JP2019009079A - Cell, cell stack device, module, and module storage device - Google Patents

Abstract

To provide a cell, a cell stack device, a module, and a module storage device with improved reliability.SOLUTION: A cell 10 according to the present disclosure includes a solid electrolyte layer 9 and an air electrode layer 1 that is stacked on the solid electrolyte layer 9 and has a first layer 1a which is dense on the solid electrolyte layer 9 side and a second layer 1b which is porous provided on the side opposite to the solid electrolyte layer 9 side, and the air electrode layer 1 has a gap X extending from the surface of the second layer 1b to at least the inside of the first layer 1a.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a cell, a cell stack device, a module, and a module housing device.

  In recent years, as a next-generation energy, a cell stack in which a plurality of fuel cells, which are one type of cells that can obtain electric power using a fuel gas (hydrogen-containing gas) and an oxygen-containing gas (air), are arranged in a manifold. A device has been proposed.

As such a fuel cell, a fuel electrode layer containing ZrO _{2 in} which Ni and a rare earth element are dissolved in a solid support on a conductive support substrate, and a solid electrolyte containing ZrO _{2 in} which a rare earth element is dissolved And an air electrode layer made of a perovskite complex oxide containing Sr are provided in this order. There has also been proposed a fuel cell in which an intermediate layer made of CeO _{2 in} which a rare earth element (excluding Ce) is dissolved is provided between the solid electrolyte layer and the air electrode layer.

  In addition, a structure in which coarse particles are connected in a three-dimensional network has been proposed for the purpose of increasing the three-phase interface in the upper layer portion with two air electrode layers (see, for example, Patent Document 1).

JP 2010-267631 A

  However, since the thermal expansion coefficient differs between the air electrode layer and the intermediate layer or solid electrolyte layer immediately below the air electrode layer, thermal stress is applied to the joint surface with the layer immediately below the air electrode layer, and the air electrode layer There was a risk that cracks would occur in the layer immediately below.

  That is, an object of the present invention is to optimize the shape of the air electrode layer and provide a highly reliable cell.

  The cell of the present disclosure is provided with a solid electrolyte layer, a first layer that is laminated on the solid electrolyte layer, and is provided on the solid electrolyte layer side, and on the opposite side of the solid electrolyte layer side. An air electrode layer having a porous second layer, and the air electrode layer has a void extending from the surface of the second layer to at least the inside of the first layer. To do.

  The cell stack device according to the present disclosure includes a plurality of the cells and is electrically connected to the plurality of cells.

  The module according to the present disclosure is characterized in that the cell stack device is stored in a storage container.

  The module storage device of the present disclosure is characterized in that the module and an auxiliary machine for operating the module are stored in an outer case.

According to the cell of the present disclosure, the thermal stress generated in the joint surface with the layer immediately below the air electrode layer by having a gap extending from the surface of the second layer of the air electrode layer to at least the inside of the first layer. Can be reduced. Thereby, a highly reliable cell can be provided.

An example of the cell of this embodiment is shown, (a) is a cross-sectional view, (b) is the perspective view which fractured | ruptured one part. It is an expansion cross-sectional view which shows typically the cross section of an intermediate | middle layer and an air electrode layer in an example of the cell of this embodiment. It is an external appearance perspective view which shows an example of the module provided with the cell of this embodiment. It is a disassembled perspective view which abbreviate | omits and shows an example of the module storage apparatus of this embodiment.

  Hereinafter, the present embodiment will be described with reference to the drawings. Note that a fuel cell (hereinafter referred to as a cell) will be described as an example of the cell.

  FIG. 1 (a) shows a cross section of a hollow plate cell 10 and FIG. 1 (b) is a perspective view of the cell partially broken. In both drawings, each member of the cell 10 is partially enlarged.

  The cell 10 includes a conductive support substrate 3 having an elliptical column shape as a whole. A plurality of fuel gas passages 5 are formed in the longitudinal direction at predetermined intervals inside the conductive support substrate 3, and the cell 10 has a structure in which various members are provided on the conductive support substrate 3. have.

