JP5377599B2 - FUEL BATTERY CELL, CELL STACK DEVICE USING THE SAME, FUEL CELL MODULE, AND FUEL CELL DEVICE - Google Patents

Description

  The present invention relates to a fuel cell having an interconnector, a fuel electrode layer, a solid electrolyte layer, and an air electrode layer on the surface of a conductive support, and a cell stack device, a fuel cell module and a fuel cell using the same. Relates to the device.

  In recent years, various fuel cell devices in which a cell stack device in which a plurality of fuel cells are electrically connected in series are accommodated in a storage container have been proposed as next-generation energy.

  As a fuel cell constituting such a cell stack device, a porous fuel electrode layer, a dense material is formed on the main surface on one side of a conductive support having a fuel gas flow path for flowing a fuel gas inside. A solid electrolyte layer and an air electrode layer are laminated in this order, and an adhesion layer and a dense interconnector are provided on the main surface on the other side, and both ends of the solid electrolyte extend to the main surface on one side. There has been proposed a fuel cell that is provided and overlaps with both end portions of the interconnector via an adhesion layer (see Patent Document 1).

  In addition, a cell stack device is proposed in which a plurality of such fuel cells are electrically connected in series via current collecting members (see, for example, Patent Document 2).

JP 2005-158529 A JP 2008-135304 A

  By the way, during the operation of the fuel cell device, the difference in thermal expansion between the fuel electrode layer and the adhesion layer and the interconnector, and the iron group metal oxide contained in the fuel electrode layer and the adhesion layer is reduced to the iron group metal. Due to the reduction shrinkage, the joining surface of the fuel electrode layer, the adhesion layer and the interconnector may be peeled off. In this case, the fuel gas flowing through the fuel gas flow path provided inside the fuel cell is porous. The fuel electrode layer and the adhesion layer may leak, and the long-term reliability of the fuel cell may be reduced.

  Therefore, the present invention is to provide a fuel cell capable of suppressing the leakage of the fuel gas flowing through the fuel gas flow path, and a cell stack device, a fuel cell module, and a fuel cell device including the fuel cell. .

In the fuel cell of the present invention, an adhesive layer containing at least one of Ni and NiO and a dense interconnector provided on the adhesive layer are formed on one main surface of a columnar conductive support. A porous fuel electrode layer containing at least one of an iron group metal and an iron group metal oxide, a dense solid electrolyte layer, and a porous air electrode layer on the other main surface. Comprising a laminated body sequentially laminated, and both ends of the solid electrolyte layer and the fuel electrode layer are extended from the other principal surface of the conductive support to the one principal surface via a side surface, wherein both ends of the solid electrolyte layer are joined and both end portions of the interconnector is a portion of the solid electrolyte layer is characterized in that interposed between the inter connctor and the fuel electrode layer.

In such a fuel cell, since the both end portions of the both end portions and the interconnector of the solid electrolyte layer are joined, fuel gas porous fuel electrode layer, to the outside of the fuel cell from the contact layer Leakage (leakage) can be suppressed or prevented. Thereby, the long-term reliability of the fuel cell can be improved.

The cell stack device of the present invention, the above-mentioned fuel cell, a plurality arranged in a state of being erected via a current collecting member, the cell stack formed by electrically connecting in series, the fuel cell And a manifold for supplying fuel gas to the fuel battery cell.

  In such a cell stack apparatus, since a plurality of fuel cells that can suppress (prevent) fuel gas leakage are arranged, a cell stack apparatus with improved long-term reliability can be obtained.

  Since the fuel cell module of the present invention is formed by housing the cell stack device described above in a storage container, the fuel cell module can be improved in long-term reliability.

  The fuel cell device according to the present invention comprises the above-described fuel cell module and an auxiliary machine for operating the fuel cell module in an outer case, and thus a fuel cell device with improved long-term reliability. can do.

Fuel cell of the present invention, since the both end portions of the both end portions and the interconnector of the solid electrolyte layer are joined, Ki de is possible to prevent the fuel gas from leaking from the fuel Ryokyokuso, adhesion layer The long-term reliability of the fuel cell can be improved. Further, by providing the fuel cell described above, a cell stack device, a fuel cell module, and a fuel cell device with improved long-term reliability can be obtained.

