JP6121895B2 - Electrolytic cell, electrolytic cell stack device, electrolytic module, and electrolytic device - Google Patents

Description

  The present invention relates to an electrolytic cell, an electrolytic cell stack device, a fuel cell module, and an electrolytic device having an intermediate layer between a conductive support and an interconnector.

  A solid oxide fuel cell, which is a kind of electrolytic cell, has a power generation element portion that is configured by sandwiching a solid electrolyte layer between a fuel electrode layer and an oxygen electrode layer.

  In the solid oxide fuel cell, for example, the power generation element portion as described above is formed on a porous conductive support having a gas passage therein, and fuel gas is formed in the gas passage inside the conductive support. By supplying a gas (for example, hydrogen-containing gas) to the fuel electrode layer through the conductive support, and simultaneously supplying an oxygen-containing gas such as air to the oxygen electrode layer, an electrode is formed at each electrode. A reaction is generated, and the generated current is taken out by an interconnector provided on the conductive support (for example, see Patent Document 1).

Conventionally, a solid oxide comprising an intermediate layer composed of Ni and ZrO ₂ containing a rare earth element between a conductive support containing Ni and Y ₂ O ₃ and an interconnector made of LaCrO _3. A physical fuel cell has also been developed (see, for example, Patent Document 2).

JP 2004-146334 A JP 2004-253376 A

  However, in the conventional solid oxide fuel cell, La in the interconnector easily diffuses to the conductive support side, so that the diffusion rate of La in the intermediate layer between the conductive support and the interconnector is slow. La may react with Zr in the intermediate layer, and the composite oxide containing La and Zr may precipitate in a dense layer form in the intermediate layer. In addition to the oxide layered, the fuel gas cannot be supplied to the intermediate layer on the interconnector side of the composite oxide layer, and NiO constituting the intermediate layer of this portion can be reduced. However, the electrical conductivity between the conductive support and the interconnector is reduced, and the power generation performance may be reduced.

  An object of the present invention is to provide an electrolysis cell, an electrolysis cell stack device, an electrolysis module, and an electrolysis device that can improve electrical conductivity between a conductive support and an interconnector.

  The electrolytic cell of the present invention includes a solid electrolyte layer, a first electrode layer containing Ni and a conductive support containing Ni, which are sequentially provided on one main surface of the solid electrolyte layer, and the solid electrolyte. A second electrode layer provided on the other main surface of the layer; an interconnector containing La provided on the conductive support and electrically connected to the first electrode layer; and the conductive support; An intermediate layer containing Zr and Ni formed between the interconnector and a composite oxide containing La and Zr is present in the intermediate layer; It is characterized by being dispersed in the layer.

  The electrolytic cell stack apparatus of the present invention is characterized in that a plurality of the above electrolytic cells are electrically connected.

  The electrolytic module of the present invention is characterized in that the electrolytic cell stack device is stored in a storage container.

  The electrolysis apparatus of the present invention is characterized in that the above-described electrolysis module and an auxiliary machine for operating the electrolysis module are housed in an outer case.

  In the electrolytic cell of the present invention, since the composite oxide containing La and Zr is present in the intermediate layer in a dispersed state, the fuel gas is interconnected between the conductive support and the composite oxide in the intermediate layer. The Ni in the intermediate layer can be reduced, and the conductivity between the interconnector and the conductive support can be improved. As a result, an electrolytic cell stack device, an electrolytic module, and an electrolytic device with improved power generation performance can be provided.

1 shows an embodiment of a solid oxide fuel cell, where (a) is a transverse sectional view and (b) is a longitudinal sectional view. It is a side view of the solid oxide fuel cell shown in FIG. 1 shows an embodiment of a fuel cell stack device, (a) is a side view schematically showing the fuel cell stack device, and (b) is a part of a portion surrounded by a broken line of the fuel cell stack device of (a). FIG. It is sectional drawing of an intermediate | middle layer and its vicinity. It is an external appearance perspective view which shows one form of a fuel cell module. It is a disassembled perspective view which shows one form of a fuel cell apparatus.

  FIG. 1 shows a solid oxide fuel cell (hereinafter, may be abbreviated as a fuel cell or a cell) which is an embodiment of an electrolytic cell, and (a) is a cross-sectional view thereof, (b) ) Is a longitudinal sectional view of (a). In both drawings, each configuration of the fuel cell 10 is partially enlarged. FIG. 2 is a side view of the fuel cell.

