JP2015138683A - Metal support type solid oxide fuel battery, and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal support type solid oxide fuel battery which is arranged so that even if a fuel electrode side goes into a condition such that a carbon component can be easily precipitated, the carbon component precipitation on a fuel electrode can be suppressed or prevented and consequently, the damage to the fuel electrode or solid electrolyte can be suppressed or prevented; and a method for manufacturing such a metal support type solid oxide fuel battery.SOLUTION: A metal support type solid oxide fuel battery comprises: a solid oxide fuel battery including a solid electrolyte, and a fuel electrode and an air electrode which sandwich the solid electrolyte therebetween; and a metal support provided adjacently to the fuel electrode and supporting the solid oxide fuel battery. The metal support has an open pore communicating from a fuel-supply flow path side face to a fuel electrode side face; a catalyst material capable of converting at least one of a hydrocarbon based fuel and carbon monoxide into carbon components is arranged in at least one of the inner surface of the open pore of the metal support and the inside thereof.

Description

  The present invention relates to a metal-supported solid oxide fuel cell and a method for manufacturing the same. More specifically, the present invention relates to a metal-supported solid oxide fuel cell provided with a predetermined metal support on the fuel electrode side and a method for producing a metal-supported solid oxide fuel cell.

  Conventionally, a metal-supported solid oxide fuel cell having a low output resistance due to a pure resistance and an electrode reaction due to an ionic conductivity and thickness of an electrolyte and a high output characteristic has been proposed (see Patent Document 1). .

  This metal-supported solid oxide fuel cell is a metal-supported solid oxide fuel cell in which a fuel electrode layer, an electrolyte layer, and an air electrode layer are sequentially formed on a metal support. The thickness of the electrolyte layer is 5 to 30 μm, the surface roughness Ra of the interface between the electrolyte layer and the fuel electrode layer is 0.5 to 3.0 μm, and the surface roughness of the interface between the electrolyte layer and the air electrode layer. Ra is 0.5 to 3.0 μm.

JP 2010-218759 A

  However, in the metal-supported solid oxide fuel cell described in Patent Document 1, when the carbon component is likely to precipitate on the fuel electrode layer side, the thin region on the metal support side of the fuel electrode layer Carbon components derived from the fuel and the like that have passed through the metal support having a porous structure and through-holes are concentrated and the volume expansion of the fuel electrode layer occurs. As the fuel electrode layer expands, the fuel electrode layer and the adjacent electrolyte layer may be damaged.

  The present invention has been made in view of such problems of the prior art. Further, the present invention suppresses or prevents the deposition of carbon at the fuel electrode and suppresses damage to the fuel electrode and the solid electrolyte even when the carbon is easily deposited on the fuel electrode side. Another object of the present invention is to provide a metal-supported solid oxide fuel cell that can be prevented and a method for manufacturing the same.

  The inventors of the present invention have made extensive studies in order to achieve the above object. As a result, the fuel electrode side has open pores that communicate from the fuel supply channel side surface to the fuel electrode side surface, and at least one of a hydrocarbon-based fuel and carbon monoxide is provided on at least one of the inner surface and inside of the open pores. The present invention has been completed by finding that the above object can be achieved by providing a metal support provided with a catalyst material that converts to carbon.

That is, the metal-supported solid oxide fuel cell of the present invention includes a solid electrolyte, a solid oxide fuel cell including a fuel electrode and an air electrode that sandwich the solid electrolyte, and a solid electrode disposed adjacent to the fuel electrode. And a metal support that supports the oxide fuel cell.
The metal support has open pores that communicate from the fuel supply channel side surface to the fuel electrode side surface.
In addition, a catalyst material that converts at least one of a hydrocarbon fuel and carbon monoxide into a carbon component is disposed on at least one of the inner surface and the inside of the open pores of the metal support.