An example of the fuel cell of this invention is shown, (a) is the cross-sectional view, (b) is a perspective view of (a). The other example of the fuel cell of this invention is shown, (a) is the cross-sectional view, (b) is a perspective view of (a). An example of the cell stack apparatus of the present invention is shown, (a) is a side view schematically showing the cell stack apparatus, and (b) is an enlarged part of a portion surrounded by a dotted frame of the cell stack apparatus of (a). It is a top view. It is an external appearance perspective view which shows an example of the fuel cell module of this invention. 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 fuel cell according to the present invention, in which (a) is a cross-sectional view and (b) is a perspective view of (a). In both drawings, each configuration of the fuel cell 1 is partially enlarged. The same members are denoted by the same reference numerals, and so on.

  The fuel cell 1 has a hollow flat plate shape, and includes a conductive support 2 having an elliptical column shape as a whole. A plurality of fuel gas passages 7 penetrating from one end to the other end in the longitudinal direction are formed in the conductive support 2 at predetermined intervals, and the fuel cell 1 is placed on the conductive support 2. It has a structure in which various members are provided.

  As understood from the shape shown in FIG. 1, the conductive support 2 is composed of a pair of flat surfaces n parallel to each other and arcuate surfaces (side surfaces) m connecting the pair of flat surfaces n. Has been.

  On one flat surface n of the conductive support 2, a dense interconnector 6 is provided from one end to the other end in the longitudinal direction of the conductive support 2. A porous fuel electrode layer 3 on the other flat surface n and both side surfaces m where the connector 6 is not provided, a solid electrolyte layer 4 dense so as to cover the outer surface of the fuel electrode layer 3, and a porous air electrode A laminated body in which the layer 5 is laminated is provided. In the fuel cell 1 shown in FIG. 1, the fuel electrode layer 3 (more specifically, the interconnector 6) is disposed on the solid electrolyte layer 4 on the other main surface of the conductive support 2 via the intermediate layer 8. The air electrode layer 5 is laminated so as to face each other.

  In the fuel cell 1 shown in FIG. 1, the fuel electrode layer 3 and the solid electrolyte layer 4 extend to both side portions in the circumferential direction (width direction) of the fuel cell 1 of the interconnector 6 via the arcuate surfaces m at both ends. It extends and is provided with a part of the solid electrolyte layer 4 interposed between the fuel electrode layer 3 and the interconnector 6 so that the surface (outer surface) of the conductive support 2 is not exposed to the outside. Are provided so as to contact each other. The fuel electrode layer 3 may be provided only in a region facing the air electrode layer 5 and the other region may be covered with the solid electrolyte 4.

The adhesion layer 9 is provided between the conductive substrate 2 and the interconnector 6. By providing the adhesion layer 9, the bonding between the conductive support 2 and the interconnector 6 can be strengthened.

  Here, the fuel cell 1 generates electric power when the facing portions of the fuel electrode layer 3 and the air electrode layer 5 function as electrodes. That is, an oxygen-containing gas such as air is allowed to flow outside the air electrode layer 5 and a fuel gas (hydrogen-containing gas) is allowed to flow through the fuel gas flow path 7 in the conductive support 2 to be heated to a predetermined operating temperature. To generate electricity. The current generated by the power generation is collected through an interconnector 6 provided on the surface of the conductive support 2.

  Below, each member which comprises the fuel battery cell 1 of this invention is demonstrated.

  Since the conductive support 2 is required to be gas permeable in order to allow the fuel gas to pass to the fuel electrode layer 3 and to be conductive in order to collect current via the interconnector 6, For example, it is preferably formed of at least one of Ni and NiO and a specific rare earth oxide.

The specific rare earth oxide is used to make the thermal expansion coefficient of the conductive support 2 close to the thermal expansion coefficient of the solid electrolyte layer 4, and is Y, Lu (lutetium), Yb, Tm (thulium). , Er (erbium), Ho (holmium), Dy (dysprosium), Gd, Sm, Pr (praseodymium), the rare earth oxide containing at least one element selected from at least one of Ni and NiO Can be 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 , almost no solid solution and reaction with at least one of Ni and NiO, and the thermal expansion coefficient is almost the same as that of the solid electrolyte layer 4. Y ₂ O ₃ and Yb ₂ O ₃ are preferable because they are available and inexpensive.