  This fuel cell 10 is a hollow plate type fuel cell 10 having a flat cross section and a porous conductive support (hereinafter referred to as a support) containing Ni having an elliptical cylindrical shape as a whole. 1) is provided. A plurality of fuel gas flow paths 2 are formed in the length direction L at appropriate intervals inside the support 1, and the fuel cell 10 has a structure in which various members are provided on the support 1. have.

  As understood from the shape shown in FIG. 1, the support 1 has a pair of opposed flat surfaces n (main surfaces) parallel to each other and arcuate surfaces (side surfaces) connecting the pair of flat surfaces n. m. Both surfaces of the flat surface n are formed substantially parallel to each other, and a fuel electrode layer (first electrode layer) 3 containing porous Ni so as to cover one flat surface n (lower surface) and the arcuate surfaces m on both sides. Further, a dense solid electrolyte layer 4 is laminated so as to cover the fuel electrode layer 3. A porous oxygen electrode layer (second electrode layer) 6 is laminated on the solid electrolyte layer 4 so as to face the fuel electrode layer 3 with the reaction preventing layer 5 interposed therebetween. On the other flat surface n (upper surface) where the fuel electrode layer 3 and the solid electrolyte layer 4 are not stacked, an interconnector 8 containing La is formed via a La diffusion promoting layer 17 and an intermediate layer 7. Yes.

  In other words, the power generating element portion 9 formed by superposing the fuel electrode layer 3 and the oxygen electrode layer 6 on both sides of the solid electrolyte layer 4 is provided on one flat surface of the support 1, and the other flat surface. In addition, a La diffusion promoting layer 17, an intermediate layer 7, and an interconnector 8 are formed.

  The interconnector 8 is electrically connected to the fuel electrode layer 3 positioned on the flat surface on one side of the support 1, and the La diffusion promoting layer 17 is interposed between the interconnector 8 and the conductive support 1. The intermediate layer 7 is formed. The La diffusion promoting layer 17 and the intermediate layer 7 are allowed to pass fuel gas.

The intermediate layer 7 contains Ni and ZrO ₂ containing rare earth elements (for example, YSZ), and is formed of a porous cermet. As shown in FIG. Insulating composite oxide (particles) 7a containing La and Zr is dispersed. An example of the composite oxide 7a containing La and Zr is lanthanum zirconate represented by La ₂ Zr ₂ O ₇ . La diffuses from the interconnector 8 toward the intermediate layer 7 during firing or during power generation, and reacts with Zr in the intermediate layer 7 to produce a composite oxide 7a containing La and Zr. . When the diffusion rate of La into the conductive support 1 in the intermediate layer 7 is slow, it easily reacts with Zr in the intermediate layer 7, and the complex oxide 7a containing La and Zr is a dense layer. It will be precipitated.

The amount of Ni in the intermediate layer 7 is preferably 65 to 35% by volume, and the amount of ZrO ₂ containing a rare earth element is preferably 35 to 65% by volume. The intermediate layer 7 may contain other metal components and oxide components as long as required characteristics are not impaired.

  The conductive support 1 and the La diffusion promoting layer 17 include Ni and ceramic particles, and the ceramic particles of the La diffusion promoting layer 17 have a larger average particle size than the ceramic particles of the conductive support 1. The La diffusion promoting layer 17 can have the same component and the same composition as the conductive support 1, but may have a different component and composition. As the ceramic particles of the La diffusion promoting layer 17, for example, rare earth oxide, alumina or the like can be used.

  Thus, since the average particle diameter of the ceramic particles of the La diffusion promoting layer 17 is larger than the average particle diameter of the ceramic particles constituting the conductive support 1, La is a particle of the ceramic particles constituting the conductive support 1. It is easier to diffuse the grain boundaries of the ceramic particles constituting the La diffusion promoting layer 17 than the boundary, and La diffused from the interconnector 8 to the intermediate layer 7 side easily diffuses from the intermediate layer 7 to the La diffusion promoting layer 17. Thus, it becomes difficult to react with Zr in the intermediate layer 7, and the composite oxide containing La and Zr does not exist in a dense layer form but exists in a dispersed state.

  For this reason, the fuel gas (hydrogen-containing gas) flowing through the fuel gas flow path 2 reaches the interconnector 8 via the conductive support 1, the La diffusion promoting layer 17, and the composite oxide 7a in the intermediate layer 7, and reaches the intermediate connector 8. Even if Ni in the layer 7 is oxidized, it can be reduced, and the conductivity between the interconnector 8 and the conductive support 1 can be improved.

