WO2005045962A1 - 固体電解質型燃料電池用発電セル - Google Patents
固体電解質型燃料電池用発電セル Download PDFInfo
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- WO2005045962A1 WO2005045962A1 PCT/JP2004/016658 JP2004016658W WO2005045962A1 WO 2005045962 A1 WO2005045962 A1 WO 2005045962A1 JP 2004016658 W JP2004016658 W JP 2004016658W WO 2005045962 A1 WO2005045962 A1 WO 2005045962A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9066—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of metal-ceramic composites or mixtures, e.g. cermets
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a power generation cell for a solid oxide fuel cell using a lanthanum gallate-based electrolyte as a solid electrolyte, and more particularly to a fuel electrode for a solid oxide fuel cell.
- a solid oxide fuel cell can use hydrogen gas, natural gas, methanol, coal gas, or the like as a fuel, so that it can promote the use of alternative energy to petroleum in power generation and use waste heat.
- the structure of this solid oxide fuel cell generally has a structure in which an air electrode is laminated on one surface of a solid electrolyte made of oxide, and a fuel electrode is laminated on the other surface of the solid electrolyte.
- Each has a structure in which separators are laminated.
- This solid oxide fuel cell generally operates at 800-1000 ° C, but in recent years, a low-temperature type having an operating temperature of 600-800 ° C has been proposed.
- the ionic conductor has the general formula: La Sr Ga Mg AO (where Al X X 1-YZ YZ 3
- the fuel electrode has a general formula: Ce B 0, wherein B is one or more of Sm, Gd, Y, and Ca.
- m is 0 ⁇ m ⁇ 0.4
- B is one or more of Sm, Gd, Y, and Ca; the same applies hereinafter
- doped ceria and nickel
- a layer having a composition or a plurality of layers having different nickel content ratios also forms a layer, and the plurality of layers having different nickel content ratios have a continuous or intermittent nickel content ratio from the innermost layer to the outermost layer. It is known that there is a structure having a structure in which the structure is gradually increased.
- Patent Document 1 Japanese Patent Application Laid-Open No. 11-335164
- Patent Document 2 Japanese Patent Application Laid-Open No. 11-297333
- B-doped ceria fixed to the nickel surface having a porous skeletal structure in a granular manner With respect to a fuel electrode having a tissue structure, the B-doped ceria fixed in a granular manner is adjacent to the B-doped ceria.
- the more B-doped ceria that is independently fixed without contacting the B-doped ceria that is fixed in the form of particles the more the characteristics of the solid oxide fuel cell can be improved.
- B-doped ceria, which is independently fixed to the nickel surface of the porous skeletal structure in the form of particles has an average particle size which is conventionally known.
- B-doped ceria grains (hereinafter referred to as large-diameter ceria grains) in addition to B-doped ceria grains (0.01-0.0.09 m) (Referred to as small-diameter ceria grains) are independently fixed in the gaps between the large-diameter ceria grains and the large-diameter ceria grains, thereby improving the characteristics of the solid oxide fuel cell. It was.
- (C) A solid electrolyte type in which a lanthanum gallate-based oxide ion conductor is used as a solid electrolyte, a porous air electrode is formed on one surface of the solid electrolyte, and a porous fuel electrode is formed on the other surface.
- the fuel electrode has a general formula: CeBO
- the sintered body of capped ceria and nickel has the general formula Ce B 0 (where B is one of Sm, Gd, Y, and Ca) on the nickel surface of the porous skeletal structure. Species or two or more, m is
- the B-doped ceria grains represented by 0 ⁇ m ⁇ 0.4) are independently fixed and have a gradient composition in which the nickel content increases in the thickness direction, and the fuel electrode in contact with the solid electrolyte
- the power generation output can be further increased by adopting a fuel electrode whose nickel ratio on the innermost surface is 0.1-20% by volume and nickel ratio on the outermost surface of the fuel electrode is 40-99% by volume.
- the fuel electrode has a general formula: CeBO
- the sintered body of capped ceria and nickel is a sintered body consisting of a plurality of cores with different nickel content ratios, in which B-doped ceria grains are independently fixed on the surface of the porous framework structure. These layers are laminated on at least the innermost layer in contact with the solid electrolyte having a nickel ratio of 0.1 to 20% by volume and the innermost layer separated from the solid electrolyte having a nickel ratio of 40 to 99% by volume.
- the power generation output can be further increased.