  The method for producing a metal-supported solid oxide fuel cell according to the present invention is a method for producing the metal-supported solid oxide fuel cell according to the present invention, wherein the fuel supply channel side surface is disposed on the fuel electrode side surface. When a catalyst material for converting at least one of a hydrocarbon-based fuel and carbon monoxide into a carbon content is disposed on at least one of the inner surface and the inside of a metal support having open pores that communicate with each other, wet impregnation It is a manufacturing method using at least one of the method and the spray coating method.

According to the present invention, a solid oxide, a solid oxide fuel cell that includes a fuel electrode and an air electrode that sandwich the solid electrolyte, and a metal support that is disposed adjacent to the fuel electrode and supports the solid oxide fuel cell. A metal support in a metal-supported solid oxide fuel cell comprising a body, and having open pores communicating from the fuel supply flow path side surface to the fuel electrode side surface, on at least one of the inner surface and the inside of the open pores, A catalyst material for converting at least one of a hydrocarbon fuel and carbon monoxide into a carbon component is provided.
Therefore, even if it becomes a condition in which carbon is likely to deposit on the fuel electrode side, it is possible to suppress or prevent carbon deposition on the fuel electrode and to suppress or prevent damage to the fuel electrode or the solid electrolyte. A metal-supported solid oxide fuel cell and a method for manufacturing the same can be provided.

FIG. 1 is a cross-sectional view schematically showing an example of a metal-supported solid oxide fuel cell according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing an example of a metal-supported solid oxide fuel cell according to the second embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing another example of the metal-supported solid oxide fuel cell according to the second embodiment of the present invention.

  Hereinafter, a metal-supported solid oxide fuel cell and a manufacturing method thereof according to an embodiment of the present invention will be described in detail.

First, a metal-supported solid oxide fuel cell according to an embodiment of the present invention will be described in detail.
The metal-supported solid oxide fuel cell according to this embodiment includes a solid oxide, a solid oxide fuel cell including a fuel electrode and an air electrode that sandwich the solid electrolyte, and a solid oxide fuel cell that is disposed adjacent to the fuel electrode. And a metal support for supporting the physical fuel cell. The metal support has open pores that communicate from the fuel supply channel side surface to the fuel electrode side surface. In addition, a catalyst material that converts one or both of a hydrocarbon-based fuel and carbon monoxide into a carbon component is disposed on one or both of the inner surface and the inner surface of the open pores of the metal support. .

  By adopting such a configuration, for example, even when a system abnormality occurs and the carbon electrode is easily deposited on the fuel electrode side, the carbonization disposed in the open pores of the metal support is performed. By precipitating carbon in the catalyst material that converts one or both of the hydrogen-based fuel and carbon monoxide into carbon, it is possible to suppress or prevent the carbon from precipitating at the fuel electrode. Thereby, the volume expansion of the fuel electrode is suppressed or prevented, and damage to the fuel electrode or the solid electrolyte can be suppressed or prevented. As a result, more stable power generation of the solid oxide fuel cell becomes possible.

  Here, representative examples of the “hydrocarbon fuel” include hydrocarbons such as methane, ethane, propane, and butane, and alcohols such as methanol and ethanol. However, it is not limited to these, and organic compounds containing carbon and hydrogen reformed from various fuels such as gasoline and light oil as constituent elements, carbon, hydrogen and hetero atoms (for example, oxygen, nitrogen, phosphorus, Organic compounds containing sulfur as a constituent element can also be applied.

  Here, the “system abnormality” means, for example, excessive supply of fuel, insufficient supply of water, temperature change of the reformer (for example, generation of fuel having 2 or more carbon atoms. Usually, normal. In some cases, the fuel cell is adjusted so as not to generate fuel having 2 or more carbon atoms.), Temperature variation of the fuel cell stack, and the like.

  An example of a condition in which carbon is likely to precipitate on the fuel electrode side is, for example, the case where the number of moles of water vapor / number of moles of carbon (S / C) on the fuel electrode side is lower than the steady state.