  The presence of dispersed composite oxide (particles) 7a containing La and Zr means a state where the composite oxides 7a are separated from each other to such an extent that fuel gas can pass through, and EPMA (emission spectroscopy analysis). ), The positions where La and Zr are present are separated from each other. In the intermediate layer 7, there may be a portion where a part of the composite oxide 7 a is aggregated.

  The thickness of the intermediate layer 7 is desirably 15 μm or less. Thereby, the diffusion of La to the conductive support 1 is further promoted, the formation of the composite oxide 7a containing La and Zr in the intermediate layer 7 is suppressed, and the composite oxide 7a is deposited in a layered manner. Further, the composite oxide 7 a can be scattered and exist in the intermediate layer 7.

  In the above embodiment, the La diffusion promoting layer 17 is formed so that La diffused from the interconnector 8 to the intermediate layer 7 side is easily diffused from the intermediate layer 7 to the conductive support 1 side. Without forming the accelerating layer 17, for example, by adjusting the firing temperature and firing time and / or by reducing the thickness of the intermediate layer 7, from the intermediate layer 7 to the La conductive support 1 side. The diffusion may be promoted, and the composite oxide 7a containing La and Zr may be dispersed in the intermediate layer 7.

  The fuel electrode layer 3 and the solid electrolyte layer 4 are formed up to the other flat surface n (upper surface) via the arcuate surfaces m at both ends, so that both ends of the interconnector 8 are located at both ends of the solid electrolyte layer 4. The solid electrolyte layer 4 and the interconnector 8 surround the support 1 so that fuel gas flowing through the inside does not leak to the outside. Both ends of the interconnector 8 may be laminated on both ends of the solid electrolyte layer 4.

  More specifically, the intermediate layer 7 is provided to improve the bonding strength between the support 1 and the interconnector 8, and is formed together with the interconnector 8 in the entire length direction L of the support 1. ing. Similarly, the La diffusion promoting layer 17 is formed over the entire length L of the support 1.

  As shown in FIG. 4, the portion located on the upstream side of the fuel cell 10 is joined to the opening on the upper surface of the gas tank 16 with a sealing material S, while the downstream side is an open end, and the central portion is A power generation element portion 9 is provided in the corresponding portion. Hereinafter, each member will be described.

(Support 1)
The support 1 is required to be gas permeable in order to allow the fuel gas to permeate to the fuel electrode layer 3 and to be conductive in order to collect current via the interconnector 8. In order to satisfy such requirements and avoid the disadvantages caused by simultaneous firing, the support 1 is preferably composed of Ni and ceramic particles, for example, a specific rare earth oxide. In particular, the conductive material is not limited to this.

The rare earth oxide is used to approximate the thermal expansion coefficient of the support 1 to the thermal expansion coefficient of the solid electrolyte layer 4, and maintains high conductivity and diffuses the element into the solid electrolyte layer 4 and the like. A rare earth oxide containing at least one rare earth element selected from the group consisting of Y, Lu, Yb, Tm, Er, Ho, Dy, Gd, Sm, and Pr in combination with Ni. It is preferred to use. 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 and Pr ₂ O ₃ can be exemplified, and Y ₂ O ₃ and Yb ₂ O ₃ are preferable in that they are particularly inexpensive.

  These rare earth oxides hardly cause solid solution or reaction with Ni or its oxide during firing or during power generation, and Ni or its oxide in the support 1 and the rare earth oxide described above. Are difficult to diffuse. Therefore, even when the support 1 and the solid electrolyte layer 4 are simultaneously fired, the diffusion of rare earth elements into the solid electrolyte layer 4 is effectively suppressed, and adverse effects on the ionic conductivity and the like of the solid electrolyte layer 4 are avoided. can do.

  In particular, the Ni is contained in the support 1 in an amount of 35 to 70% by volume in that the thermal expansion coefficient of the support 1 is approximated to the thermal expansion coefficient of the solid electrolyte layer 4. Is preferably contained in the support 1 in an amount of 30 to 65% by volume. The support 1 may contain other metal components and oxide components as long as required characteristics are not impaired.

  Since the support 1 is required 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%. Further, the conductivity of the support 1 is preferably 300 S / cm or more, and particularly preferably 440 S / cm or more.

