JP2009187764A - Solid oxide fuel cell sub-module, and solid oxide fuel cell composite module - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an SOFC module in which each SOFC sub-module can be stabilized similarly to generate power more easily compared with a conventional one. <P>SOLUTION: In the module M, at least a pair of sub-modules 10 are arranged in opposition with a gap 16 in a nearly vertical direction to the axial direction of a tubular body 12. A second gas A supplied to the gap 16 flows in a second electrode body 14 of each sub-module 10 arranged on both sides of the gap 16 and is discharged to the outside. A first gas F supplied from one end side of the tubular body 12 flows in the tube and is discharged from the other end side of the tubular body 12. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a solid oxide fuel cell sub-module and a solid oxide fuel cell composite module.

  In recent years, solid oxide fuel cells (hereinafter sometimes referred to as “SOFC”) using solid electrolytes (solid oxides) have been actively developed as fuel cells.

  Single cells used for SOFC can be broadly classified into flat plate types and tubular types. Flat cells can be integrated relatively easily by stacking. On the other hand, tubular cells cannot be integrated with the same structure. Therefore, conventionally, so-called vertical stripe type and horizontal stripe type cells are often used.

  However, in order to integrate vertical stripe type and horizontal stripe type cells, a complicated manufacturing process is required, and miniaturization is difficult. Therefore, for example, in Patent Document 1, a plurality of electrolyte electrode joint tubes in which a solid electrolyte layer is laminated on the outer surface of a fuel electrode tube are integrally solidified with an air electrode material to form an SOFC submodule. Simplification of process and miniaturization can be realized.

  The SOFC submodule is further integrated and used. For example, Patent Document 2 discloses a SOFC module in which a fuel gas manifold or the like is attached to the SOFC submodule and a plurality of these are arranged and connected. In this SOFC module, each gas (fuel gas, air) is supplied from the SOFC sub-module disposed on the upstream side to the SOFC sub-module disposed on the downstream side in a continuous manner. It is said that.

JP 2004-335277 A JP 2005-166470 A (FIG. 14 etc.)

  However, the conventional SOFC module has room for improvement in the following points.

  That is, in the SOFC module, air that has passed through the air electrode material of the upstream SOFC submodule is supplied to the air electrode material of the downstream SOFC submodule. Therefore, it is difficult to supply air uniformly to the air electrode material of each SOFC submodule. Further, in order to supply air one after another from the upstream side to the downstream side, a relatively large differential pressure is often required, and an extra device such as a compressor may be required.

  On the other hand, in the SOFC module, fuel gas is used in the upstream SOFC submodule, and unused fuel gas is supplied to the downstream SOFC submodule. For this reason, the concentration of the fuel gas supplied into the fuel electrode tube tends to decrease as the position becomes downstream. Therefore, it is difficult to uniformly supply the fuel gas to the fuel electrode tube of each SOFC submodule.

  As described above, the structure of the SOFC module is difficult to supply each gas to each SOFC submodule under substantially the same conditions. As a result, there is a problem that it is technically difficult to stably generate power in each SOFC submodule.

  The present invention has been made in view of the above problems, and the problem to be solved by the present invention is to provide an SOFC module that can stabilize each SOFC sub-module in the same manner and can easily generate electric power as compared with the prior art. is there.

  In order to solve the above-described problems, an SOFC module according to the present invention includes a plurality of tubular bodies in which a solid electrolyte layer is laminated on an outer peripheral surface of a first electrode tube to which a first gas is supplied. A SOFC module comprising a plurality of SOFC submodules, each of which has a plurality of SOFC submodules, each of which has a second electrode body to which a second gas is supplied. A pair of the submodules are arranged to face each other with a gap in a direction substantially perpendicular to the axial direction, and the second gas supplied to the gap is the second gas of each submodule arranged on both sides of the gap. The gist is that it has a structure that flows through the two-electrode body and is discharged to the outside.

  Here, it is preferable that the outer surface of the second electrode body other than the surface serving as the flow path for the second gas is covered with a dense member.

  Further, the outer periphery of the pair of submodules is covered with a covering member so that the gap is formed as one closed space, and the covering member is formed with a communication hole for communicating the gap and the outside. Preferably it is.

  The pair of submodules may be configured by a part of a pair of stacks formed by electrically connecting the plurality of submodules.

  In the SOFC module according to the present invention, the above structure may be stacked via a first gas supply manifold that supplies a first gas into the first electrode tube.

  In the submodule, both end portions of the tubular body protrude from the outer surface of the second electrode body, and one side of the protruding portion is disposed inside the first gas supply manifold. Is preferred.

  In the SOFC module according to the present invention, it is preferable that the unused first gas that has flowed through the first electrode tube reacts with the second gas that has flowed through the second electrode body and discharged to the outside. The obtained reaction heat is preferably used as reforming energy of a reformer that generates fuel gas.

  In the SOFC module according to the present invention, a first gas discharge manifold is provided on the first gas outlet side of the tubular body, and the unused first gas flowing in the first electrode pipe is discharged from the first gas discharge. It is preferably recovered by a manifold.