- the present invention has been made based on the results of vigorous research,
- the B-doped ceria grains according to (1) or the B-doped ceria grains constituting the large-diameter ceria grains and the small-diameter ceria grains according to (2) are represented by a general formula: Ce BO (where B
- 1- mm 2 is one or more of Sm, Gd, Y, and Ca, and m is a solid oxide fuel cell made of B-doped ceria represented by 0 ⁇ m ⁇ 0.4) Fuel cell anode,
- the fuel electrode is the fuel electrode according to the above (1), (2) or (3);
- the lanthanum gallate-based oxide ion conductor has a general formula: La Sr Ga Mg A O
- the power generation cell for a solid oxide fuel cell according to the above (4) which is an oxide conductor represented by the formula (4).
- a lanthanum gallate-based oxide ion conductor is used as a solid electrolyte, and one of the solid electrolytes is used.
- a porous air electrode is formed on one side and a porous fuel electrode is formed on the other side.
- the fuel electrode has a general formula: Ce B 0 (where B is one or more of Sm, Gd, Y, and Ca,
- m is a sintered body of B-doped ceria and nickel represented by 0 ⁇ m ⁇ 0.4), and this sintered body has B-doped ceria particles on the surface of a porous nickel skeleton having a skeleton structure. It has a gradient composition in which the nickel content increases in the thickness direction, and the nickel content of the innermost surface of the sintered body in contact with the solid electrolyte is 0.1-20% by volume. Power generation cell for a solid oxide fuel cell, in which the nickel ratio of the outermost surface of the sintered body with the most solid electrolyte power is 40-99% by volume,
- the fuel electrode has a general formula: Ce B 0 (where B is one or more of Sm, Gd, Y, and Ca,
- m is a sintered body of B-doped ceria and nickel represented by 0 ⁇ m ⁇ 0.4), and this sintered body has B-doped ceria particles on the surface of a porous nickel skeleton having a skeleton structure.
- a plurality of layers having different nickel contents are also independently fixed, and the layers having different nickel contents are in contact with the solid electrolyte and have a nickel content of 0.1 to 20% by volume.
- the fuel electrode has a general formula: Ce B 0 (where B is one or more of Sm, Gd, Y, and Ca)
- M is a sintered body of B-doped ceria and nickel represented by 0 ⁇ m ⁇ 0.4), and this sintered body has B-doped ceria particles on the surface of the porous nickel skeleton having a skeletal structure.
- M is a sintered body of B-doped ceria and nickel represented by 0 ⁇ m ⁇ 0.4), and this sintered body has B-doped ceria particles on the surface of the porous nickel skeleton having a skeletal structure.
- the plurality of layers having different nickel content ratios are in contact with the solid electrolyte and have a nickel ratio of 0.1-20 volume%.
- the B-doped ceria particles which are independently fixed to the skeleton surface of the porous nickel having the skeleton structure are B-doped seria particles having two particle size distribution peaks having greatly different particle diameters. Is more preferable,
- the fuel electrode has a general formula: CeBO
- the sintered body of capped ceria and nickel has a general formula Ce B 0 (where B is Sm, Gd, Y, Ca 1
- m is an average particle diameter represented by 0 ⁇ m ⁇ 0.4): 0.2-0.6 m B-doped ceria grains (hereinafter, this average particle diameter: 0.2) -0.6 m of B-doped ceria grains are independently adhered to “large-diameter ceria grains”, and are further inserted into gaps between the large-diameter ceria grains and the large-diameter ceria grains.
- B is one or more of Sm, Gd, Y, Ca, m is 0 ⁇ m ⁇ 0.
- B-doped ceria grains having an average grain size of 0.01-0.09 m (hereinafter referred to as 0.01-0.09 / zm B-doped ceria grains having a small diameter Ceria particles) are fixed independently, and the nickel composition has a gradient composition that increases in the thickness direction.
- the nickel ratio on the innermost surface of the fuel electrode in contact with the solid electrolyte is 0.1. — 20% by volume, and the nickel ratio on the outermost surface of the anode is 40—99% by volume.
- T A solid electrolyte in which a lanthanum gallate-based oxide ion conductor is used as a solid electrolyte, a porous air electrode is formed on one surface of the solid electrolyte, and a porous fuel electrode is formed on the other surface.
- B is one or more of Sm, Gd, Y and Ca, and m is the sintered body force of B-doped ceria and nickel expressed by 0 ⁇ m ⁇ 0.4
- the large diameter ceria grains are independently fixed to the nickel surface having a high quality skeleton structure, and the small diameter ceria grains are independently fixed to the gap between the large diameter ceria grains and the large diameter ceria grains.