  Further, the length of the flat surface n of the support 1 is usually 15 to 35 mm, and the height of the support 1 is appropriately set according to the application, but is used for power generation in a general household. In some cases, the height is usually set to about 100 to 150 mm. Furthermore, arc-shaped surfaces m are formed at both ends of the flat surface n in order to prevent chipping at the corners and further increase the mechanical strength. In order to prevent peeling of the solid electrolyte layer 4 described later. The radius of curvature of the arcuate surface m is 5 mm or less, preferably 1 to 5 mm, more preferably 1 to 4 mm. In order to effectively prevent the solid electrolyte layer 4 from being peeled off, the thickness of the support 1 (the distance between the two flat surfaces n) is preferably in the range of 2 to 10 mm.

(Fuel electrode layer 3)
The fuel electrode layer 3 causes an electrode reaction, and is formed of a known porous cermet. For example, it is formed from ZrO ₂ or CeO ₂ containing rare earth elements and Ni and / or NiO.

The ZrO ₂ or CeO ₂ content in the fuel electrode layer 3 is preferably in the range of 35 to 65% by volume, and the Ni or NiO content is preferably 65 to 35% by volume. Further, the open porosity of the fuel electrode layer 3 should be 15% or more, particularly in the range of 20 to 40%. The thickness of the fuel electrode layer 3 is 1 to prevent deterioration in performance and peeling due to a difference in thermal expansion. 30 μm is desirable.

Further, as the rare earth elements dissolved in ZrO ₂ or CeO ₂ (the rare earth elements dissolved in CeO ₂ excludes Ce), the rare earth oxide used in the support 1 is shown as can be exemplified the same ones, in that to lower the polarization value of the cells, Y is about 3 to 10 mol% for ZrO _2, Sm for CeO ₂ is from 5 to 20 mol% What is dissolved to a certain extent is preferable.

  Further, it is sufficient that the fuel electrode layer 3 exists at least at a position facing the oxygen electrode layer 6. That is, in the example of FIG. 1, the fuel electrode layer 3 extends from the flat surface n on one side of the support 1 to the other flat surface n and extends to both ends of the interconnector 8, but is flat on one side. It may be formed only on the surface n.

(Solid electrolyte layer 4)
The solid electrolyte layer 4 has a function as an electrolyte for bridging electrons between the electrodes, and at the same time has gas barrier properties to prevent leakage of fuel gas and oxygen-containing gas such as air. is necessary. Therefore, as the solid electrolyte used to form the solid electrolyte layer 4, a dense oxide ceramic having such characteristics, for example, stabilized zirconia in which 3 to 15 mol% of a rare earth element is dissolved is used. Is preferred. Examples of rare earth elements in the stabilized zirconia include Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Td, Dy, Ho, Er, Tm, Yb, and Lu. However, Y and Yb are preferable in that they are inexpensive.

Furthermore, a perovskite-type lanthanum gallate complex oxide containing La and Ga can also be used as the solid electrolyte. This composite oxide has high oxygen ion conductivity, and high power generation efficiency can be obtained by using it as a solid electrolyte. This lanthanum gallate complex oxide is composed of La and Sr at the A site and Ga at the B site.
And those having a Mg, for example, the following general _{formula: (La 1-x Sr x} ) (Ga 1-y Mg y) O 3 ( where, x is a number of 0 <x <0.3, It is desirable that y has a composition represented by 0 <y <0.3. High power generation performance can also be exhibited by using a composite oxide having such a composition as a solid electrolyte.

  Such a solid electrolyte layer 4 desirably has a relative density (according to Archimedes method) of 93% or more, particularly 95% or more from the viewpoint of preventing gas permeation.

(Oxygen electrode layer 6)
The oxygen electrode layer 6 formed on the solid electrolyte layer 4 causes the electrode reaction described above, and as shown in FIG. 1, the fuel electrode layer described above with the solid electrolyte layer 4 interposed therebetween. 3 is arranged so as to face 3. That is, it is arranged at least on a portion located on one flat surface n of the support 1.

The oxygen electrode layer 6 is formed of sintered particles of a so-called ABO ₃ type perovskite oxide. As such a perovskite type oxide, at least one of transition metal type perovskite oxides, particularly LaMnO ₃ oxides, LaFeO ₃ oxides, and LaCoO ₃ oxides having La at the A site is preferable. 600 (La, Sr) (Co, Fe) O ₃ system because of its high electrical conductivity at a relatively low temperature of about ˜1000 ° C. and excellent surface diffusion function and volume diffusion function for oxygen ions. oxides, for example, the following general _{formula: La y Sr 1-y Co} Z Fe 1-Z O 3 ( where, y is the number of 0.5 ≦ y ≦ 0.7, z is 0.2 ≦ A composite oxide having a composition represented by: z ≦ 0.8 is particularly preferable.