  In addition, a second gas discharge manifold is provided on the second gas discharge surface side of the outer surface of the second electrode body, and the unused second gas flowing through the second electrode body is the second gas body. It is preferably recovered by a gas exhaust manifold.

  The SOFC composite module according to the present invention includes a plurality of SOFC modules provided with the second gas exhaust manifold, and each module has a second gas flow in the second gas exhaust manifold alternately between the modules. The gist is that the second gas discharge manifolds are arranged in contact with each other so as to be oriented.

  In the SOFC module according to the present invention, a pair of SOFC submodules are arranged to face each other with a gap in a direction substantially perpendicular to the axial direction of the tubular body, and the second gas supplied to the gap is in the gap. The sub-modules arranged on both sides flow through the second electrode body and are discharged to the outside.

  In the SOFC module, the surface facing the gap among the outer surfaces of the second electrode bodies of the submodules becomes the inflow surface of the second gas. Therefore, the second gas can be supplied to the second electrode body of each submodule under substantially the same conditions. In addition, since the tubular bodies included in the submodules are aligned in the axial direction, the first gas is supplied to the first electrode bodies from either one side of the tubular bodies under substantially the same conditions. Can do.

  Therefore, according to the SOFC module, each gas can be supplied to each submodule under substantially the same condition as compared with the conventional case. As a result, each submodule can be similarly stabilized and allowed to generate power.

  Here, of the outer surface of the second electrode body of each sub-module, the surface that becomes the flow path of the second gas (the inflow surface of the second gas facing the gap, the discharge surface of the second gas facing this inflow surface) In the case where the other parts are covered with the dense member, it is easy to form the gas flow path only inside the gas-tight dense member. Therefore, the second gas can surely flow only in the second electrode tube.

  In addition, when the outer periphery of the pair of submodules is covered with the covering member, the gap is made one closed space, and the covering member is formed with a communication hole that connects the gap and the outside. The gap can be partitioned with a relatively simple structure, and the second gas can be supplied to the gap from the outside through the communication hole. Further, the second gas supplied to the gap can be made to flow into the second electrode body relatively easily.

  In addition, when the pair of submodules is constituted by a part of a pair of stacks formed by electrically connecting a plurality of submodules, it is easy to contribute to high integration of the SOFC module. .

  Further, in the case where the structure is stacked via a first gas supply manifold that supplies a first gas into the first electrode tube, it contributes to high integration, and on both sides of the first gas supply manifold. It becomes easy to supply the first gas into each first electrode tube in substantially the same condition.

  In the sub-module, both end portions of the tubular body protrude from the outer surface of the second electrode body, and one side of the protruding portion is disposed inside the first gas supply manifold. Since the end portion of the tubular body is covered with the first gas supply manifold, the first gas can be easily supplied into the first electrode tube.

  In addition, when the unused first gas that has flowed through the first electrode tube and the second gas that has flowed through the second electrode body and discharged outside, the reaction heat obtained is used as heat. can do.

  As a specific form of heat utilization, for example, when this SOFC module is applied to a fuel cell system, a form of utilizing the reaction heat as reforming energy of a reformer for generating fuel gas, etc. It is done.

  When the first gas discharge manifold is provided on the first gas outlet side of the tubular body, and the unused first gas flowing through the first electrode tube is recovered by the first gas discharge manifold. It is easy to effectively use the first gas, such as reusing the first gas or using it as energy of another device.

  In addition, a second gas discharge manifold is provided on the second gas discharge surface side of the outer surface of the second electrode body, and unused second gas flowing in the second electrode pipe is transferred to the second electrode body. When recovered by the gas discharge manifold, it is easy to effectively use the second gas, for example, by reusing the second gas or using it as energy for another device.

  On the other hand, the SOFC composite module according to the present invention includes a plurality of SOFC modules provided with the above-described second gas discharge manifold, and each module has a second gas flow in the second gas discharge manifold. The gist is that the second gas discharge manifolds are arranged in contact with each other so as to be alternately oriented.

  In the SOFC module, the temperature rises due to heat generation during power generation as it goes downstream of the flow of the discharged second gas. According to the SOFC composite module, since the arrangement is as described above, heat exchange occurs between the second gas upstream side and the downstream side of the adjacent modules. Therefore, the imbalance of the temperature distribution in each module can be reduced, and each module can be similarly stabilized and easily generate power.

  Hereinafter, an SOFC module (hereinafter sometimes referred to as “the present module”) and an SOFC composite module (hereinafter sometimes referred to as “the present composite module”) according to an embodiment of the present invention will be described in detail.

1. This module This module includes a plurality of submodules.

  FIG. 1 is a diagram schematically showing an example of the appearance of a submodule. As shown in FIG. 1, the submodule 10 is formed in a substantially rectangular shape, and includes a plurality of tubular bodies 12 and a second electrode body 14.

  FIG. 2 is an enlarged view of a part of the cross section of the submodule shown in FIG. As shown in FIG. 2, the tubular body 12 has a first electrode tube 12a and a solid electrolyte layer 12b.