  Further, in the metal-supported solid oxide fuel cell of the present embodiment, it is preferable that the whole or part of the inner surface of the open pores is covered with a catalyst material. By adopting such a configuration, for example, even when a system abnormality occurs and the carbon electrode is easily deposited on the fuel electrode side, the inner surface of the open pores of the metal support is covered. Suppressing or preventing carbon deposition at the fuel electrode by precipitating carbon in the catalyst material that converts either or both of the hydrocarbon-based fuel and carbon monoxide disposed to carbon. Can do. Thereby, the volume expansion of the fuel electrode is suppressed or prevented, and damage to the fuel electrode or the solid electrolyte can be suppressed or prevented. As a result, more stable power generation of the solid oxide fuel cell becomes possible. Further, there is an advantage that the amount of the catalyst material used can be reduced.

  Furthermore, in the metal-supported solid oxide fuel cell of this embodiment, at least some of the open pores are filled with a catalyst material so that the open pores are not sealed. Is preferred. With such a configuration, for example, even when a system abnormality occurs and the carbon electrode is likely to precipitate on the fuel electrode side, open pores are formed inside the open pores of the metal support. By depositing carbon in a catalyst material that converts either or both of hydrocarbon-based fuel and carbon monoxide, which are filled and arranged so as to be in an unsealed state, into carbon, The precipitation of carbon can be suppressed or prevented. Thereby, the volume expansion of the fuel electrode is suppressed or prevented, and damage to the fuel electrode or the solid electrolyte can be suppressed or prevented. As a result, more stable power generation of the solid oxide fuel cell becomes possible. Further, there is an advantage that it is easy to adjust the specifications of the catalyst material provided.

  Further, in the metal-supported solid oxide fuel cell of the present embodiment, the metal support includes a catalyst material disposition region in which the catalyst material is disposed on the inner surface or inside of the open pores, and the open pores. A catalyst material non-arrangement region in which no catalyst material is arranged on the inner surface and inside, and the catalyst material non-arrangement region is located on the fuel supply flow path side and the fuel electrode side of the metal support. Is preferred. By adopting such a configuration, for example, even when a system abnormality occurs and the carbon electrode is likely to precipitate on the fuel electrode side, the inner surface of the open pores of the metal support is coated. Or a hydrocarbon-based fuel and carbon monoxide or both of which are filled in the open pores so that the open pores are not sealed. By precipitating the carbon content in the catalyst material converted into the minute, it is possible to suppress or prevent the carbon content from precipitating at the fuel electrode. Thereby, the volume expansion of the fuel electrode is suppressed or prevented, and damage to the fuel electrode or the solid electrolyte can be suppressed or prevented. As a result, more stable power generation of the solid oxide fuel cell becomes possible. In addition, by precipitating carbon in the middle of the metal support that is not on the fuel supply flow path side and the fuel electrode side of the metal support, the volume expansion due to carbon deposition is suppressed in the metal support that easily relaxes the volume expansion. There is an advantage that you can.

  Furthermore, in the metal-supported solid oxide fuel cell of this embodiment, it is preferable that the catalyst material contains at least one of nickel and cobalt. By adopting such a configuration, for example, even when a system abnormality occurs and the carbon electrode is likely to precipitate on the fuel electrode side, the inner surface of the open pores of the metal support is coated. Or a hydrocarbon-based fuel and carbon monoxide or both of which are filled in the open pores so that the open pores are not sealed. By precipitating the carbon content in the catalyst material containing nickel or cobalt that is converted into a minute amount, it is possible to suppress or prevent the carbon content from precipitating at the fuel electrode. Thereby, the volume expansion of the fuel electrode is suppressed or prevented, and damage to the fuel electrode or the solid electrolyte can be suppressed or prevented. As a result, more stable power generation of the solid oxide fuel cell becomes possible.

  Hereinafter, a metal-supported solid oxide fuel cell according to some embodiments of the present invention will be described in detail with reference to the drawings.