  As understood from the shape shown in FIG. 1A, the conductive support substrate 3 includes a flat portion n and arc-shaped portions m at both ends of the flat portion n. Both surfaces of the flat portion n are formed substantially parallel to each other, and a fuel electrode layer 7 is provided so as to cover one surface (lower surface) of the flat portion n and the arc-shaped portions m on both sides. A dense solid electrolyte layer 9 is laminated so as to cover the layer 7. Further, the air electrode layer 1 is laminated on the solid electrolyte layer 9 so as to face the fuel electrode layer 7 with the intermediate layer 4 interposed therebetween. An interconnector 2 is formed on the other surface of the flat portion n where the fuel electrode layer 7 and the solid electrolyte layer 9 are not stacked. As is apparent from FIGS. 1A and 1B, the fuel electrode layer 7 and the solid electrolyte layer 9 extend to both sides of the interconnector 2 via the arc-shaped portions m at both ends, and the conductive support substrate. 3 is configured so as not to be exposed to the outside.

  Here, in the cell 10, the portion of the fuel electrode layer 7 facing (facing) the air electrode layer 1 functions as a fuel electrode layer to generate power. That is, an oxygen-containing gas such as air is flowed outside the air electrode layer 1 and a fuel gas (hydrogen-containing gas) is flowed into the gas passage 5 in the conductive support substrate 3 to generate power by heating to a predetermined operating temperature. To do. The current generated by the power generation is collected via the interconnector 2 attached to the conductive support substrate 3. Below, each member which comprises the cell 10 is demonstrated in order.

  Since the conductive support substrate 3 is required to be gas permeable in order to allow the fuel gas to pass to the fuel electrode layer 7 and to be conductive in order to collect current via the interconnector 2, For example, it can be formed of an iron group metal component and a rare earth element 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. In the present embodiment, any of them can be used, but Ni and / or NiO can be contained as an iron group component because it is inexpensive and stable in fuel gas. A plurality of iron group metal components can also be contained.

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

In addition, the volume ratio after firing-reduction is the iron group metal component: rare earth element oxide in that the good conductivity of the conductive support substrate 3 is maintained and the thermal expansion coefficient is approximated to that of the solid electrolyte layer 9. (For example, Ni: Y ₂ O ₃ ) is in a volume ratio of 35:65 to 65:35 (for example, iron group metal component / (iron group metal component + Y) is 65 to 86 mol% in molar ratio) can do. The conductive support substrate 3 may contain other metal components and oxide components as long as required characteristics are not impaired.

  Moreover, since the electroconductive support substrate 3 needs to have fuel gas permeability, the open porosity can usually be 20% or more, particularly 25 to 50%. Further, the conductivity of the conductive support substrate 3 can be 50 S / cm or more, particularly 300 S / cm or more, and further 440 S / cm or more.

  In the hollow plate cell 10 shown in FIG. 1, the length of the flat portion n of the conductive support substrate 3 (length in the width direction of the conductive support substrate 3) is 15 to 35 mm, and the length of the arc-shaped portion m (arc). Is 2 to 8 mm, the thickness of the conductive support substrate 3 (the thickness between both surfaces of the flat portion n) can be 1.5 to 5 mm.

The fuel electrode layer 7 causes an electrode reaction, and can be formed of a well-known porous conductive ceramic. For example, it can be formed from ZrO ₂ in which a rare earth element (excluding Zr) is dissolved or CeO _{2 in} which a rare earth element (excluding Ce) is dissolved, and Ni and / or NiO.

The content of ZrO ₂ in which the rare earth elements (excluding Zr) are dissolved in the fuel electrode layer 7 or CeO ₂ in which the rare earth elements (excluding Ce) are dissolved, and the content of Ni or NiO are calcined and reduced. The volume ratio of Ni: rare earth elements (excluding Zr) ZrO ₂ (Ni: YSZ) or CeO ₂ in which rare earth elements (excluding Ce) are solid solution is 35:65 to 65 by volume ratio. : 35. Further, the open porosity of the fuel electrode layer 7 can be 15% or more, particularly 20 to 40%, and the thickness thereof can be 1 to 30 μm. For example, the power generation performance can be improved by setting the thickness of the fuel electrode layer 7 in the above range, and the difference in thermal expansion between the solid electrolyte layer 9 and the fuel electrode layer 7 by setting the thickness in the above range. It is possible to suppress peeling and the like.

  Further, in the example of FIGS. 1A and 1B, the fuel electrode layer 7 extends to both side surfaces of the interconnector 2, but exists at a position facing the air electrode layer 1 so as to face the fuel electrode. Since the layer 7 only needs to be formed, the fuel electrode layer 7 may be formed only in the flat portion n on the side where the air electrode layer 1 is provided, for example. The interconnector 2 can also be provided directly on the flat portion n of the conductive support substrate 3 on the side where the solid electrolyte layer 9 is not provided. In this case, the interconnector 2 and the conductive support substrate 3 The potential drop between them can be suppressed.