- a plurality of layers having different compounding ratios may be formed, and the plurality of layers may have at least a nickel ratio:
- a fuel electrode consisting of an innermost layer in contact with a solid electrolyte of 0.1 to 20% by volume and an outermost layer laminated on the innermost layer separated from a solid electrolyte with a nickel ratio of 40 to 99% by volume should be used. Power generation output can be further increased,
- (H) One or two or more intermediate layers are formed between the innermost layer and the outermost layer having different nickel compounding ratios as described in (e), and the nickel ratio of the innermost layer is 0.
- the nickel ratio of the outermost layer is within the range of 40-99% by volume, and the nickel ratio of the outermost layer is in the range of 40-99% by volume, and is one or more intermediate layers formed between the innermost layer and the outermost layer.
- the power generation output can be further increased by employing anodes that are stacked so that the nickel content ratio increases continuously or intermittently from the innermost layer to the outermost layer. The research results were obtained.
- the fuel electrode has a general formula: Ce B 0 (where B is one or more of Sm, Gd, Y, and Ca,
- m is a sintered body of B-doped ceria and nickel represented by 0 ⁇ m ⁇ 0.4), and this sintered body has an average particle diameter of 0.4 ⁇ m on the surface of the porous nickel skeleton having a skeleton structure. 2-0.
- B-doped ceria particles (hereinafter referred to as B-doped ceria particles having an average particle size of 0.2-0.6 m are referred to as “large-diameter ceria particles”), and are independently fixed.
- B-doped ceria grains having an average grain size of 0.01-0.09 m (hereinafter referred to as B-doped ceria grains having an average grain diameter of 0.01-0.09 / zm) “Small-diameter ceria grains”) are independently fixed, and have a gradient composition in which the nickel content increases in the thickness direction. The nickel ratio on the innermost surface of the sintered body in contact with the solid electrolyte is reduced.
- the fuel electrode has a general formula: Ce B 0 (where B is one or more of Sm, Gd, Y, and Ca,
- m is a sintered body of B-doped ceria and nickel represented by 0 ⁇ m ⁇ 0.4), and the sintered body has the large-diameter ceria particles on the surface of a porous nickel skeleton having a skeleton structure. It is composed of a plurality of layers having different nickel content ratios in which the small diameter ceria particles are independently fixed in the gaps between the large diameter ceria particles and the large diameter ceria particles.
- the solid layers are in contact with the solid electrolyte and consist of an innermost layer with a nickel ratio of 0.1 to 20% by volume and an outermost layer with a solid electrolyte layer separated from the innermost layer with a nickel ratio of 40 to 99% by volume. Power generation cells for electrolyte fuel cells,
- the fuel electrode has a general formula: Ce B 0 (where B is one or more of Sm, Gd, Y, and Ca)
- m is a sintered body of B-doped ceria and nickel represented by 0 ⁇ m ⁇ 0.4), and this sintered body is formed on the surface of the porous nickel skeleton having a skeleton structure by the large-diameter ceria particles.
- the small-diameter ceria grains are independently fixed in the gaps between the large-diameter ceria grains and the large-diameter ceria grains to form a plurality of layers having different nickel content ratios.
- the plurality of layers having different ratios are the innermost layer in contact with the solid electrolyte and having a nickel ratio of 0.1 to 20% by volume, the outermost layer having a nickel ratio of 40 to 99% by volume laminated farthest from the solid electrolyte, and It is composed of one or more intermediate layers formed between the innermost layer and the outermost layer, and the one or more intermediate layers are directed to the outermost layer laminated farthest from the innermost layer.
- V is stacked so that the nickel content ratio increases continuously or intermittently.
- the power generation cell for a solid oxide fuel cell is characterized in that:
- the thickness of the innermost layer is preferably as thin as possible, and the thickness of the innermost layer is in the range of 0.5 to 5 ⁇ m, and the thickness of the outermost layer is 10 to 50 ⁇ m.
- the thickness of the innermost layer is in the range of 0.5 to 5 m, and the thickness of the outermost layer is in the range of 10 to 50 m (8), (9), ( 11) or a power generation cell for a solid oxide fuel cell according to (12),
- the lanthanum gallate-based oxidant ion conductor has a general formula: La Sr Ga Mg A
- the fuel electrode of the power generation cell for a solid oxide fuel cell according to the present invention has a structure in which doped ceria particles are independently fixed to the nickel surface of the porous skeleton structure.
- the characteristics of the solid oxide fuel cell can be improved. The reasons are as follows. In other words, if the doped ceria particles are independently fixed to the porous skeletal structure of the nickel surface as described above, and if the fuel electrode is adopted, nickel is locally localized during operation of the solid oxide fuel cell. Thermal expansion due to the large amount of heat generated.On the other hand, although the valence of ceria changes from +3 to +4 and the volume shrinks, ⁇ The effect of the difference in expansion coefficient is due to the fact that the doped ceria grains are independent. Little appeared, ⁇ ⁇ No peeling of ceria and nickel.