  The first electrode tube 12a is a porous body formed in a tubular shape from the first electrode material. The first electrode tube 12a has a function as a first electrode and also has a function as a support tube.

  The first gas is supplied into the first electrode tube 12a. Specifically, the first electrode tube 12a is either a fuel electrode tube formed of a fuel electrode material or an air electrode tube formed of an air electrode material.

  Accordingly, when the first electrode tube 12a is a fuel electrode tube, a fuel gas such as hydrogen, carbon monoxide, methane, city gas (13A) is selected as the first gas. On the other hand, when the first electrode tube 12a is an air electrode tube, an oxidant gas such as air or oxygen is selected as the first gas.

As the fuel electrode material, for example, a catalyst such as Ni, NiO, Co, Cu, Ru, Pt, Au, Pd, or an alloy containing two or more of these elements can be used. Ni, NiO, Co, Cu and the like are preferable. More preferably, Ni, NiO, etc. are used from the viewpoint of being inexpensive compared with other metals and having good reactivity with fuel gas. A composite material of a catalyst and a solid electrolyte can also be used. In this case, the solid electrolyte includes, for example, zirconia (YSZ, ScSZ, etc.) stabilized with Y ₂ O ₃ , Sc ₂ O _3, or the like, or an oxide of a second element such as CeO ₂ , Y ₂ O _3. Scandia-stabilized zirconia (ScCeSZ, ScYSZ, etc.), CeO ₂ (SDC, GDC, etc.) containing oxides such as Sm ₂ O ₃ , Gd ₂ O ₃ , LaSrGaMgO ₃ (LSGM), and the like can be given. The mixing ratio (% by weight) of the catalyst and the solid electrolyte is preferably in the range of 80:20 to 30:70. More preferably, it is good in the range of 70: 30-40: 60.

On the other hand, as the air electrode material, for example, LaSrMnO ₃ , LaCaMnO ₃ , LaMgMnO ₃ , LaSrCoO ₃ , LaCaCoO ₃ , LaSrFeO ₃ , LaSrCoFeO ₃ , LaSrNiO ₃ , LaNiFeOr ₃ O ₃ Can do. A composite material of a transition metal perovskite oxide and a solid electrolyte can also be used. In this case, examples of the solid electrolyte include YSZ, ScSZ, ScCeSZ, ScYSZ, SDC, GDC, and LSGM. The mixing ratio (% by weight) of the transition metal perovskite oxide and the solid electrolyte is preferably in the range of 90:10 to 50:50. More preferably, it is in the range of 90:10 to 80:20.

  For example, the first electrode tube 12a is prepared by mixing various material powders at a predetermined ratio, adding a binder such as methyl cellulose, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, a pore-generating agent such as carbon powder, and the like with water. Kneading and manufacturing the obtained plastic material by extruding, etc. into a tubular molded body with a predetermined tube diameter, tube length and tube thickness, and firing this at an optimum temperature according to the composition. Can do.

  The solid electrolyte layer 12b is a dense body formed in a thin film shape from a solid electrolyte material, and is laminated along the outer peripheral surface of the first electrode tube 12a. Examples of the solid electrolyte material include YSZ, ScSZ, ScCeSZ, ScYSZ, SDC, GDC, and LSGM.

  As shown in FIGS. 1 and 2, the solid electrolyte layer 12 b is laminated on the first electrode tube 12 b so as to be exposed from the outer surface of the second electrode body 14 when being fixed to the second electrode body 14. ing. Thereby, it is possible to easily prevent a short circuit between the first electrode tube 12 a and the second electrode body 14. Moreover, the solid electrolyte layer 12b is laminated | stacked on the 1st electrode tube 12b so that the outer surface of the both ends side of the 1st electrode tube 12a may be exposed. Thereby, when modularizing, it is made possible to contact with the below-mentioned electroconductive member and to collect electricity easily.

  The solid electrolyte layer 12b is obtained by attaching a slurry containing a solid electrolyte material to a predetermined position of the first electrode tube 12a (sintered body) or a tubular molded body (unfired body) that is a precursor thereof, and then forming the composition into the composition. It can be formed by firing at an optimum temperature corresponding to the temperature. In addition, when the slurry containing solid electrolyte material is made to adhere to a tubular molded object and it bakes (co-sintering method), it becomes easy to suppress battery manufacturing cost.

  As a method for attaching the slurry containing the solid electrolyte material, specifically, for example, a substance (such as a polymer) that can disappear during firing is used to seal the end of the first electrode tube 12a or the like, After applying a mask to a portion where the layer 12b is not formed, a dipping method in which the first electrode tube 12a and the like are immersed in a slurry containing a solid electrolyte material, and a spray method, a brush coating method, a roll coating method, or the like is used. Examples of the method include applying a slurry containing a solid electrolyte material to the first electrode tube 12a and the like.

  The 2nd electrode body 14 is a porous body with the air permeability formed from the 2nd electrode material. A second gas is supplied into the second electrode body 14.