In the present invention, the volume ratio after firing-reduction is Ni: rare earth element in terms of maintaining good conductivity of the conductive support 2 and approximating the thermal expansion coefficient to that of the solid electrolyte layer 4. It is preferable that the oxide (for example, Ni: Y ₂ O ₃ ) is in the range of 35:65 to 65:35 (Ni / (Ni + Y) is 65 to 86 mol% in molar ratio). The conductive support 2 may contain other metal components and oxide components as long as required characteristics are not impaired.

  Moreover, since the electroconductive support body 2 needs to have gas permeability, it is usually preferable that the porosity is 30% or more, particularly 35 to 50%. The conductivity of the conductive support 2 is 50 S / cm or more, more preferably 300 S / cm or more, and particularly preferably 440 S / cm or more.

  Note that the length of the flat surface n of the conductive support 2 (length in the width direction of the conductive support 2) is usually 15 to 35 mm, and the length of the arcuate surface m (arc length) is 2. The thickness of the conductive support 2 (thickness between the flat surfaces n) is preferably 1.5 to 5 mm.

The fuel electrode layer 3 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 3, 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 3 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 4 is too thin, the performance may be deteriorated. If the thickness is too thick, peeling or cracks due to a difference in thermal expansion coefficient between the solid electrolyte layer 4 and the fuel electrode layer 3 described later. May occur.

The solid electrolyte layer 4 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 4 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 4 and the air electrode layer 5 are firmly joined between the solid electrolyte layer 4 and the air electrode layer 5 described later, and the components of the solid electrolyte layer 4 and the components of the air electrode layer 5 are The intermediate layer 8 can be provided for the purpose of suppressing the formation of a reaction layer having a high electrical resistance by reaction, and the fuel cell 1 shown in FIG. 1 shows an example provided with the intermediate layer 8. .

Here, the intermediate layer 8 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 , Y, Yb, and Gd, and x preferably has a composition represented by 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 8 can be composed of, for example, two layers. In this case, after the first layer is provided by co-firing with the solid electrolyte layer 4, the second layer is separately provided at a temperature lower by 200 ° C. or more than the co-firing. It is preferable to fire.

  Further, the air electrode layer 5 needs to have gas permeability. Therefore, the conductive ceramic (perovskite oxide) forming the air electrode layer 5 has a porosity of 20% or more, particularly 30 to 50%. It is preferable to be in the range. Furthermore, the thickness of the air electrode layer 5 is preferably 30 to 100 μm from the viewpoint of current collection.

  An interconnector 6 is laminated on the surface (one flat surface n) opposite to the air electrode layer 5 side of the conductive support 2 with an adhesion layer 9 interposed therebetween.

The interconnector 6 is preferably formed of conductive ceramics, but is required to have reduction resistance and oxidation resistance because it contacts the fuel gas (hydrogen-containing gas) and the oxygen-containing gas. . For this reason, lanthanum chromite-based perovskite oxides (LaCrO ₃ -based oxides) are generally used as conductive ceramics having reduction resistance and oxidation resistance. In particular, the conductive support 2 and the solid electrolyte layer 4 are used. LaCrO ₃ -based oxides are used for the purpose of bringing the coefficient of thermal expansion closer to the above.

  Further, the thickness of the interconnector 6 is preferably 10 to 50 μm from the viewpoint of prevention of gas leakage and electrical 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.

Furthermore, between the conductive substrate 2 and the interconnector 6, that has contact layer 9 is provided for such to reduce the difference in thermal expansion coefficient between the interconnector 6 and the electrically conductive substrate 2.

The adhesion layer 9 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.

  Although not shown, it is preferable to provide a P-type semiconductor layer on the outer surface (upper surface) of the interconnector 6. By connecting the current collecting member to the interconnector 6 via the P-type semiconductor layer, the contact between the two becomes an ohmic contact, the potential drop can be reduced, and the deterioration of the current collecting performance can be effectively avoided. .

As such a P-type semiconductor layer, a layer made of a transition metal perovskite oxide can be exemplified. Specifically, P having a high electron conductivity, for example, P made of at least one kind of LaMnO ₃ -based oxide, LaFeO ₃ -based oxide, LaCoO ₃ -based oxide in which Mn, Fe, Co, etc. exist at the B site. Type semiconductor ceramics can be used. In general, the thickness of such a P-type semiconductor layer is preferably in the range of 30 to 100 μm.