  Further, such an oxygen electrode layer 6 must have gas permeability. Therefore, the conductive ceramics (perovskite oxide) has an open porosity of 20% or more, particularly 30 to 50. It is desirable to be in the range of%. The thickness of the oxygen electrode layer 6 is preferably 30 to 100 μm from the viewpoint of current collection.

The oxygen electrode layer 6 may be formed on the solid electrolyte layer 4, but a reaction preventing layer 5 is provided on the solid electrolyte layer 4, and the oxygen electrode layer 6 is interposed via the reaction preventing layer 5. Can also be laminated on the solid electrolyte layer 4. Such a reaction preventing layer 5 is for blocking element diffusion from the oxygen electrode layer 6 to the solid electrolyte layer 4, and is formed of an oxide sintered body having an element diffusion preventing function. As such an oxide for a reaction preventing layer, for example, an oxide containing Ce as a constituent element can be exemplified, and in particular, a Ce-based composite oxide in which a rare earth element oxide is dissolved in CeO ₂ is a high element. It is preferably used in that it has excellent oxygen ion conductivity and electronic conductivity in addition to diffusion barrier properties.

(Interconnector 8)
The interconnector 8 provided on the flat surface n on the support 1 is made of conductive ceramics, but has contact with fuel gas (hydrogen) and oxygen-containing gas, and therefore has resistance to reduction and oxidation. It is necessary to be. For this reason, lanthanum chromite perovskite oxides (LaCrO ₃ oxides) are generally used as the conductive ceramics. The interconnector 8 may be, for example, a LaSrTiO ₃ perovskite complex oxide containing Ti, and is not particularly limited. Further, in order to prevent leakage of the fuel gas passing through the inside of the support 1 and the oxygen-containing gas passing through the outside of the support 1, the conductive ceramics must be dense, for example, 93% or more, particularly 95%. It is preferable to have the above relative density.

  The thickness of the interconnector 8 is preferably 10 to 200 μm from the viewpoint of preventing gas leakage and electric resistance.

(Manufacture of fuel cells)
The fuel cell 10 having the above-described structure includes, for example, a mixed powder (Ni or a mixed powder of an oxide powder thereof and a rare earth oxide powder) for forming the support 1 described above, an organic binder, a solvent, Then, if necessary, a slurry is prepared by mixing with a dispersant such as methylcellulose, and the slurry is extruded to produce a columnar support body having a fuel gas passage, which is dried, and 800-1100 Calcination in the temperature range of ℃.

A sheet for a solid electrolyte layer (hereinafter referred to as a solid electrolyte sheet) is prepared. For example, solid electrolyte powder such as ZrO ₂ (YSZ) containing Y is mixed with an organic binder and a solvent such as toluene to prepare a molding slurry, and a solid electrolyte sheet is molded using this slurry.

  Next, a fuel electrode layer sheet is prepared using a slurry prepared by mixing an organic binder and a solvent with a fuel electrode layer forming powder (for example, a mixed powder of NiO powder and YSZ powder). A layer sheet is laminated on one surface of the above solid electrolyte sheet, and this is wound around a predetermined position of the above-mentioned support molded body (calcined body) so that the fuel electrode layer sheet is inside, and dried. To do.

Thereafter, for example, an interconnector powder such as a LaCrO ₃ based material is mixed with an organic binder and a solvent to prepare a slurry, and an interconnector sheet is prepared using this slurry according to a conventional method.

  Next, a slurry is prepared by mixing an organic binder and a solvent with a mixed powder (a mixed powder of Ni or an oxide powder thereof and a rare earth oxide powder) for forming a La diffusion promoting layer. Then, it is applied to a portion of a predetermined surface of the calcined body of the molded body for support to form a La diffusion promoting layer molded body.

Next, a mixed powder (for example, a mixed powder of Ni and / or NiO powder and a ZrO ₂ powder in which a rare earth element is dissolved) is mixed with a predetermined organic binder and a solvent to prepare a slurry. This slurry is applied onto the La diffusion promoting layer molded body to form an intermediate layer sheet. An interconnector sheet is laminated on the intermediate layer sheet and dried.

  Next, the laminated molded body is subjected to heat treatment for debinding, and then co-fired at 1300 to 1600 ° C. in an oxygen-containing atmosphere, whereby the fuel electrode layer 3 and the solid electrolyte layer 4 are formed on the support 1. Further, a La diffusion promoting layer 17, an intermediate layer 7, and an interconnector 8 are laminated, and if necessary, a sintered structure provided with an element diffusion preventing layer and a reaction preventing layer 5 can be obtained.