  The second electrode body 14 constitutes an electrode type different from that of the first electrode tube 12a. That is, when the first electrode tube 12a is a fuel electrode tube, the second electrode body 14 is made of an air electrode material and functions as an air electrode. Therefore, in this case, an oxidant gas such as air or oxygen is selected as the second gas.

  On the other hand, when the first electrode tube 12a is an air electrode tube, the second electrode body 14 is made of a fuel electrode material and functions as a fuel electrode. Therefore, in this case, a fuel gas such as hydrogen, carbon monoxide, methane, city gas (13A) is selected as the second gas.

  Examples of the air electrode material and the fuel electrode material may include the same materials as those described for the first electrode tube 12a.

  In addition, as this module, it is preferable that the 1st electrode pipe | tube 12a is a fuel electrode tube and the 2nd electrode body 14 is an air electrode body from a viewpoint that a high performance is acquired and manufacture is easy.

  The second electrode body 14 is integrally fixed by arranging a plurality of tubular bodies 12 in the same direction. That is, in the second electrode body 14, each tubular body 12 is arranged in a direction substantially perpendicular to the axial direction of the tubular body 12 so that the axial directions thereof are substantially parallel to each other. The tubular bodies 12 are arranged so as to be separated from each other so that their outer surfaces do not contact each other. And the 2nd electrode body 14 is solidifying each tubular body 12 so that the clearance gap formed between the outer surfaces of each tubular body 12 may be filled up, maintaining the arrangement | sequence of each tubular body 12. FIG. In the second electrode body 14, if the tubular bodies 12 are separated from each other in a direction substantially perpendicular to the flow direction of the second gas A, which will be described later, the flow direction of the second gas A and the direction substantially parallel to each other The tubular bodies 12 may not be separated from each other.

  Moreover, the 2nd electrode body 14 is fixing each tubular body 12 integrally in the state which made the both ends of each tubular body 12 protrude from the outer surface.

  In addition, although the case where each tubular body 12 was made into the arrangement | sequence of 4 rows x 2 columns is illustrated in FIG. 1, it is not specifically limited to this arrangement | sequence. Each tubular body 12 may be arranged in the second electrode body 14 in a plurality of rows × plural columns, a single row × multiple columns, and a plurality of columns × single rows.

  The outer shape of the second electrode body 14 is preferably a substantially rectangular shape such as a cube or a rectangular parallelepiped from the viewpoints of ease of forming the gap 16 described later, a three-dimensional structure when modularized, and integration.

  As a manufacturing method of the submodule having the above structure, for example, the following method can be adopted.

  That is, the plurality of tubular bodies 12 are arranged and fixed apart from each other so that the axial directions thereof are substantially parallel to the axial direction of the tubular body 12. In the array fixing, for example, fitting holes for fitting the end portions of the tubular bodies 12 are formed in advance on the surface of the base made of a metal such as stainless steel or a ceramic such as zirconia or alumina, and the tubular is formed on the base. For example, the body 12 may be erected. At this time, the standing state of the tubular body 12 may be appropriately adjusted so that the end surface on one side of the second electrode body 14 to be formed substantially coincides with the surface of the base body. In addition, you may seal between the tubular body 12 and a base | substrate as needed, or you may fix with an adhesive agent.

  Next, the outermost periphery of the tubular bodies 12 that are arranged and fixed is covered with a container made of resin or the like. In addition, the external shape of the 2nd electrode body 14 can be determined with the shape of this container.

  Next, a slurry containing the second electrode material is poured into the container, and the slurry is filled in the gaps between the arranged tubular bodies 12. The distance between the end surface on one side and the end surface on the other side of the second electrode body 14 to be formed can be determined by the filling amount of the slurry.

  Next, the slurry filled in the container is dried to obtain a dry body, and the substrate is removed.

  Next, the dried body is fired at an optimum temperature according to the composition of the second electrode material. At this time, the container may be baked together with the dried body or may be removed, and is not particularly limited. In addition, when a dry body is baked with a resin container attached, the container itself disappears when the temperature is raised during baking.

  As described above, the submodule 10 can be manufactured.

  In addition, for example, the following method can be employed. That is, a polymer material (for example, polymethyl methacrylate) is added to the second electrode material as necessary, and this is mixed with water to obtain a clay-like plastic material.

  Next, a molded body having an insertion hole into which the tubular body 12 can be inserted is formed by extruding the plastic material using a mold or the like.

  Next, the tubular body 12 is inserted into the insertion hole of the obtained molded body, and this is fired at an optimal temperature according to the composition of the second electrode material.

  The submodule 10 can be manufactured also by the above.

  Here, this module has a specific basic structure so that the first gas and the second gas are supplied to the plurality of submodules 10 under substantially the same conditions. FIG. 3 is a diagram schematically showing the conceptual structure of this module.