(First embodiment)
First, the metal-supported solid oxide fuel cell according to the first embodiment will be described in detail.
FIG. 1 is a cross-sectional view schematically showing an example of a metal-supported solid oxide fuel cell according to the first embodiment. As shown in FIG. 1, the metal-supported solid oxide fuel cell 1 </ b> A of this example includes a solid oxide fuel cell 10 and a metal support 20. The solid oxide fuel cell 10 includes a solid electrolyte 11, a fuel electrode layer 12, and an air electrode layer 13, and the solid electrolyte layer 11 is sandwiched between the fuel electrode layer 12 and the air electrode layer 13. . The metal support 20 is disposed adjacent to the fuel electrode layer 11 and supports the solid oxide fuel cell 10.
Further, the metal support 20 has open pores 20c that communicate from the fuel supply flow channel side surface 20a to the fuel electrode side surface 20b, and the inner surface 20d of the open pores 20c is covered with the catalyst material 22 and disposed. . In this example, the metal support 20 is constituted by an aggregate of granular support constituting materials 21. U in the figure indicates a fuel supply channel.

  By adopting such a configuration, for example, even when a system abnormality occurs and the carbon electrode is easily deposited on the fuel electrode side, the inner surface of the open pores of the metal support is covered. Suppressing or preventing carbon deposition at the fuel electrode by precipitating carbon in the catalyst material that converts either or both of the hydrocarbon-based fuel and carbon monoxide disposed to carbon. Can do. Thereby, the volume expansion of the fuel electrode is suppressed or prevented, and damage to the fuel electrode or the solid electrolyte can be suppressed or prevented. As a result, more stable power generation of the solid oxide fuel cell becomes possible. Further, there is an advantage that the amount of the catalyst material used can be reduced. For example, the catalyst material does not need to be coated on the entire surface, and may be coated on a part.

  Here, each configuration will be described in more detail.

First, as the solid electrolyte layer 11 in the solid oxide fuel cell 10, a material having gas impermeability and ability to pass oxide ions without passing electrons can be suitably used. As a constituent material of the solid electrolyte layer, for example, yttria (Y ₂ O ₃ ), neodymium oxide (Nd ₂ O ₃ ), samaria (Sm ₂ O ₃ ), gadria (Gd ₂ O ₃ ), scandia (Sc ₂ O _3). ) Or the like can be applied as stabilized zirconia. In addition, ceria solid solutions such as samaria doped ceria (SDC), yttria doped ceria (YDC), gadria doped ceria (GDC), bismuth oxide (Bi ₂ O ₃ ), lanthanum strontium magnesium gallate (La _1-x Sr _{x Ga 1-y Mg y O 3} : LSMG) or the like may be applied. However, it is not limited to these, and conventionally known solid electrolyte layer materials can be applied. In addition, these can be applied individually by 1 type or in combination of multiple types.

  Further, as the fuel electrode layer 12, one that is strong in a reducing atmosphere, permeates the fuel gas, has high electrical conductivity, and has a catalytic action for converting hydrogen molecules into protons can be suitably used. As a constituent material of the fuel electrode layer, for example, a metal such as nickel (Ni) may be applied alone, but a cermet in which an oxide ion conductor typified by yttria stabilized zirconia (YSZ) is mixed. Is preferably applied, which increases the reaction area and improves the electrode performance. At this time, a ceria solid solution such as samaria doped ceria (SDC) or gadria doped ceria (GDC) can be applied instead of yttria stabilized zirconia (YSZ). In addition, since the oxide oxide conductor made of ceramic is easily broken, the effect of the present invention is particularly remarkable when the fuel electrode layer is a cermet. However, it is not limited to these, and conventionally known fuel electrode layer materials can be applied. In addition, these can be applied individually by 1 type or in combination of multiple types.