The solid electrolyte layer 9 provided on the fuel electrode layer 7 is a partially stabilized or stabilized ZrO containing 3 to 15 mol% of rare earth elements such as Y (yttrium), Sc (scandium), Yb (ytterbium). _A dense ceramic made of ₂ can be used. Further, Y can be used as the rare earth element because it is inexpensive. Furthermore, the solid electrolyte layer 9 can have 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 3 to 50 μm. can do.

  As shown in FIG. 1, the air electrode layer 1 is laminated on a solid electrolyte layer 9 via an intermediate layer 4 described later, and has a two-layer structure. A dense layer provided on the solid electrolyte layer 9 side is the first layer 1a. The porous layer provided on the side opposite to the solid electrolyte layer side is the second layer 1b. The first layer 1a is a layer in which ceramic particles having ion conductivity and electron conductivity and ceramic particles made of a perovskite oxide having electron conductivity are mixed. The second layer 1b is a layer made of ceramic particles having electronic conductivity formed by connecting porous coarse particles in which a large number of conductive ceramic fine particles are aggregated in a three-dimensional network.

The ceramic particles having ion conductivity and electron conductivity are, for example, CeO ₂ in which Gd or Sm is dissolved. The raw material powder is (CeO ₂ ) _1-x (SmO _1.5 ) _x or (CeO ₂ ) _1-x (GdO _1.5 ) _x (x is a number satisfying 0 <x ≦ 0.3). ). Furthermore, CeO ₂ in which 10 to 20 mol% of GdO _1.5 or SmO _1.5 is dissolved may be used from the viewpoint of reducing electric resistance.

As ceramic particles made of perovskite type oxide having electron conductivity, LaFeO ₃ type oxide is used because it is a transition metal perovskite type oxide and has high electrical conductivity at an operating temperature of about 600 to 1000 ° C. Has been. In the perovskite oxide, Sr and the like may exist together with La at the A site, and Co and Mn may exist together with Fe at the B site. For example, it is a composite oxide represented by La _y Sr _1-y Co _z Fe _1-z O ₃ , and y and z are 0.5 ≦ y ≦ 0.7 and 0.2 ≦ z ≦ 0, respectively. May be in the range of .8.

  The first layer 1a may have a porosity of 15 to 30% so as to have gas permeability. Further, the thickness of the first layer 1a may be 10 to 20 μm. The second layer 1b may have a porosity of 40 to 60% so as to have gas permeability. The thickness of the second layer 1b may be 50 to 120 μm.

The intermediate layer 4 is provided between the solid electrolyte layer 9 and the air electrode layer 1. The intermediate layer 4 can be made of CeO _{2 in} which Gd and Sm are dissolved, and the raw material powder thereof is (CeO ₂ ) _1-x (SmO _1.5 ) _x or (CeO ₂ ) _1-x (GdO _{1 .5) x} (x may have a composition represented by 0 <a number satisfying x ≦ 0.3). Furthermore, CeO ₂ in which 10 to 20 mol% of GdO _1.5 or SmO _1.5 is dissolved may be used from the viewpoint of reducing electric resistance.

  Although not shown, the intermediate layer 4 may be composed of an inner layer located on the solid electrolyte layer 9 side and an outer layer provided on the inner layer and located on the air electrode layer 1 side. The concentration of rare earth element Gd may be higher. The concentration of the rare earth element in the inner layer can be 1.05 to 3 times the concentration of the rare earth element in the outer layer. The thickness of the entire intermediate layer 4 may be 3 μm to 5 μm, and the thickness of the first layer 4 a may be 0.06 μm to 2.5 μm.

The interconnector 2 can be formed of conductive ceramics, but since it is in contact with the fuel gas (hydrogen gas) and the oxygen-containing gas (air), the interconnector 2 must have reduction resistance and oxidation resistance. is there. For this reason, lanthanum chromite-based perovskite complex oxides (LaCrO ₃ -based oxides) are generally used as conductive ceramics having reduction resistance and oxidation resistance. Further, in order to suppress leakage of the fuel gas passing through the inside of the conductive support substrate 3 and the oxygen-containing gas passing through the outside of the conductive support substrate 3, such conductive ceramics must be dense, for example, 93% or more In particular, it is preferable to have a relative density of 95% or more.