Furthermore, a coating solution for the oxygen electrode layer in which LaFeO ₃ oxide powder or the like is dispersed in a solvent is sprayed on the solid electrolyte layer 4 (or the reaction preventing layer 5) of the sintered body obtained above. (Or dipping) to form a coating layer for the oxygen electrode layer, and baking at 1000 to 1300 ° C. to obtain the fuel cell 10 having the oxygen electrode layer 6. In the obtained fuel battery cell 10, the conductor component contained in the support 1 or the like becomes an oxide such as NiO by firing in an oxygen-containing atmosphere. It will be reduced by the reduction process and power generation.

FIG. 4 shows an example of a fuel cell stack device configured by electrically connecting a plurality of the above-described fuel cells 10 in series via a current collecting member 13, and (a) Is a side view schematically showing the fuel cell stack device 11, (b) is a partially enlarged cross-sectional view of the fuel cell stack device 11 of (a), the portion surrounded by the broken line shown in (a) An excerpt is shown. In addition, in (b), the part corresponding to the part surrounded by the broken line shown in (a) is indicated by an arrow, and in the fuel cell 10 shown in (b), the above-described reaction prevention is shown. Some members such as the layer 5 are omitted.

  In the fuel cell stack device 11, the cell stack 12 is configured by arranging the fuel cells 10 via the current collecting members 13, and the lower end of each fuel cell 10 is shown in FIG. As shown, the sealing material S is fixed to the opening of the upper wall of the gas tank 16 for supplying fuel gas to the fuel cell 10. That is, the upper wall of the gas tank 16 is formed with an opening into which the lower end of the cell stack 12 is inserted. With the lower end of the cell stack 12 inserted into the opening, glass, glass ceramics, etc. Bonded with a sealing material S.

  In addition, an elastically deformable conductive member 14 having a lower end portion fixed to the gas tank 16 is provided so as to sandwich the fuel cell stack 12 from both ends in the arrangement direction of the fuel cells 10.

  Further, in the conductive member 14 shown in FIG. 4, in order to draw out the current generated by the power generation of the fuel cell stack 12 (fuel cell 10) in a shape extending outward along the arrangement direction of the fuel cells 10. Current extraction part 15 is provided.

  Here, in the fuel cell stack device 11 of the present embodiment, the fuel cell stack device 11 with improved power generation performance is formed by configuring the fuel cell stack 12 using the fuel cell 10 described above. Can do.

  FIG. 5 is an external perspective view showing an example of the fuel cell module 18 in which the fuel cell stack device 11 is accommodated in the storage container 19, and the fuel shown in FIG. 4 is placed inside the rectangular parallelepiped storage container 19. The battery cell stack device 11 is accommodated.

  Note that a reformer 20 for reforming raw fuel such as natural gas or kerosene to generate fuel gas is provided above the fuel cell stack 12 in order to obtain fuel gas used in the fuel cell 10. It is arranged. The fuel gas generated by the reformer 20 is supplied to the gas tank 16 via the gas flow pipe 21 and supplied to the fuel gas passage 2 provided inside the fuel cell 10 via the gas tank 16. The

  FIG. 5 shows a state where a part (front and rear surfaces) of the storage container 19 is removed and the fuel cell stack device 11 and the reformer 20 housed inside are taken out rearward. In the fuel cell module 18 shown in FIG. 5, the fuel cell stack device 11 can be slid and stored in the storage container 19. The fuel cell stack device 11 may include the reformer 20.

Further, in FIG. 5, the oxygen-containing gas introduction member 22 provided inside the storage container 19 is disposed between the fuel cell stacks 12 juxtaposed to the gas tank 16, and the oxygen-containing gas flows into the flow of the fuel gas. In addition, an oxygen-containing gas is supplied to the lower end of the fuel cell 10 so that the side of the fuel cell 10 flows from the lower end toward the upper end. Then, the temperature of the fuel cell 10 is raised by reacting the fuel gas discharged from the fuel gas channel 2 of the fuel cell 10 with the oxygen-containing gas and burning it on the upper end side of the fuel cell 10. Thus, the start-up of the fuel cell stack device 11 can be accelerated. Further, by burning the fuel gas and the oxygen-containing gas discharged from the fuel gas flow path 2 of the fuel battery cell 10 on the upper end side of the fuel battery cell 10, the fuel battery cell 10 (fuel battery cell stack 12) is burned.
) Can be warmed. Thereby, the reforming reaction can be efficiently performed in the reformer 20.