Furthermore, as the air electrode layer 13, a material that is strong in an oxidizing atmosphere, permeates the oxidant gas, has high electrical conductivity, and has a catalytic action to convert oxygen molecules into oxide ions can be suitably used. The constituent material of the air electrode layer may be composed of, for example, an electrode catalyst or a cermet of an electrode catalyst and an electrolyte material. For example, a metal such as silver (Ag) or platinum (Pt) may be used as the electrode catalyst, but lanthanum strontium cobaltite (La _1-x Sr _x CoO ₃ : LSC) or lanthanum strontium cobalt ferrite ( _{La 1-x Sr x Co 1} -y Fe y O 3: LSCF), samarium strontium cobaltite _{(Sm x Sr 1-x CoO} 3: SSC), lanthanum strontium manganite _{(La 1-x Sr x MnO} 3: LSM It is preferable to apply a perovskite oxide such as However, it is not limited to these, and a conventionally known air electrode layer material can be applied. In addition, these can be applied individually by 1 type or in combination of multiple types. Examples of the electrolyte material include, but are not limited to, cerium oxide (CeO ₂ ), zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), and lanthanum oxide (La ₂ O ₃ ). Instead, a mixture with the above-mentioned various stabilized zirconia and oxides such as ceria solid solution can also be suitably used.

  In addition, the metal support 20 has an open pore that communicates from the side of the fuel supply channel to the side of the fuel electrode that can ensure gas permeability, and has sufficient strength as a support. It is not particularly limited. In addition, a metal support having a high electrical conductivity can be suitably used. For example, a plate-shaped member made of a corrosion-resistant alloy, corrosion-resistant steel, stainless steel, or the like containing nickel or chromium and having a plurality of open pores can be applied. Specifically, a punching metal substrate, an etching metal substrate, an expanded metal substrate, a foamed metal body, a metal (particle) powder sintered body, a metal mesh such as a wire mesh, a metal nonwoven fabric, etc., constituted by the support member constituting material 21. Can be used. Moreover, these may laminate | stack the same kind or a different kind as needed.

  In the present invention, the “open pores communicating from the fuel supply channel side surface to the fuel electrode side surface” in the metal support means, for example, when the metal support is a punching metal substrate, an etching metal substrate, an expanded metal substrate, or the like. Open pores (continuous pores) in the case of through-holes, metal foams and sintered metal powders, open pores between strands in the case of metal mesh, and gaps between metal fibers in the case of metal nonwoven fabrics. Each means.

  Further, the catalyst material 22 is not particularly limited as long as either one or both of a hydrocarbon fuel and carbon monoxide can be converted into a carbon content. For example, nickel and cobalt can be mentioned. In addition, these can also be applied individually or in combination. In addition, since the catalyst material 22 is disposed on the inner surface (or inside) of the open pores separately from the support component 21 that is the skeleton of the metal support 20, the carbon component is deposited. However, the mechanical strength of the metal support is hardly impaired.

(Second Embodiment)
Next, the metal-supported solid oxide fuel cell according to the second embodiment will be described in detail. In addition, about the thing equivalent to what was demonstrated in 1st Embodiment, the code | symbol same as them is attached | subjected and description is abbreviate | omitted.

  FIG. 2 is a cross-sectional view schematically showing an example of a metal-supported solid oxide fuel cell according to the second embodiment. As shown in FIG. 2, in the metal-supported solid oxide fuel cell 1B of this example, the inside 20e of all the open pores 20c is filled with the catalyst material 22 so that the open pores 20c are not sealed. Is different from the above-described embodiment.

  FIG. 3 is a cross-sectional view schematically showing another example of the metal-supported solid oxide fuel cell according to the second embodiment. As shown in FIG. 3, in the solid oxide fuel cell 1C of this example, the metal support 20 is provided with a catalyst material 22 on the inner surface 20d or the inside 20e of the open pore 20c. There is a region 20A and a catalyst material non-arranged region 20B in which the catalyst material 22 is not disposed on the inner surface 20d and the inside 20e of the open pore 20c, and the catalyst material non-arranged region 20B is a metal support. The structure located in the fuel supply flow path side and the fuel electrode side of 20 is different from the embodiment described above.