  The thickness of the interconnector 2 can be set to 3 to 200 μm from the viewpoint of preventing gas leakage and preventing the electrical resistance from becoming too large. By setting the thickness within this range, gas leakage hardly occurs and the electrical resistance does not become too high, so that the current collecting function can be enhanced.

  In addition, in order to reduce the difference in thermal expansion coefficient between the interconnector 2 and the conductive support substrate 3 between the interconnector 2 and the conductive support substrate 3, an adhesion layer having a composition similar to that of the fuel electrode layer 7 is used. 8 may be formed. 1A and 1B show a state in which an adhesion layer 8 having a composition similar to that of the fuel electrode layer 7 is formed between the interconnector 2 and the conductive support substrate 3.

  Although not shown, a P-type semiconductor layer can be provided on the outer surface (upper surface) of the interconnector 2. By connecting the current collecting member to the interconnector 2 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, those having higher electron conductivity than LaCrO ₃ oxides constituting the interconnector 2, for example, LaMnO ₃ oxides and LaFeO ₃ oxides in which Mn, Fe, Co, etc. exist at the B site P-type semiconductor ceramics made of at least one of LaCoO ₃ -based oxides can be used. The thickness of such a P-type semiconductor layer can generally be in the range of 30 to 100 μm.

  As described above, since the air electrode layer 1 and the intermediate layer 4 are made of different materials, the thermal expansion coefficients of the respective layers are different. Therefore, thermal stress is applied to the joint surface between the air electrode layer 1 and the intermediate layer 4 immediately below the air electrode layer 1, cracks are generated in the intermediate layer 4 immediately below the air electrode layer 1, and the reliability of the cell 10 is increased. There was a risk that the performance would decrease.

  Therefore, as shown in FIG. 2, according to the cell 10 of the present embodiment, the air electrode layer 1 has a gap X extending from the surface of the second layer 1b to at least the inside of the first layer 1a.

  With this configuration, by having the gap X extending in the stacking direction of the air electrode layer 1, even if the air electrode layer 1 expands or contracts in a direction orthogonal to the stacking direction of the air electrode layer 1, Due to the presence, the thermal stress is dispersed, and the thermal stress generated on the joint surface with the layer immediately below the air electrode layer 1 can be reduced. As a result, the reliability of the cell 10 can be improved.

  Further, the gap X may extend over the entire length in the stacking direction of the air electrode layer 1. With this configuration, it is possible to reduce the bonding area between the air electrode layer 1 and the intermediate layer 4 immediately below, so that the thermal stress generated on the bonding surface can be further reduced.

  FIG. 3 shows a cell stack device 15 including a cell stack 13 that is electrically connected in series via a plurality of current collecting members (not shown) of the cell 10 of the present embodiment. FIG. 2 is an external perspective view showing an example of a module 11 housed in 12.

  The cell 10 and the current collecting member are joined by the adhesive layer Y. The adhesive layer Y is a layer that is laminated immediately above the air electrode layer 1 of the cell 10 and has a smaller thermal expansion coefficient than the air electrode layer 1. The cell 10 including the adhesive layer Y may be used.

The adhesive layer Y can be made of a material mainly composed of ceramic particles made of a perovskite oxide having electronic conductivity (50 mass% or more). As ceramic particles made of perovskite type oxide having electron conductivity, LaFeO ₃ type oxide is used because it is a transition metal perovskite type oxide and has high electrical conductivity at an operating temperature of about 600 to 1000 ° C. Has been. In the perovskite oxide, Sr and the like may exist together with La at the A site, and Co and Mn may exist together with Fe at the B site. For example, it is a composite oxide represented by La _y Sr _1-y Co _z Fe _1-z O ₃ , and y and z are 0.5 ≦ y ≦ 0.7 and 0.2 ≦ z ≦ 0, respectively. May be in the range of .8. Further, the material of the adhesive layer Y contains ceramic particles having a smaller thermal expansion coefficient than that of ceramic particles made of perovskite oxide having electron conductivity as a subcomponent. The secondary component, for example, _Al 2 _{O 3} (alumina), SiO ₂ (silica), may be contained SiC (silicon carbide).