  As shown in FIG. 3, in the present module M, at least a pair of submodules 10 are arranged to face each other with a gap 16 provided in a direction substantially perpendicular to the axial direction of the tubular body 12. The second gas A supplied to the gap 16 flows through the second electrode body 14 of each submodule 10 disposed on both sides of the gap 16 and is discharged to the outside (on the opposite side to the gap 16). The first gas F supplied from one end side of the tubular body 12 flows through the pipe and is discharged from the other end side of the tubular body 12. Hereinafter, this module will be described in detail using the first module as the first embodiment and the second module as the second embodiment.

  In the following description, the first electrode tube 12a is a fuel electrode tube (-), the second electrode body 14 is an air electrode body (+), fuel gas is supplied as the first gas, and oxidant gas is supplied as the second gas. This will be described assuming the case.

(First embodiment)
4 to 7 are diagrams schematically showing the first module M1. 4 is a front view of the first module, FIG. 5 is a plan view of the first module, FIG. 6 is an XX sectional view of FIG. 4, and FIG. 7 is a YY sectional view of FIG.

  As shown in FIGS. 4 to 7, the first module M <b> 1 uses two submodules 10. The two submodules 10 are arranged to face each other with a predetermined gap 16 in a direction substantially perpendicular to the axial direction of the tubular body 12. Here, in order to connect the submodules 10 in series, the submodules 10 are arranged so as to be alternately oriented to each other.

  In the first module M 1, the second gas A supplied to the gap 16 flows through the second electrode bodies 14 of the submodules 10 arranged on both sides of the gap 16 and is discharged to the outside. The first gas F supplied from one end side flows through the pipe and is discharged from the other end side of the tubular body 12.

  Here, the first module M1 secures a flow path for each gas by using various members having a plate shape, a housing shape, and the like in consideration of gas leakage, electrical connection, and the like. This will be specifically described below.

  As shown in FIG. 6, the surface in contact with the gap 16 among the outer surfaces of the second electrode body 14 becomes an inflow surface 14 a into which the second gas A flows. The surface facing the inflow surface 14a is a discharge surface 14b from which the second gas A is discharged. That is, the inflow surface 14a and the discharge surface 14b are surfaces that exist on the flow path of the second gas A.

  Of the outer surface of the second electrode body 14, the surfaces (surfaces other than the inflow surface 14a and the discharge surface 14b) that do not exist on the flow path of the second gas A are basically gas-tight as shown in FIG. The dense member 18 is covered. As a result, a gas flow path is formed only on the inner side surrounded by the dense member 18, and the second gas A can easily flow through only the second electrode tube 14.

As the material of the dense member 18, various conductive materials and insulating materials are selected according to the conductivity and insulation required for the outer surface of the second electrode body 14. Examples of the conductive material include metals such as ferritic stainless steel, austenitic stainless steel, nickel alloy, metal foil, and conductive ceramics. Examples of the insulating material include ceramics such as MgO, Al ₂ O ₃ , and ZrO ₂ , and glass such as heat resistant glass.

  Here, of the outer surfaces that do not exist on the flow path of the second gas A, one of the surface substantially perpendicular to the tubular body 12 and the surface substantially parallel to the tubular body 12 is sealed by the insulating dense member 18a. . Further, the other surface substantially parallel to the tubular body 12 is sealed with a conductive dense member 18b. The dense member 18b becomes a positive side by power generation.

  Furthermore, the outer peripheral surface of the insulating dense member 18a is covered with a conductive member 20 such as metal. Further, the conductive member 20 is electrically connected to the first electrode tube 12 a exposed at both ends of the tubular body 12. Therefore, the conductive member 20 becomes a negative side due to power generation.

  The conductive member 20 is not in contact with the conductive dense member 18b by interposing the step portion 19 of the insulating dense member 18a (the conductive dense member 18b). Insulated).

  The opposing submodules 10 are electrically connected via a current collecting member 21. At this time, as the current collecting member 21, a conductive dense member such as metal can be suitably used. Thereby, the submodules 10 are connected in series. If the submodules 10 are arranged in the same direction, they are connected in parallel. In the current collection, a metal wire (for example, Pt wire, Au wire, Ag wire, etc.) is connected to the conductive dense member 18b and the conductive member 20 by welding or winding, and this is connected to the second gas. By taking out in the direction of the discharge surface 14b from which A is discharged or the inflow surface 14a into which the second gas A flows, it can be performed relatively easily.

  As described above, the outer periphery of the pair of submodules 10 covered with various members is further covered with the covering member 22, so that the gap 16 is formed as one closed space. That is, the covering member 22 is disposed so as to surround the gap 16. However, the discharge surface 14b of the second electrode body 14 is not covered in a state of being in direct contact with the covering member 22 in order to enable the discharge of the second gas A, and between the covering member 22 and the discharge surface 14b. Is formed with a predetermined gap 22a.

According to the covering member 22, the gap 16 can be partitioned into a closed space with a simple structure. In addition, there is an effect of reinforcing the submodule 10 disposed inside, and stacking and the like are facilitated. As the material of the covering member 22, an insulating material can be suitably used. Specific examples include ceramics such as MgO and Al ₂ O ₃ .