  As described above, in the present embodiment, by adopting a configuration in which the open pores are filled and arranged so that the open pores are in an unsealed state, for example, a system abnormality is caused. Even when the condition is such that carbon is likely to precipitate on the fuel electrode side, the open pores of the metal support are filled and disposed so that the open pores are not sealed. By precipitating carbon content in the catalyst material, it is possible to suppress or prevent carbon content precipitation at the fuel electrode. Thereby, the volume expansion of the fuel electrode is suppressed or prevented, and damage to the fuel electrode or the solid electrolyte can be suppressed or prevented. As a result, more stable power generation of the solid oxide fuel cell becomes possible. In addition, by precipitating carbon in the middle of the metal support that is not on the fuel supply flow path side and the fuel electrode side of the metal support, the volume expansion due to carbon deposition is suppressed in the metal support that easily relaxes the volume expansion. There is an advantage that you can.

Next, a method for manufacturing a metal-supported solid oxide fuel cell according to an embodiment of the present invention will be described in detail.
In addition, if the metal support type solid oxide fuel cell of this invention has the structure mentioned above, it manufactures with the manufacturing method of the metal support type solid oxide fuel cell which concerns on one Embodiment of this invention mentioned later. It is not limited to what was done.

(Third embodiment)
The method for producing a metal-supported solid oxide fuel cell according to the third embodiment is a preferred embodiment of the method for producing a metal-supported solid oxide fuel cell according to one embodiment of the present invention described above. A catalyst for converting at least one of a hydrocarbon fuel and carbon monoxide into a carbon component on at least one of an inner surface and an inner surface of an open pore of a metal support having an open pore communicating from a fuel supply channel side surface to a fuel electrode side surface This is a manufacturing method using at least one of a wet impregnation method and a spray coating method when disposing the material.

  When the wet impregnation method or the spray coating method is applied in this way, the catalyst material can be easily disposed on at least one of the inner surface and the inside of the open pores of the metal support. Although not particularly limited, it is preferable to apply the wet impregnation method in the manufacture of the metal-supported solid oxide fuel cell according to the first embodiment described above, and the second implementation described above. In manufacturing the metal-supported solid oxide fuel cell according to the embodiment, either a wet impregnation method or a spray coating method may be applied.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples.

Example 1
First, in order to obtain a metal support (substrate), a green sheet for forming a metal support was prepared. Specifically, it was created as follows.
A substrate material mainly composed of powder having the same composition as SUS430 (Cr: 18% by mass) is further added with a water-soluble acrylic binder as a binder and polyethylene glycol (PEG) as a pore former, and mixed. A green sheet for forming a metal support was obtained by a tape casting method. In addition, the thickness of the green sheet for metal support formation is 600 micrometers, and the ratio of board | substrate material, a binder, and a pore making material is board | substrate material: binder: pore forming agent = 60: 20: 20 (volume ratio).

Next, in order to obtain a fuel electrode layer, a green sheet for forming a fuel electrode layer was prepared. Specifically, it was created as follows.
The ratio of nickel (Ni) and (YSZ) to nickel oxide (NiO) having an average particle diameter of 0.5 μm and yttria stabilized zirconia (YSZ) having an average particle diameter of 1 μm is Ni: YSZ = 7: 3 (mass ratio) ), And these were mixed to obtain a fuel electrode layer material. To this, a water-soluble acrylic binder as a binder and polyethylene glycol (PEG) as a pore-forming agent are further added, mixed, and formed into a fuel electrode layer containing NiO and YSZ by a tape-cast method. A sheet was obtained. Note that the ratio of the fuel electrode layer material, the binder, and the pore former is fuel electrode layer material: binder: pore former = 80: 10: 10 (volume ratio).

The green sheet for forming the fuel electrode layer was laminated on the green sheet for forming the metal support, and was baked for 2 hours in an electric furnace of 1000 ° C. and 50% H ₂ (Ar base) to be integrated. A metal support / fuel electrode layer was obtained.

  A disc having a diameter of 30 mm was cut out from the obtained substrate / fuel electrode layer by laser cutting. The thickness of the disc is 500 μm, the thickness of the fuel electrode layer is 50 μm, and the porosity of the metal support is 35% by volume.