By the way, in the conventional fuel cell, the difference in thermal expansion between the fuel electrode layer 3 , the adhesion layer 9 and the interconnector 6, the fuel electrode layer 3 , Due to the reduction contraction accompanying the reduction of the iron group metal oxide contained therein to the iron group metal, the joining surfaces of the fuel electrode layer 3 , the adhesion layer 9 and the interconnector 6 may be peeled off, and the fuel cell 1 may leak from the porous fuel electrode layer 3 and the adhesion layer 9, and the long-term reliability of the fuel cell 1 may be reduced.

In the fuel cell 1 shown in FIG. 1, both end portions of the interconnector 6 in the circumferential direction (width direction) of the fuel cell 1 are laminated and joined to both end portions of the solid electrolyte layer 4 in the width direction of the fuel cell 1. since that, it is possible to prevent the fuel gas porous fuel electrode layer 3, leaks from the contact layer 9. Therefore, the long-term reliability of the fuel cell 1 can be improved.

  By the way, when the fuel cell 1 described above is manufactured and the reduction treatment is performed by flowing the fuel gas through the fuel gas flow path 7, the NiO contained in the fuel electrode layer 3 and the adhesion layer 9 is reduced and the NiO is reduced. As a result, voids are generated in the fuel electrode layer 3 and the adhesion layer 9, and the fuel gas may leak from the fuel electrode layer 3 and the adhesion layer 9.

However, in the fuel cell 1 shown in FIG. 1, since both ends of the solid electrolyte layer 4 and both ends of the interconnector 6 are joined , NiO contained in the fuel electrode layer 3 and the adhesion layer 9 is Ni. Even when the air gap is generated in the fuel electrode layer 3 and the adhesion layer 9, the fuel gas can be prevented from leaking and the power generation efficiency of the fuel cell 1 can be prevented from being lowered.

2, both end portions of the solid electrolyte layer 4 in the width direction of the fuel cell 1 are stacked and joined to both end interconnectors 6 in the width direction of the fuel cell 1. Thereby, the joining area of the solid electrolyte layer 4 and the interconnector 6 can be increased, and it can suppress that the interconnector 6 and a laminated body (solid electrolyte layer 4) peel.

As a result, the fuel gas can be prevented from leaking from the fuel electrode layer 3 and the adhesion layer 9 , and a fuel cell having improved long-term reliability can be obtained.

  A method for producing the fuel cell 1 of the present invention described above will be described.

First, a clay is prepared by mixing at least one powder of Ni and NiO, a powder of a rare earth oxide such as Y ₂ O ₃ , an organic binder, and a solvent, and using this clay, extrusion molding is performed. A conductive support molded body is prepared and dried. In addition, as the conductive support molded body, a calcined body obtained by calcining the conductive support molded body at 900 to 1000 ° C. for 2 to 6 hours may be used.

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

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 4 compact is produced. The fuel electrode layer slurry is applied on the obtained sheet-shaped solid electrolyte layer molded body to form a laminate molded body in which the fuel electrode layer molded body is formed, and this laminate molded body is formed into the fuel electrode layer molded body. The body is laminated on the conductive support compact with the bottom surface. At this time, by making the size of the solid electrolyte layer molded body larger than that of the fuel electrode layer 3 molded body, the fuel cell 1 covers the outer surface of the fuel electrode layer molded body and is formed later as an interconnector. A part of the solid electrolyte layer may be interposed between the fuel electrode layer and the fuel electrode layer.

  In addition, the slurry for the fuel electrode layer is applied to a predetermined position of the conductive support molded body and dried, so that the solid electrolyte layer molded body is not exposed to the outer surface. You may laminate | stack on an extreme layer molded object.

  Subsequently, an intermediate layer 8 molded body disposed between the solid electrolyte layer 4 and the air electrode layer 5 is formed.