  As shown in FIG. 2, the adhesive layer Y having a smaller thermal expansion coefficient than that of the air electrode layer 1 is filled in the gap extending from the surface of the second layer 1b opposite to the solid electrolyte layer 9 to the inside of the first layer 1a. It may be. With this configuration, since the adhesive layer Y, which is less likely to thermally expand and contract than the air electrode layer 1, is deeply filled in the gap X, the air electrode layer 1 can be prevented from being thermally expanded and contracted. That is, the thermal stress generated at the joint surface between the air electrode layer 1 and the intermediate layer 4 can be reduced. The adhesive layer Y may be filled up to the bottom X1 of the gap X.

  In the present embodiment, the “void” refers to a gap in the air electrode layer 1. That is, even in the case where the gap X is filled with the adhesive layer Y, it is referred to as the gap X in the present embodiment.

  Here, an example of a method for comparing the thermal expansion coefficient between the material filled in the gap of the air electrode layer 1 and the air electrode layer 1 will be described below. First, a portion including an element not contained in the first layer 1a and the second layer 1b is specified by semi-quantitative mapping by EPMA analysis in an arbitrary cross section of the first layer 1a and the second layer 1b. When the thermal expansion coefficient of the oxide of the element not contained in the first layer 1a and the second layer 1b is lower than the thermal expansion coefficient of the material of the first layer 1a and the second layer 1b, the material filled in the gap X It can be considered that the thermal expansion coefficient of is lower than that of the air electrode layer.

  Note that, since the gap X extends in a direction orthogonal to the stacking direction of the air electrode layer 1, thermal stress generated on the joint surface between the air electrode layer 1 and the intermediate layer 4 can be further reduced.

  Although not shown, the total area of the gap X may be larger at the center than at the edge of the air electrode layer 1 in plan view. With this configuration, by concentrating the gap X in the central portion of the air electrode layer 1, the thermal stress in the central portion where the temperature is higher than that of the edge portion and the thermal stress is larger can be reduced. The “edge” refers to an annular region of 20 μm from the edge of the entire circumference of the air electrode layer 1 in plan view. “Center” means a region other than the edge. “The total area is large” means that, in an arbitrary cross section of the air electrode layer 1 in the stacking direction of the air electrode layer 1, the total area of the air gap in the central portion is larger than the total area of the air gap in the edge portion.

  In the present embodiment, the intermediate layer 4 is provided immediately below the air electrode layer 1, but a layer different from the thermal expansion coefficient of the air electrode layer 1 such as a solid electrolyte layer is provided immediately below the air electrode layer 1. It is also possible to use the cell that is provided.

The manufacturing method of the air electrode layer 1 in this embodiment is demonstrated below. A plurality of materials of the first layer 1a (ceramic powder made of perovskite oxide having electronic conductivity and ceramic powder having ion conductivity and electron conductivity) described above are mixed, and the resulting slurry is fired in advance. After applying to the surface of the intermediate layer, it is dried. Next, a slurry obtained by mixing a plurality of materials of the second layer 1b (a ceramic powder made of a perovskite oxide having a low thermal expansion coefficient material such as Al ₂ O ₃ and the above-described electronic conductivity) A single layer is applied on the molded body. Next, the first layer molding is performed by a method such as pressing the mesh-shaped member or the like against the first layer molded body and the second layer molded body, or piercing the needle-shaped member into the first layer molded body and the second layer molded body. The space | gap X is provided in a body and a 2nd layer molded object. Then, it can bake and the cell 10 provided with the air electrode layer which has the 1st layer 1a and the 2nd layer 1b can be produced.

  As shown in FIG. 3, in order to obtain fuel gas used in the cell 10, a reformer 16 for reforming raw fuel such as natural gas or kerosene to generate fuel gas is provided above the cell stack 13. Is arranged. The fuel gas generated by the reformer 16 is supplied to the manifold 14 via the gas flow pipe 17 and supplied to the fuel gas flow path 5 provided inside the cell 10 via the manifold 14.

  In such a cell stack 13, since a plurality of cells 10 with improved reliability are electrically connected in series, the cell stack 13 with improved reliability can be obtained.

  FIG. 3 shows a state in which a part (front and rear walls) of the storage container 12 is removed, and the cell stack device 15 and the reformer 16 housed inside are taken out rearward. Here, in the module 11 shown in FIG. 3, the cell stack device 15 can be slid and stored in the storage container 12. Note that the cell stack device 15 may include the reformer 16.