  Furthermore, in the fuel cell module 18 of the present embodiment, since the fuel cell stack device 11 described above is housed in the housing container 19, the fuel cell module 18 with improved power generation performance can be obtained.

  6 is an exploded perspective view showing an example of a fuel cell device in which the fuel cell module 18 shown in FIG. 5 and an auxiliary machine for operating the fuel cell stack device 11 are housed in an outer case. is there. In FIG. 6, a part of the configuration is omitted.

  A fuel cell device 23 shown in FIG. 6 has a module housing chamber in which an outer case made up of support columns 24 and an outer plate 25 is divided into upper and lower portions by a partition plate 26 and the upper side thereof stores the above-described fuel cell module 18. 27, the lower side is configured as an auxiliary equipment storage chamber 28 for storing auxiliary equipment for operating the fuel cell module 18. In addition, auxiliary machines stored in the auxiliary machine storage chamber 28 are omitted.

  In addition, the partition plate 26 is provided with an air circulation port 29 for flowing the air in the auxiliary machine storage chamber 28 to the module storage chamber 27 side, and a part of the exterior plate 25 constituting the module storage chamber 27 An exhaust port 30 for exhausting the air in the module storage chamber 27 is provided.

  In such a fuel cell device 23, as described above, the fuel cell module 18 that can improve the power generation performance is housed in the module storage chamber 27, thereby forming the fuel cell device 23 with improved power generation performance. be able to.

  It should be noted that the present invention is not limited to the above-described embodiment, and various changes and improvements can be made without departing from the scope of the present invention.

  For example, in the above embodiment, the hollow plate type solid oxide fuel cell has been described, but it is needless to say that it may be a cylindrical or flat plate type solid oxide fuel cell.

Furthermore, although the fuel cell, the fuel cell stack device, the fuel cell module, and the fuel cell device have been described in the above embodiment, the present invention is not limited to this, and water vapor and voltage are applied to the electrolysis cell. The present invention can also be applied to an electrolysis cell (SOEC) that generates hydrogen and oxygen (O ₂ ) by electrolyzing water vapor (water), and an electrolysis module and electrolysis apparatus including the electrolysis cell.

First, a kneaded material prepared by mixing 46% by volume of NiO powder having an average particle size of 0.5 μm, 54% by volume of Y ₂ O ₃ powder, an organic binder and a solvent is molded by an extrusion molding method and dried. A molded body for a support was produced by degreasing. In the molded article for support, the volume ratio after reduction was 48% by volume for Ni and 52% by volume for Y ₂ O ₃ .

Next, using a slurry obtained by mixing ZrO ₂ powder (solid electrolyte layer powder) having a particle diameter of 0.8 μm in which 8 mol% Y is solid-dissolved by a microtrack method, an organic binder, and a solvent, A solid electrolyte sheet having a thickness of 30 μm was prepared by a blade method.

Next, a slurry for a fuel electrode layer is prepared by mixing 50% by volume of NiO powder having an average particle size of 0.5 μm, 50% by volume of ZrO ₂ powder (YSZ) in which Y is dissolved, and a solvent, and applying the slurry onto a solid electrolyte sheet Thus, a fuel electrode layer molded body was formed. Then, it laminated | stacked on the predetermined position of the support body molded object with the surface at the side of a fuel electrode layer molded object facing down.

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

The slurry for forming the reaction preventing layer molded body uses a composite oxide containing 90 mol% of CeO ₂ and 10 mol% of rare earth element oxide (GdO _1.5 ), and isopropyl alcohol (IPA) as a solvent. The mixture was pulverized with a vibration mill or a ball mill, calcined at 900 ° C. for 4 hours, pulverized again with a ball mill, and an organic binder and a solvent were added to the powder and mixed. .

  This slurry for reaction prevention layer was apply | coated by the screen printing method on the solid electrolyte layer calcined body of the obtained laminated calcined body.

_{Subsequently,} the _{La (Mg 0.3 Cr 0.7) 0.96} O 3, to prepare a slurry of a mixture of organic binder and a solvent, to prepare a interconnector sheet.

  A slurry for La diffusion promoting layer obtained by mixing 46% by volume of NiO powder having an average particle size of 0.5 μm, 54% by volume of ceramic particle powder shown in Table 1, an organic binder and a solvent, This was applied to a portion where the fuel electrode layer (and the solid electrolyte layer) was not formed (a portion where the support was exposed) to form a compact for the La diffusion promoting layer.