- the ⁇ -doped ceria grains are independently fixed to the nickel surface! /, Whereby nickel grain growth is suppressed, and therefore, the exposed area of nickel metal generated due to nickel grain growth is reduced. ⁇ ⁇ is prevented from increasing, and the distribution density of doped ceria particles is prevented from decreasing, and the area of reaction with hydrogen as fuel decreases, resulting in a solid electrolyte fuel. It is possible to prevent the characteristics of the battery from deteriorating.
- the fuel electrode in the conventional solid oxide fuel cell shown in FIG. 3 has a porous skeletal structure nickel surface because the cells are connected in a network.
- the exposed surface area of the nickel surface is reduced and the conductivity is hindered.
- the internal stress is built in due to the effect of the difference in expansion rate and immediately after receiving the tensile stress of the ceria forming a network.
- the desired characteristics of the solid oxide fuel cell cannot be obtained.
- Fig. 1 is a model drawing of a more preferred basic structure of the fuel electrode according to (2), (4)-(6) in the power generation cell for a solid oxide fuel cell according to the present invention. It is something.
- the fuel electrode of the power generation cell for a solid oxide fuel cell according to the present invention has a large diameter ceria particle having a B-doped ceria force fixed independently to the nickel surface having the porous skeleton structure.
- the small-diameter ceria grains that have been B-doped are independently fixed in the gaps between the large-diameter ceria and the large-diameter ceria that are independently fixed, and incorporate a fuel electrode with a strong structure.
- B-doped large-diameter ceria grains as shown in FIG. 1 are independently fixed on the nickel surface of the porous skeleton structure, and B-doped large-diameter ceria grains are interposed between the large-diameter ceria grains.
- the doped small-diameter ceria grains are independently fixed, ceria is more firmly fixed on the nickel surface of the porous skeletal structure, thereby further increasing the reaction area with hydrogen as fuel.
- nickel at the fuel electrode locally expands due to a large amount of heat generation, and on the other hand, while the valence of ceria changes from +3 to +4, the volume shrinks.
- fine B-doped small-diameter ceria grains are independently fixed to the nickel surface in the gap between the large-diameter ceria and the large-diameter ceria, so that the porous nickel Since the exposing property is ensured and the conductivity is not reduced because of this, the characteristics of the power generation cell are further improved.
- the nickel ratio of the innermost surface or the innermost layer is set to 0.1 to 20% by volume because the innermost surface is Alternatively, if the nickel ratio of the innermost layer is less than 0.1% by volume, the nickel as the skeleton is too small to obtain sufficient strength, while the nickel ratio of the innermost surface or the innermost layer is 20% by volume. It is not preferable to exceed the value, because the nickel content is too large and the characteristics as the fuel electrode are greatly reduced. Further, the nickel ratio of the outermost surface and the outermost layer, which is the farthest solid electrolyte force, is set to 40-99% by volume.
- the nickel ratio force is less than 0% by volume, sufficient strength as a fuel electrode cannot be obtained.
- the content exceeds 99% by volume, although sufficient strength can be obtained, the characteristics as a fuel electrode are significantly reduced, which is not preferable.
- the thickness of the innermost layer is 0.5-.
- the thickness of the innermost layer is preferably as small as possible, but the thickness is limited to 0.5 m in order to form the innermost layer at low cost.
- the thickness is more than 5 ⁇ m, the innermost layer is too thick and the characteristics as a fuel electrode are deteriorated, which is not preferable.
- the thickness of the outermost layer which is farthest from the solid electrolyte, is limited to 10 to 50 m. If the thickness is less than 10 m, the surface area of Ni is small and a sufficient effective electrode reaction area cannot be obtained. On the other hand, if the thickness of the outermost layer exceeds 50 / zm, the expansion of Ni causes stress in the whole cell and increases the diffusion resistance of the fuel gas in the electrode, which is not preferable.
- the power generation cell for a solid oxide fuel cell according to the present invention has a general formula: La Sr Ga Mg Al-X X 1-Y-Z Y z
- M contains B-doped ceria and nickel represented by 0 ⁇ m ⁇ 0.4), and the B-doped ceria grains are porous on the surface of a porous nickel skeleton structure forming a network.
- One of the features of the present invention is that they are combined as a fuel electrode independently fixed to the nickel surface having a high quality skeleton structure.
- B-doped ceria is compatible with lanthanum gallate solid electrolytes.
