connected to the air electrode layer of one of the adjacent fuel cells and the interconnector of the other fuel cell via a conductive bonding material, respectively. A cell stack electrically connected in series by a current collecting member,
Said conductive bonding material has an average particle diameter of 1μm or less of the LaSrCoO ₃ perovskite of oxide fines and an average particle diameter 3μm or more LaSrAO ₃ perovskite oxide (A is, Mn, Co, of Al and Fe A mixture of coarse powder comprising at least one kind), the thermal expansion coefficient of the coarse powder is smaller than the thermal expansion coefficient of the fine powder, and the coarse powder is contained more than the fine powder. And cell stack. The cell stack according to claim 1, wherein the coarse powder is made of a LaSrMnO ₃ -based perovskite oxide. 2. The cell according to claim 1, wherein the coarse powder is made of a LaSrCoO ₃ -based perovskite oxide, and a composition ratio of Co constituting the fine powder is larger than a composition ratio of Co constituting the coarse powder. stack.   A fuel cell module comprising the cell stack according to any one of claims 1 to 3 housed in a housing container.   5. A fuel cell device, comprising: the fuel cell module according to claim 4; and an auxiliary machine that controls the operation of the fuel cell module.

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