  Next, a solid electrolyte layer made of yttria-stabilized zirconia (YSZ) was formed on the disk fuel electrode layer by sputtering. Specifically, yttria-stabilized zirconia (8YSZ) having a yttria content of 8 mol% is used as a sputtering target, argon gas (gas pressure: 0.2 Pa) is used as a sputtering gas, room temperature (25 ° C.), A solid electrolyte layer was formed at an output of 300 W. Further, an air electrode layer made of lanthanum strontium cobalt ferrite (LSCF) was formed on the solid electrolyte layer by sputtering. Specifically, lanthanum strontium cobalt ferrite (LSCF) is used as a sputtering target, argon gas (gas pressure: 0.2 Pa) is used as a sputtering gas, an air electrode layer is formed at room temperature (25 ° C.) and an output of 300 W. Thus, a metal-supported solid oxide fuel cell in which no catalyst material was disposed was obtained. After that, a nickel (Ni) -containing solvent (high) is formed on the surface opposite to the surface on which the fuel electrode layer is formed of the metal support (substrate) of the metal support solid oxide fuel cell in which the catalyst material is not disposed. The solution prepared by using a MOD coating agent (manufactured by Junsei Kagaku Co., Ltd.) is dripped, dipped and dried three times, and the catalyst material is disposed as shown in FIG. A solid oxide fuel cell was obtained.

(Comparative Example 1)
Nickel (Ni) is formed on the surface opposite to the surface on which the fuel electrode layer is formed of the metal support (substrate) of the metal support solid oxide fuel cell in which the catalyst material obtained in Example 1 is not disposed. The metal-supported solid oxidation of the present example in which the catalyst material is not disposed by repeating the drying step three times without dripping the solution prepared using the solvent containing (high purity chemical, MOD coating agent) A physical fuel cell was obtained.

(Example 2)
Nickel oxide (NiO) is formed on the surface opposite to the surface on which the fuel electrode layer is formed of the metal support (substrate) of the metal support solid oxide fuel cell in which the catalyst material obtained in Example 1 is not disposed. ) The process of hanging a mixed liquid of fine particles and butyl carbitol acetate (NiO content: 10% by mass), dipping, and drying was repeated 10 times to dispose the catalyst material as shown in FIG. A metal-supported solid oxide fuel cell of this example was obtained.

(Comparative Example 2)
Nickel oxide (NiO) is formed on the surface opposite to the surface on which the fuel electrode layer is formed of the metal support (substrate) of the metal support solid oxide fuel cell in which the catalyst material obtained in Example 1 is not disposed. ) The metal-supported mold of this example, in which the catalyst material is not disposed by repeating the drying step 10 times without dripping the mixed liquid of fine particles and butyl carbitol acetate (NiO content: 10 mass%) A solid oxide fuel cell was obtained.

(Example 3)
Nickel oxide (NiO) is formed on the surface opposite to the surface on which the fuel electrode layer is formed of the metal support (substrate) of the metal support solid oxide fuel cell in which the catalyst material obtained in Example 1 is not disposed. 3) Spray a mixed solution of fine particles and butyl carbitol acetate (NiO content: 5% by mass), soak into the support, wait for 10 minutes, and repeat the drying process 5 times, as shown in FIG. A catalyst material was disposed on the metal-supported solid oxide fuel cell of this example.

(Comparative Example 3)
Nickel oxide (NiO) is formed on the surface opposite to the surface on which the fuel electrode layer is formed of the metal support (substrate) of the metal support solid oxide fuel cell in which the catalyst material obtained in Example 1 is not disposed. ) The metal support of this example in which the catalyst material is not disposed by repeating the drying process 5 times without spraying a mixed liquid of fine particles and butyl carbitol acetate (NiO content: 5 mass%) Type solid oxide fuel cell was obtained.

[Performance evaluation]
(Open circuit voltage measurement)
The metal-supported solid oxide fuel cell of each of the above examples was installed in an evaluation machine, and the decrease value of the open circuit voltage (OCV) after maintaining the open circuit state for 15 minutes under the following measurement conditions was measured. The obtained results are shown in Table 1. A reformer having a rhodium-based reforming catalyst is disposed in the fuel supply channel of the evaluator.