For example, CeO ₂ powder in which GdO _1.5 is dissolved is heat-treated at 800 to 900 ° C. for 2 to 6 hours, and then wet pulverized to adjust the aggregation degree to 5 to 35, thereby forming an intermediate layer molded body. Prepare raw material powder for use. The wet crushing is desirably ball milled for 10 to 20 hours using a solvent. The same applies when the intermediate layer is formed of CeO ₂ powder in which SmO _1.5 is dissolved.

  Then, toluene is added as a solvent to the raw material powder of the intermediate layer molded body whose cohesion degree is adjusted to prepare a slurry for the intermediate layer, and this slurry is applied onto the solid electrolyte layer molded body to obtain the intermediate layer molded body. Make it. In addition, a sheet-like intermediate layer molded body may be prepared and laminated on the solid electrolyte layer molded body.

Subsequently, a material for an interconnector (for example, LaCrMgO ₃ oxide powder), an organic binder, and a solvent are mixed to prepare a slurry, and an interconnector sheet is prepared.

Then, the adhesion layer 9 molded body located between the electroconductive support body 2 and the interconnector 6 is formed. For example, ZrO ₂ in which Y is dissolved and NiO are mixed and dried so that the volume ratio is in the range of 40:60 to 60:40, and an organic binder or the like is added to adjust the slurry for the adhesion layer. The adjusted adhesion layer slurry is applied to the interconnector sheet to form the adhesion layer 9 molded body, and the surface on the adhesion layer molded body side is laminated on the conductive support molded body.

In the case of the fuel battery cell 10 shown in FIG. 2, after forming the conductive support 2 molded body, the interconnector sheet is laminated on the conductive support molded body through the adhesion layer molded body, and then the solid The electrolyte 4 molded body and the fuel electrode layer molded body are laminated on the conductive support molded body so that a part of the solid electrolyte layer 4 is interposed between the fuel electrode layer 3 and the interconnector 6. do it.

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

  When the intermediate layer 8 is formed of two layers, the intermediate layer on the air electrode layer side is obtained by applying the above-described intermediate layer slurry on the upper surface of the co-fired intermediate layer 8 (first layer). And firing at a temperature lower by 200 ° C. or more than the temperature at the time of the simultaneous firing.

Next, a slurry containing an air electrode layer material (for example, LaCoO ₃ oxide powder), a solvent, and a pore increasing agent is applied on the intermediate layer 8 by dipping or the like. Further, a slurry containing a P-type semiconductor layer material (for example, LaCoO ₃ oxide powder) and a solvent, if necessary, is applied to a predetermined position of the interconnector 6 by dipping or the like. By baking for 6 hours, the fuel cell 1 of the present invention having the structure shown in FIG. 1 can be produced. In addition, it is preferable that the fuel cell 1 thereafter causes hydrogen gas to flow therein to perform reduction treatment of the conductive support 2 and the fuel electrode layer 3. In that case, it is preferable to perform a reduction process at 750-1000 degreeC for 5 to 20 hours, for example.

As described above, at the time of producing the fuel cell 1 of the present invention, the fuel cell 1 has the porous fuel electrode layer 3 bonded to the both ends of the solid electrolyte layer 4 and the both ends of the interconnector 6 . Since the adhesion layer 9 is sealed with a dense interconnector and a dense solid electrolyte layer, the fuel gas can be prevented from leaking from the porous fuel electrode layer 3 and the adhesion layer 9 . Thereby, it can be set as the fuel cell 1 with improved long-term reliability.

  Further, since both end portions of the interconnector 6 are laminated on both end portions of the solid electrolyte layer 4 in the width direction of the fuel cell 1, the joining area between the solid electrolyte layer 4 and the interconnector 6 can be increased. It can suppress and it can suppress that the interconnector 6 and a laminated body (solid electrolyte layer 4) peel.

In addition, since both end portions of the solid electrolyte layer 4 in the circumferential direction (width direction) of the fuel cell 1 are laminated and joined to both end portions of the interconnector 6 in the width direction of the fuel cell 10, the solid electrolyte layer 4 is solid. The joining area of the electrolyte layer 4 and the interconnector 6 can be increased, and it can suppress that the interconnector 6 and a laminated body (solid electrolyte layer 4) peel.

  Note that “between the fuel electrode layer 3 and the interconnector 6” means a region on the surface of the conductive support 2 where the fuel electrode layer 3 and the interconnector 6 are not provided.