  The covering member 22 has a communication hole 22b that allows the gap 16 to communicate with the outside (outside). The communication hole 22b may be formed at any position of the covering member 22 as long as the gap 16 and the outside (outside) can communicate with each other. Preferably, the tubular body 12 is formed on a surface other than the exposed surface. Moreover, the magnitude | size, hole shape, etc. of the communicating hole 22b to form are not specifically limited.

  When the communication hole 22b is formed, the second gas A can be supplied to the gap 16 from the outside through the communication hole 22b. Further, if the outer periphery of the pair of submodules 10 is covered with such a covering member 22, the second gas A supplied to the gap 16 can flow into the second electrode body 14 relatively easily.

  In the first module M1, the tubular bodies 12 included in the submodules 10 are arranged in parallel with the axial direction aligned. Further, both end portions of each tubular body 12 protrude from the covering member 22.

  The first module M1 is provided with a first gas supply manifold 24 so as to cover one side of the projecting surfaces of the tubular bodies 12. Here, the first gas supply manifold 24 is illustrated as being formed from a hollow housing. The 1st gas supply manifold 24 is for supplying the 1st gas F in the pipe | tube of each tubular body 12 from the outer side (external) via the supply hole 24a. Inside the first gas supply manifold 24, one end of each tubular body 12 is disposed. In the first module M1, the first gas F can be easily and simultaneously supplied to all the tubular bodies 12.

  FIG. 8 is a ZZ cross-sectional view of FIG. Of the wall surfaces of the first gas supply manifold 24, insertion holes 24 b through which the tubular bodies 12 can be inserted are formed on the wall surface on the tubular body 12 side in accordance with the arrangement of the tubular bodies 12. Each tubular body 12 is inserted into each insertion hole 24 b, so that an end portion thereof is disposed in the first gas supply manifold 24.

  FIG. 9 is a view showing a modification of the first gas supply manifold. In the first gas supply manifold 24 ′, an opening 24 ′ a is formed on the wall surface on the tubular body 12 side, and the end of each tubular body 12 is accommodated in the opening 26 ′ a. Note that the peripheral wall surface of the opening 24'a plays a role of restricting the pair of submodules 10 from entering the first gas supply manifold 24 '.

  When the end of each tubular body 12 is accommodated in the opening 24'a, each tubular body is purposely inserted into the insertion hole 24b, compared to the case where each tubular body 12 is inserted into the insertion hole 24b. 12 need not be inserted. In addition, the manifold structure is simplified, the machining accuracy can be lowered, and there are advantages such as increased practicality.

  In the first module M1, a gap 22a formed between the covering member 22 and the discharge surface 14b is used as the second gas discharge manifold 26. However, instead of providing the covering member 22 on the discharge surface 14b side, the discharge surface 14b may be covered separately using, for example, a second gas discharge manifold such as a housing having an opening surface. In this case, the covering member 22 and the second gas discharge manifold 26 may be made of the same material or different materials.

  In addition, the second gas discharge manifold 26 has an opening 26a formed on the wall surface around the end of the tubular body 12 from which the unused first gas F is discharged. Therefore, the first module M1 can discharge the unused second gas A to the vicinity of the end of the tubular body 12 through the opening 26a.

  When the second gas discharge manifold 26 is formed in this way, it is easy to discharge the unused second gas A that has flowed through the second electrode body 14. Further, the unused second gas A can be recovered by the second gas discharge manifold 26.

  Next, the operation of the first module M1 will be described.

  When the first gas F is supplied from the supply hole 24 a of the first gas supply manifold 24, the first gas F is filled in the first gas supply manifold 24. The first gas F filled in the first gas supply manifold 24 flows into the pipe under substantially the same conditions from the end of each tubular body 12 arranged side by side in the first gas supply manifold 24. The first gas F that has flowed into the pipe of each tubular body 12 flows downstream while being used for power generation, and the unused first gas F is externally supplied from the end of the tubular body 12 opposite to the inflow side. To be discharged.

  On the other hand, when the second gas A is supplied from the communication hole 22 b of the covering member 22, the second gas A is filled in the gap 16 between the submodules 10 arranged to face each other. The gap 16 functions as a second gas supply manifold. The second gas A filled in the gap 16 flows into the second electrode body 14 under substantially the same conditions from the inflow surface 14a of the second electrode body 14 disposed on both sides of the gap 16. The second gas A flowing into the second electrode body 14 flows downstream while being used for power generation, and the unused second gas A flows from the discharge surface 14b of the second electrode body 14 to the second gas discharge manifold. 26 flows in. The unused second gas A flowing into the second gas discharge manifold 26 is collected and discharged to the outside through the opening 26a. The current collection is performed by connecting a metal wire (for example, Pt wire, Au wire, Ag wire, etc.) to the conductive dense member 18b and the conductive member 20 by welding or winding, and this is connected to the opening 26a. This can be done by taking it out.