  Further, in FIG. 3, the oxygen-containing gas introduction member 18 provided inside the storage container 12 is disposed between the cell stacks 13 juxtaposed to the manifold 14, and the oxygen-containing gas is adapted to the flow of the fuel gas. The oxygen-containing gas is supplied to the lower end portion of the cell 10 so that the side of the cell 10 flows from the lower end portion toward the upper end portion. The temperature of the cell 10 can be increased by burning the fuel gas and the oxygen-containing gas discharged from the fuel gas flow path 5 of the cell 10 on the upper end side of the cell 10. Start-up can be accelerated. Further, the fuel gas discharged from the fuel gas flow path 5 of the cell 10 and the oxygen-containing gas are combusted on the upper end side of the cell 10, so that the modification arranged above the cell 10 (cell stack 13) is performed. The quality device 16 can be warmed. Thereby, the reforming reaction can be efficiently performed in the reformer 16.

  Further, in the module 11 of the present invention, since the cell stack device 15 including the cell stack 13 configured using the cell 10 with improved reliability is stored in the storage container 12, the reliability is improved. An improved module 11 can be obtained.

  FIG. 4 shows the fuel cell of this embodiment in which the module 11 shown in FIG. 3 and an auxiliary machine (not shown) for operating the cell stack 13 (cell stack device 15) are housed in an outer case. It is a disassembled perspective view which shows an example of an apparatus. In FIG. 4, a part of the configuration is omitted.

The module storage device 19 shown in FIG. 4 divides the inside of the exterior case composed of the support column 20 and the exterior plate 21 by a partition plate 22, and the upper side thereof serves as a module storage chamber 23 that houses the module 11 described above. The lower side is configured as an auxiliary equipment storage chamber 24 for storing auxiliary equipment for operating the module 11. The auxiliary equipment stored in the auxiliary equipment storage chamber 24 includes a water supply device for supplying water to the module 11, a supply device for supplying fuel gas, air, and the like. Is omitted.

  In addition, the partition plate 22 is provided with an air circulation port 25 for allowing the air in the accessory storage chamber 24 to flow toward the module storage chamber 23, and a part of the exterior plate 21 constituting the module storage chamber 23 is An exhaust port 26 for exhausting air in the module storage chamber 23 is provided.

  In such a module storage device 19, as described above, the module storage device 19 with improved reliability can be obtained by storing the module 11 with improved reliability in the module storage chamber 23. it can.

  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 scope of the present invention.

For example, in the above description, the hollow plate type fuel cell having the conductive support substrate 3 has been described as the cell 10 of the present embodiment. However, a flat plate type cell having no conductive support substrate 3 can be used. A cylindrical cell can also be used. Further, for example, in the above-described embodiment, a cell called a so-called vertical stripe type has been described, but a horizontal stripe type cell in which a plurality of power generation element portions generally called a horizontal stripe type are provided on a support substrate can also be used. Furthermore, by applying water vapor and voltage to the cell to electrolyze water vapor (water), an electrolysis cell (SOEC) that generates hydrogen and oxygen (O ₂ ), and an electrolysis cell stack apparatus and electrolysis equipped with this electrolysis cell The present invention can also be applied to a module and an electrolytic device that is a module housing device.

1: air electrode layer 1a: first layer 1b: second layer X: gap 4: intermediate layer 7: fuel electrode layer 9: solid electrolyte layer 10: cell 11: module 15: cell stack device 19: module storage device

Claims (8)

A solid electrolyte layer;
A dense first layer laminated on the solid electrolyte layer and provided on the solid electrolyte layer side; and a porous second layer provided on the opposite side of the solid electrolyte layer side. An air electrode layer having,
The cell, wherein the air electrode layer has a gap extending from the surface of the second layer to at least the inside of the first layer.   The cell according to claim 1, wherein the gap extends over the entire length in the stacking direction of the air electrode layer.   The material having a smaller coefficient of thermal expansion than that of the air electrode layer is filled from the gap on the second layer opposite to the solid electrolyte layer side to the gap on the first layer side. Item 3. The cell according to item 1 or 2.   The cell according to any one of claims 1 to 3, wherein the gap extends in a direction orthogonal to a stacking direction of the air electrode layers.   The cell according to any one of claims 1 to 4, wherein a total area of the gap is larger in a central portion than in an edge portion of the air electrode layer in a plan view.   A cell stack device comprising a plurality of the cells according to claim 1 and electrically connecting the plurality of cells.   A module comprising the cell stack device according to claim 6 stored in a storage container.   A module storage device, wherein the module according to claim 7 and an auxiliary machine for operating the module are stored in an outer case.

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