  FIG. 3 shows an example of a cell stack device configured by electrically connecting a plurality of the above-described fuel cells 1 in series via a current collecting member 14, and (a) shows a cell stack. The side view which shows the stack apparatus 12 schematically, (b) is a partial enlarged plan view of the cell stack apparatus 12 of (a), and shows the part surrounded by the dotted frame shown in (a). Yes. In addition, in (b), in order to clarify, the part corresponding to the part enclosed with the dotted-line frame shown by (a) is shown with the arrow.

  In the cell stack device 12, each fuel battery cell 1 is arranged via a current collecting member 14 to constitute a cell stack 13, and the lower end of each fuel battery cell 1 is fueled to the fuel battery cell 1. It is fixed to a manifold 15 for supplying gas by an adhesive such as a glass sealing material. Further, an elastically deformable conductive member 16 having a lower end fixed to the manifold 15 is provided so as to sandwich the cell stack 13 from both ends in the arrangement direction of the fuel cells 1 via the current collecting member 14.

  Further, in the conductive member 16 shown in FIG. 3, a current for drawing out a current generated by power generation of the cell stack 13 (fuel cell 1) in a shape extending outward along the arrangement direction of the fuel cells 1. A drawer portion 17 is provided.

Here, in the cell stack device 12 of the present invention, the cell stack 13 is configured by using the fuel cell 1 described above, whereby the porous fuel electrode layer 3 and the adhesion layer 9 are dense interconnectors and By being sealed with a dense solid electrolyte layer, the fuel stack can be prevented from leaking from the porous fuel electrode layer 3 and the adhesion layer 9 , and the long-term reliability of the cell stack device 12 is improved. It can be.

  FIG. 4 is an external perspective view showing an example of a fuel cell module 20 in which the cell stack device 12 of the present invention is housed in a housing container. The cell shown in FIG. The stack device 12 is accommodated.

  In order to obtain fuel gas used in the fuel cell 1, a reformer 22 for reforming raw fuel such as natural gas or kerosene to generate fuel gas is disposed above the cell stack 13. ing. The fuel gas generated by the reformer 22 is supplied to the manifold 15 via the gas flow pipe 23 and supplied to the fuel gas flow path 7 provided inside the fuel battery cell 1 via the manifold 15. The

  FIG. 5 shows a state where a part (front and rear surfaces) of the storage container 21 is removed and the cell stack device 12 and the reformer 22 housed inside are taken out rearward. Here, in the fuel cell module 20 shown in FIG. 4, the cell stack device 12 can be slid and stored in the storage container 21. The cell stack device 12 may include a reformer 22.

  In addition, the oxygen-containing gas introduction member 24 provided inside the storage container 21 is disposed between the cell stacks 13 juxtaposed to the manifold 15 in FIG. 5, and the oxygen-containing gas matches the flow of the fuel gas. The oxygen-containing gas is supplied to the lower end of the fuel cell 1 so that the fuel cell 1 flows laterally from the lower end toward the upper end. And the temperature of the fuel cell 1 can be raised by burning the fuel gas discharged from the fuel gas flow path of the fuel cell 1 and the oxygen-containing gas on the upper end side of the fuel cell 1, The activation of the cell stack device 12 can be accelerated. Further, the fuel gas discharged from the fuel gas flow path of the fuel battery cell 1 and the oxygen-containing gas are combusted on the upper end side of the fuel battery cell 1 so that the upper side of the fuel battery cell 1 (cell stack 13). It is possible to efficiently warm the reformer 22 disposed in the. Thereby, the reforming reaction can be efficiently performed in the reformer 22.

  Furthermore, in the fuel cell module 20 of the present invention, since the cell stack device 12 configured using the fuel cell 1 with improved power generation efficiency is stored in the storage container 21, the fuel with improved power generation efficiency. The battery module 20 can be obtained.

  FIG. 5 is an exploded perspective view showing an example of the fuel cell device of the present invention in which the fuel cell module 20 shown in FIG. 5 and an auxiliary machine for operating the fuel cell stack device 12 are housed in an outer case. FIG. In FIG. 5, a part of the configuration is omitted.