  Here, in the first module M1 described above, it is easy to react (combust) the unused first gas F and the unused second gas A discharged to the outside. When both gases are reacted, the obtained reaction heat (combustion heat) can be used as heat. Specifically, for example, by providing a reformer (not shown) for generating fuel gas on the discharge side of the first gas F of the tubular body 12, as reforming energy (heat source) of the reformer, The heat of reaction can be used efficiently. In general, the reforming reaction by the reformer is an endothermic reaction. Therefore, when a reformer is provided, the first module M1 can be cooled by an endothermic reaction.

  Further, in the first module M1 described above, a first gas discharge manifold (not shown) may be provided so as to cover the first gas discharge surface side of each tubular body 12. Examples of the first gas discharge manifold include those formed from a hollow housing similar to the first gas supply manifold 24. The connection between each tubular body 12 and the first gas discharge manifold may be performed in the same manner as the connection between each tubular body 12 and the first gas supply manifold 24 described above, and detailed description thereof is omitted.

  When the first gas discharge manifold is provided and the unused first gas F is recovered, the first gas F can be reused or used as energy for other devices, etc. Effective use can be achieved.

(Second Embodiment)
10 to 13 are diagrams schematically showing the second module M2. 10 is a front view of the second module, FIG. 11 is a plan view of the second module, FIG. 12 is an XX sectional view of FIG. 10, and FIG. 13 is a YY sectional view of FIG.

  As shown in FIGS. 10 to 13, the second module M <b> 2 uses six submodules 10.

  The second module M2 is significantly different from the first module M1 described above in two points, that is, a point using a pair of stacks 30 and a point having a laminated structure. Therefore, different parts will be mainly described below.

  In the second module M2, one stack 30 is configured by electrically connecting the three submodules 10, and a pair of stacks 30 are arranged to face each other with a gap 16 therebetween. Therefore, it is in a state where three pairs of opposing submodules 10 are combined. Note that the number of submodules 10 constituting the stack 30 is not particularly limited. In addition, here, in order to connect the stacks 30 in series, the stacks 30 are arranged so as to be alternately oriented.

  Specifically, as shown in FIG. 13, the stack 30 is substantially perpendicular to the axial direction of the tubular body 12 so that the inflow surface 14a of the second gas A of the second electrode body 14 is substantially in the same plane. Three submodules 10 are arranged in the direction. Adjacent submodules 10 are connected in series by contacting one conductive member 20 and the other second electrode body 14. In this case, a dense member can be suitably used as the conductive member 20 in order to prevent the second gas A from leaking from the second electrode body 14. At this time, from the viewpoint of improving electrical contact between the second electrode body 14 and the conductive member 20, a dense contact material is interposed between the second electrode body 14 and the conductive member 20. It doesn't matter. The outermost periphery of the pair of stacks 30 is covered with the covering member 22, and the gap 16 is a single closed space.

  In the second module M2, the specific basic structure described above is stacked above and below the first gas supply manifold 32. Therefore, higher integration is achieved than in the first module M1. However, the first module M <b> 1 can be similarly stacked through the first gas supply manifold 24.

  Specifically, the first gas supply manifold 32 is formed from a hollow housing. One end of the tubular body 12 of each stack 30 disposed in the upper stage of the first gas supply manifold 32 and one end of the tubular body 12 of each stack 30 disposed in the lower stage of the first gas supply manifold 32 The first gas supply manifold 32 is disposed inside. That is, in the second module M2, the first gas supply manifold 32 is shared between specific basic structures stacked with the first gas supply manifold 32 interposed therebetween.

  According to the second module M2, the first gas F supplied from the supply hole 32a of the first gas supply manifold 32 flows into the pipes of the tubular bodies 12 of the upper and lower stacks 30 under substantially the same conditions. In addition, if it is set as the structure which supplies 1st gas F from several supply holes, such as forming another supply hole (not shown) in the opposing position of the supply hole 32a of the 1st gas supply manifold 32, etc. The first gas F can be caused to flow into the tube of the 30 tubular bodies 12 under the same conditions. In addition, the second gas A supplied into the gaps 16 from the communication holes 22b of the upper and lower stacks 30 from the inflow surfaces 14b of the second electrode bodies 14 of the stacks 30 disposed on both sides of the gaps 16, respectively. It flows into each second electrode body 14 under substantially the same conditions. Thereafter, in the same manner as in the first module M1, each gas flows to generate power, and each unused gas is discharged.

2. The present composite module The present composite module includes a plurality of present modules including a second gas exhaust manifold that collects unused second gas that has flowed through the second electrode body. In the composite module, the modules are arranged such that the second gas discharge manifolds are in contact with each other so that the flow of the second gas in the second gas discharge manifold is alternately directed between the modules.

  FIG. 14 is a plan view of the composite module MC. The case where the composite module MC uses a plurality of the second modules M2 described above will be described. However, the opening 26 a (not shown in FIG. 14) of the second gas discharge manifold 26 is formed on the side surface of the second gas discharge manifold 26.

  As shown in FIG. 14, in the composite module MC, four second modules M <b> 2 are arranged in a direction substantially perpendicular to the axial direction of the tubular body 12. The second modules are arranged alternately, and the adjacent second gas discharge manifolds 26 are in contact with each other.