<Measurement conditions>
-Solid oxide fuel cell temperature: 750 ° C
-Reformer inlet gasoline flow rate: 0.64cc / min
-Reformer feed water (H ₂ O) amount: 0.22 g / min
-Reformer temperature (outlet): 700 ° C

(Visual observation)
The metal-supported solid oxide fuel cells of Example 1 and Comparative Example 1 after the open circuit voltage measurement were visually observed. The obtained results are also shown in Table 1. The “carbon content not detected in the fuel electrode layer” in Example 1 is a result of cutting the metal-supported solid oxide fuel cell and performing microscopic Raman spectroscopic analysis on the cross section of the fuel electrode layer. .

From the results of open circuit voltage measurement in Table 1, Examples 1 to 3 belonging to the scope of the present invention are capable of stable power generation as compared with Comparative Examples 1 to 3 outside the present invention. I understand that.
In addition, from the results of visual observation in Table 1, in Example 1 belonging to the scope of the present invention, carbon carbon deposition at the fuel electrode is suppressed or prevented, and damage to the fuel electrode layer or the like is suppressed or prevented. I understand that.

  As mentioned above, although this invention was demonstrated with some embodiment and an Example, this invention is not limited to these, A various deformation | transformation is possible within the range of the summary of this invention.

  That is, in the above-described embodiments and examples, the metal-supported solid oxide fuel cell has been described by taking a metal-supported single cell as an example, but the present invention is not limited to this, and a plurality of metal-supported-type fuel cells The present invention can also be applied to a metal-supported solid oxide fuel cell having a structure in which single cells are stacked, that is, a stack structure.

1A, 1B, 1C Metal-supported solid oxide fuel cell 10 Solid oxide fuel cell 11 Solid electrolyte layer 12 Fuel electrode layer 13 Air electrode layer 20 Metal support 20A Catalyst material disposition region 20B Catalyst material disposition region 20a Fuel supply channel side surface 20b Fuel electrode side surface 20c Open pore 20d Inner surface 20e Interior 21 Support member constituting material 22 Catalyst material U Fuel supply channel

Claims (6)

A solid oxide, a solid oxide fuel cell comprising a fuel electrode and an air electrode sandwiching the solid electrolyte; and
A metal support that is disposed adjacent to the fuel electrode and supports the solid oxide fuel cell;
The metal support has open pores communicating from the fuel supply channel side surface to the fuel electrode side surface, and at least one of a hydrocarbon-based fuel and carbon monoxide is provided on at least one of the inner surface and the inside of the open pores. A metal-supported solid oxide fuel cell, characterized in that a catalyst material that converts to carbon is disposed.   2. The metal-supported solid oxide fuel cell according to claim 1, wherein the catalyst material is coated on the entire or part of the inner surface of the open pores.   3. The metal support according to claim 1 or 2, wherein at least a part of the open pores is filled with the catalyst material so that the open pores are not sealed. Type solid oxide fuel cell. The metal support has a catalyst material disposition region where the catalyst material is disposed on the inner surface or inside of the open pores, and the catalyst material is disposed on the inner surface and inside of the open pores. And no catalyst material non-arranged region,
4. The metal-supported solid oxidation according to claim 1, wherein the catalyst material non-arranged regions are located on a fuel supply flow path side and a fuel electrode side of the metal support. Physical fuel cell.   The metal-supported solid oxide fuel cell according to any one of claims 1 to 4, wherein the catalyst material contains at least one of nickel and cobalt. A method for producing a metal-supported solid oxide fuel cell according to any one of claims 1 to 5,
At least one of a hydrocarbon-based fuel and carbon monoxide is converted into a carbon component on at least one of the inner surface and the inner surface of the open pores of the metal support having open pores communicating from the fuel supply flow path side surface to the fuel electrode side surface. A method for producing a metal-supported solid oxide fuel cell, wherein at least one of a wet impregnation method and a spray coating method is used when disposing the catalyst material.

Images