A fuel cell device 25 shown in FIG. 5 has a module housing chamber 29 in which an inside of an exterior case composed of a support column 26 and an exterior plate 27 is vertically divided by a partition plate 28 and the upper side thereof accommodates the fuel cell module 20 described above. The lower side is configured as an auxiliary equipment storage chamber 30 for storing auxiliary equipment for operating the fuel cell module 20. It should be noted that auxiliary equipment stored in the auxiliary equipment storage chamber 28 is omitted.

  Further, the partition plate 28 is provided with an air circulation port 31 for flowing the air in the auxiliary machine storage chamber 30 to the module storage chamber 29 side, and a part of the exterior plate 27 constituting the module storage chamber 29 An exhaust port 32 for exhausting air in the module storage chamber 29 is provided.

  In such a fuel cell device 25, as described above, the fuel cell module 20 that can improve the power generation efficiency is configured to be stored in the module storage chamber 29, thereby improving the power generation efficiency. 25.

  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 1 of the present invention, a hollow flat plate is shown, but the present invention can also be used in a cylindrical fuel battery cell. Moreover, in the fuel cell 1 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 6 is provided has been shown. However, both ends of the solid electrolyte layer and both ends of the interconnector are What is necessary is just to join, and it can be set as the fuel cell which does not leak fuel gas.

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 to a volume ratio of 48% by volume of NiO and 52% by volume of 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. Sample No. In No. 1, the volume ratio of the Y ₂ O ₃ powder after calcination and reduction was such that NiO was 45% by volume and Y ₂ O ₃ was 55% by volume.

Next, using a slurry obtained by mixing a ZrO ₂ powder (solid electrolyte layer raw material powder) having a particle diameter of 0.8 μm by solid micro-solution method in which 8 mol% of Y is 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.

Next, a slurry for a fuel electrode layer is prepared by mixing a NiO powder having an average particle size of 0.5 μm, a ZrO ₂ powder in which Y ₂ O ₃ is dissolved, an organic binder, and a solvent, and the fuel electrode layer is formed on the solid electrolyte layer sheet. A layered product formed by applying the layer slurry to form a fuel electrode layered product was formed. In each sample, the solid electrolyte sheet and the fuel electrode layer sheet are a part of the solid electrolyte layer between the interconnector to be produced later and the laminate in which the fuel electrode layer and the solid electrolyte layer are laminated. As shown in Table 1, it was appropriately adjusted and formed so as to be interposed. Then, it laminated | stacked on the predetermined position of the electroconductive support body molded body with the surface at the side of a fuel electrode layer molded body facing down.

  Subsequently, the laminated molded body in which the fuel electrode layer molded body and the solid electrolyte layer molded body were laminated as described above was calcined at 1000 ° C. for 3 hours.

Next, a composite oxide containing 85 mol% of CeO ₂ and 15 mol% of another rare earth element oxide (GdO _1.5 ) is pulverized by a vibration mill or a ball mill using isopropyl alcohol (IPA) as a solvent. Then, calcination was performed at 900 ° C. for 4 hours, and pulverization was performed again with a ball mill to adjust the degree of aggregation of the ceramic particles, thereby obtaining a raw material powder for an intermediate layer. A slurry for an intermediate layer produced by adding and mixing an acrylic binder and toluene to this powder was applied onto the solid electrolyte layer calcined body of the laminated calcined body by a screen printing method. A layer molded body was produced.

Next, a slurry for an adhesion layer was prepared by mixing NiO powder having an appropriately adjusted particle size, ZrO ₂ powder in which 8 mol% of Y ₂ O ₃ was dissolved, an organic binder, and a solvent.

Subsequently, an interconnector sheet having a thickness of 30 μm was prepared by a doctor blade method using an interconnector slurry obtained by mixing a LaCrO ₃ oxide, an organic binder, and a solvent. The surface of the interconnector sheet coated with the above-mentioned adhesion layer slurry is coated with the adhesion layer slurry, and the conductive electrode layer molded body and the solid electrolyte layer molded body are not formed. On the other flat portion of the support molded body, the both ends of the interconnector were laminated so as to be positioned on the solid electrolyte layer. A laminate in which the layers for 1 and 2 were laminated was produced.