In Table 1, Sample No. 1 to ₃ use Y ₂ O ₃ as ceramic particles of the La diffusion promoting layer. 4 uses Yb ₂ O ₃ and sample no. 5 _Al 2 _{O 3} was used powder.

An intermediate layer slurry was prepared by mixing 45% by volume of NiO powder having an average particle size of 0.5 μm, 55% by volume of ZrO ₂ powder (YSZ) in which Y was dissolved, and an organic binder and a solvent. The prepared intermediate layer slurry was applied onto the La diffusion promoting layer formed body to laminate the intermediate layer formed body. An interconnector sheet was laminated on the intermediate layer molded body.

  Next, the above-mentioned laminated molded body was subjected to binder removal treatment and fired at 1500 ° C. for 2 hours in the air.

Next, a mixed liquid composed of La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O ₃ powder having an average particle diameter of 2 μm and isopropyl alcohol was prepared, and the surface of the reaction preventing layer of the laminated sintered body Was spray-coated to form an oxygen electrode layer molded body and baked at 1100 ° C. for 4 hours to form an oxygen electrode layer, thereby producing the fuel cell shown in FIG.

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

  Next, hydrogen gas was allowed to flow inside the fuel cell, and the support and the fuel electrode layer were subjected to reduction treatment at 850 ° C. for 10 hours.

Thereafter, the composite oxide of La and Zr (La ₂ Zr ₂ O ₇ ) in the intermediate layer was confirmed by emission spectroscopic analysis (EPMA), and it was confirmed whether it was present in a layered manner or dispersed. . When the composite oxide particles alone or agglomerated aggregates of a plurality of composite oxide particles exist at intervals, it is assumed that they are dispersed.

The fuel gas is circulated through the fuel gas flow path of the fuel cell, the air is circulated outside the fuel cell, and the fuel cell is 750 ° C., Uf 75%, 0.3 A / cm ² using an electric furnace, The case where the difference between the voltage of the whole cell and the voltage between the oxygen electrode layer not including the interconnector and the support was 40 mV or more was determined to be a high resistance, and is indicated by x in Table 1.

  The average particle diameters of the ceramic particles in the support and the La diffusion promoting layer were determined by a scanning electron microscope (SEM) photograph and an image analyzer in the sintered body, and are shown in Table 1.

  From the results shown in Table 1, sample No. 1 in which a composite oxide containing La and Zr is present in the intermediate layer in a layered form. 1 and 2 show that the electrical resistance between the interconnector and the support is high. On the other hand, sample No. 2 in which a composite oxide containing La and Zr is present in the intermediate layer is dispersed. In 3-5, it turns out that the electrical resistance between an interconnector and an electroconductive support body is low, and can improve electric power generation performance.

1: conductive support 3: fuel electrode layer 4: solid electrolyte layer 6: oxygen electrode layer 7: intermediate layer 7a: composite oxide 8: interconnector 10: solid oxide fuel cell 11: fuel cell stack device 17: La diffusion promoting layer 18: Fuel cell module 23: Fuel cell device

Claims (7)

  A solid electrolyte layer, a first electrode layer containing Ni and a conductive support containing Ni, which are sequentially provided on one of the opposing main surfaces of the solid electrolyte layer; and the other main surface of the solid electrolyte layer A second electrode layer provided; an interconnector including La that is provided on the conductive support and is electrically connected to the first electrode layer; and the conductive support and the interconnector. An intermediate layer containing Zr and Ni that is formed, and a composite oxide containing La and Zr is present in the intermediate layer, and the composite oxide is dispersed in the intermediate layer. An electrolytic cell characterized by that.   The electrolysis according to claim 1, wherein a La diffusion promoting layer that promotes diffusion of La into the conductive support is formed between the intermediate layer and the conductive support. cell.   The conductive support and the La diffusion promoting layer contain Ni and ceramic particles, and the average particle size of the ceramic particles of the La diffusion promoting layer is larger than the average particle size of the ceramic particles of the conductive support. The electrolysis cell according to claim 2, which is large.   The electrolytic cell according to claim 1, wherein the intermediate layer has a thickness of 15 μm or less.   5. An electrolysis cell stack apparatus comprising a plurality of electrolysis cells according to claim 1 electrically connected.   An electrolytic module comprising the electrolytic cell stack device according to claim 5 housed in a housing container.   An electrolysis apparatus comprising the electrolysis module according to claim 6 and an auxiliary machine for operating the electrolysis module in an outer case.

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