  In the composite module MC, the second gas A supplied to the gap 16 passes through the second electrode body 14 and is discharged into the second gas discharge manifold 26. The unused second gas A discharged into the second gas discharge manifold 26 is discharged from the opening 26 a of the second gas discharge manifold 26. At this time, the flow of the second gas A discharged between the adjacent second modules M2 is alternately directed between the second modules M2.

  In each of the second modules M2, the temperature tends to increase due to the heat generated during power generation as it goes to the downstream side of the flow of the discharged second gas A. Therefore, according to the composite module MC, heat exchange occurs between the second gas upstream side and the downstream side of the adjacent second module M2. Therefore, the imbalance of the temperature distribution in each second module M2 can be reduced, and each second module M2 can be similarly stably generated.

  As mentioned above, although embodiment of this invention was described in detail, this invention is not limited to the said embodiment at all, A various change is possible in the range which does not deviate from the summary of this invention.

It is the figure which showed typically an example of the external appearance of the submodule with which this module is provided. It is the figure which expanded and showed a part of cross section of the submodule shown in FIG. It is the figure which showed the schematic structure of this module typically. It is a front view of the 1st module M1 concerning a 1st embodiment. It is a top view of the 1st module M1 concerning a 1st embodiment. It is XX sectional drawing of FIG. It is YY sectional drawing of FIG. It is ZZ sectional drawing of FIG. It is the figure which showed the modification of the 1st gas supply manifold. It is a front view of the 2nd module M2 concerning a 2nd embodiment. It is a top view of the 2nd module M2 concerning a 2nd embodiment. It is XX sectional drawing of FIG. It is YY sectional drawing of FIG. It is a top view of compound module MC.

Explanation of symbols

10 Submodule 12 Tubular body 12a First electrode tube 12b Solid electrolyte layer 14 Second electrode body 14a Inflow surface 14b Outlet surface 16 Gap 18 Dense member 18a Insulating dense member 18b Conductive dense member 19 Step 20 Conductive member 21 Current collecting member 22 Cover member 22a Gap 22b Communication hole 24 First gas supply manifold 24a Supply hole 24b Insertion hole 24 'First gas supply manifold 24'a Opening 26 Second gas discharge manifold 26a Opening 30 Stack 32 First 1 gas supply manifold M module M1 first module M2 second module MC composite module F first gas A second gas

Claims (11)

A plurality of tubular bodies in which a solid electrolyte layer is laminated on the outer peripheral surface of a first electrode tube to which a first gas is supplied into the tube, and the plurality of tubular bodies are arranged in the same direction and fixed integrally. A solid oxide fuel cell module comprising a plurality of solid oxide fuel cell submodules having a second electrode body to which a second gas is supplied,
A pair of the submodules are arranged to face each other with a gap in a direction substantially perpendicular to the axial direction of the tubular body,
The second gas supplied to the gap flows through the second electrode body of each submodule disposed on both sides of the gap and is discharged to the outside. Fuel cell module.   2. The solid oxide fuel cell module according to claim 1, wherein a portion of the outer surface of the second electrode body other than a surface serving as a flow path for the second gas is covered with a dense member. . The outer periphery of the pair of submodules is covered with a covering member so that the gap is a closed space,
3. The solid oxide fuel cell module according to claim 1, wherein the covering member is formed with a communication hole that communicates the gap with the outside. The pair of submodules includes:
The solid oxide fuel cell module according to any one of claims 1 to 3, wherein the solid oxide fuel cell module is configured by a part of a pair of stacks formed by electrically connecting the plurality of submodules.   5. The solid oxide fuel cell according to claim 1, wherein the structure is stacked via a first gas supply manifold that supplies a first gas into the first electrode tube. 6. module. In the submodule, both end portions of the tubular body protrude from the outer surface of the second electrode body,
6. The solid oxide fuel cell module according to claim 5, wherein one side of the projecting portion is disposed inside the first gas supply manifold.   The unused first gas that has flowed through the first electrode tube is reacted with the second gas that has flowed through the second electrode body and discharged to the outside. The solid oxide fuel cell module described.   8. The solid oxide fuel cell module according to claim 7, wherein the reaction heat is used as reforming energy of a reformer that generates fuel gas. A first gas discharge manifold is provided on the first gas outlet side of the tubular body;
9. The solid oxide fuel cell module according to claim 1, wherein unused first gas that has flowed through the first electrode tube is recovered by the first gas discharge manifold. 10. Of the outer surface of the second electrode body, a second gas discharge manifold is provided on the discharge surface side of the second gas,
10. The solid oxide fuel cell module according to claim 1, wherein unused second gas that has flowed through the second electrode body is recovered by the second gas discharge manifold. 11. A plurality of the solid oxide fuel cell modules according to claim 10,
Each module is
The solid oxide fuel, wherein the second gas discharge manifolds are arranged in contact with each other so that the flow of the second gas in the second gas discharge manifold is alternately directed between the modules. Battery composite module

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