  On the other hand, the interconnector sheet coated with the adhesion layer slurry is laminated at a predetermined position of the conductive support molded body, and then the fuel electrode layer slurry is coated on the solid electrolyte layer sheet. Laminate molded body in which the layer molded body is formed is laminated so that both end portions of the solid electrolyte layer are located on both end portions of the interconnector, and subsequently, an intermediate layer molded body is created on the solid electrolyte layer molded body, Sample No. A laminate in which the layers for 3 and 4 were laminated was produced.

  And sample No. with which these each layer was laminated | stacked. Each of the laminates 1 to 4 was co-fired at 1510 ° C. in the air 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 fuel cells having the structure shown in Table 1 were produced.

  The size of the produced fuel cell is 25 mm × 200 mm, the thickness of the conductive support (thickness between the flat surfaces n) is 2 mm, the porosity is 35%, the thickness of the fuel electrode layer is 10 μm, and the porosity is 24%. The thickness of the air electrode layer was 50 μm, the porosity was 40%, and the relative density of the solid electrolyte layer was 97%.

  Here, 10 fuel cells were prepared for each sample, and a leak test was performed in order to confirm whether or not a gas leak occurred in each fuel cell.

In the leak test, a fuel cell in which one side of the fuel gas flow path is sealed by a predetermined member is placed in water and applied to 1.5 to 3.5 kg / cm ² from the other side of the fuel cell. In this test, pressurized He gas is supplied for 30 to 60 seconds. A gas leak occurred when bubbles were generated from the fuel cells, and no gas leak occurred when bubbles were not generated from the fuel cells.

  Next, in a state where hydrogen gas (fuel gas) was allowed to flow inside the fuel cell, heating was performed at 850 ° C. for 10 hours to reduce the conductive support and the fuel electrode layer.

  And even after the reduction treatment, a leak test similar to that described above was performed.

  From the results in Table 1, sample No. Nos. 2 and 4 show that fuel gas leaks to three of the ten fuel cells when the fuel cells were manufactured. However, after the reduction process, fuel gas leaks to seven of the ten fuel cells. There was a leak. On the other hand, the sample No. provided with a part of the solid electrolyte layer interposed between the fuel electrode layer and the interconnector. In Nos. 1 and 3, fuel gas leaks were not detected both in the production of the fuel cells and after the reduction treatment.

  As a result, it was found that leakage of fuel gas can be suppressed by providing a part of the solid electrolyte layer between the fuel electrode layer and the interconnector.

  In addition, when the interconnector is provided after the fuel electrode layer and the solid electrolyte layer are provided, and between the fuel electrode layer and the interconnector, both in the case where the fuel electrode layer and the solid electrolyte layer are provided after the interconnector is provided. It was found that fuel gas leakage can be suppressed by providing a solid electrolyte layer on the surface.

DESCRIPTION OF SYMBOLS 1, 10, 11, 32: Fuel cell 2: Conductive support 3: Fuel electrode layer 4: Solid electrolyte layer 5: Air electrode layer 6: Interconnector 7: Fuel gas flow path 8: Intermediate layer 9: Adhesion layer 12: Cell stack device 20: Fuel cell module 25: Fuel cell device

Claims (5)

On one side main surface of the columnar conductive support, provided with an adhesion layer containing at least one of Ni and NiO, and a dense interconnector provided on the adhesion layer, on the other side main surface, Provided with a laminate in which a porous fuel electrode layer containing at least one of an iron group metal and an iron group metal oxide, a dense solid electrolyte layer, and a porous air electrode layer are laminated in this order. The both ends of the solid electrolyte layer and the fuel electrode layer are extended from the other main surface of the conductive support to the one main surface via the side surface, and both the end portions of the solid electrolyte layer and the joining both end portions of the interconnector, the fuel cell a part of the solid electrolyte layer is characterized in that interposed between said fuel electrode layer inter connctor.   The fuel cell according to claim 1, wherein the adhesion layer is provided only on the conductive support between both end portions of the solid electrolyte layer.   A cell stack formed by arranging a plurality of the fuel cells according to claim 1 or 2 in a state of being erected via a current collecting member and electrically connected in series, and a lower end portion of the fuel cells And a manifold for supplying fuel gas to the fuel cell.   A fuel cell module comprising the cell stack device according to claim 3 stored in a storage container.   5. A fuel cell device comprising: the fuel cell module according to claim 4; and an auxiliary machine for operating the fuel cell module.

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