- the fuel electrode of the power generation cell for a solid oxide fuel cell according to the present invention is characterized in that B-doped ceria particles are independently fixed to the nickel surface having a porous skeleton structure as described above.
- the B-doped ceria grains independently fixed to the porous skeletal structure nickel surface become large-diameter ceria grains and small-diameter ceria grains, and the large-diameter seria grains have a large diameter.
- fine small-diameter ceria grains are fixed on the nickel surface in the crevice gaps, and the average diameter of the large-diameter ceria grains is 0.2-0.
- the average particle size of B-doped ceria may be within the range of 0.1-2 m !, but the average particle size of small-diameter ceria particles is extremely fine 0.01-1-0.09 m Is even better.
- the average particle diameter of the large-diameter ceria particles and the small-diameter ceria particles can be determined by image analysis.
- a solid oxide fuel cell incorporating a power generation cell provided with a fuel electrode according to the present invention can be applied to low-temperature operation of a solid oxide fuel cell, and furthermore, a compact fuel cell power generation module And high efficiency can be achieved.
- the mixture was heated and maintained at 1350 ° C. for 3 hours in the air, and the obtained massive sintered body was coarsely pulverized with a Nommer mill and then finely pulverized with a ball mill to obtain an average particle size of 1 .
- a 3 ⁇ m lanthanum gallate-based electrolyte raw material powder was produced.
- a mixture of 8 parts of a 0.5 mol / L cerium nitrate aqueous solution and 2 parts of a 0.5 mol / L samarium nitrate aqueous solution was added dropwise with stirring to a 1 mol / L aqueous sodium hydroxide solution while stirring. After co-precipitating and filtering samarium, the washing and stirring with pure water and filtration were repeated six times to wash and oxidize.
- a coprecipitated powder of cerium and samarium samarium was produced, and this was heated and maintained in air at 1000 ° C. for 3 hours, and was doped with an average particle size of about 0.8 / zm having a composition of (Ce Sm) 0 Ceria powder 1
- a 1 mol / L sodium hydroxide aqueous solution was added dropwise to the 1 mol / L nickel nitrate aqueous solution with stirring, to precipitate the hydroxide sodium chloride, filtered, and then stirred and washed with pure water six times.
- the resultant was repeatedly washed with water, and heated and kept at 900 ° C. for 3 hours in the air to produce nickel oxide powder having an average particle size of 1.1 ⁇ m.
- Powders of reagent grades of samarium oxide, strontium carbonate, and cobalt oxide were prepared, weighed to have a composition represented by (Sm Sr) CoO, mixed with a ball mill, and then mixed in air.
- the obtained powder was heated and maintained at 1000 ° C. for 3 hours, and the obtained powder was finely pulverized with a ball mill to produce a samarium strontium cobaltite-based air electrode raw material powder having an average particle diameter of 1.1 ⁇ m.
- a power generation cell was manufactured using the prepared raw materials by the following method.
- the lanthanum gallate-based electrolyte raw material powder produced in ⁇ is mixed with an organic binder solution in which polyvinyl butyral and dioctyl phthalate are dissolved in a mixed solvent of toluene and ethanol to form a slurry, which is formed into a thin plate by a doctor blade method.
- an organic binder solution in which polyvinyl butyral and dioctyl phthalate are dissolved in a mixed solvent of toluene and ethanol
- Sintering was performed by heating at 1450 ° C for 4 hours to produce a disk-shaped lanthanum gallate-based electrolyte having a thickness of 200 / ⁇ and a diameter of 120 mm.
- a slurry is prepared by mixing polyvinyl butyral and N-octyl phthalate in a mixed solvent of toluene and ethanol to form a slurry, and the slurry is screen-printed on the disc-shaped lanthanum gallate-based electrolyte.
- a slurry film having a thickness of 30 m was formed and dried, and then heated and maintained at 1250 ° C. for 3 hours in the air, and the fuel electrode was formed and baked on the disc-shaped lanthanum gallate-based electrolyte. .
- the powder obtained by wet (coprecipitation) is a dispersed ultrafine powder. However, since the powder is agglomerated immediately after drying, it is mixed with the nickel oxide as fine powder while avoiding agglomeration. An ethanol solution containing ultrafine SDC powder is used for the slurry. After molding, when dried, SDC agglomerates on the surface of the nickel powder, forming an independent ceria state. When it is fired, the fuel electrode of the present invention is obtained. A part of the microstructure of the fuel electrode of the present invention thus obtained was observed with a scanning electron microscope, and a micrograph of the structure with the scanning electron microscope is shown in FIG.
- the diameters of the large-diameter ceria grains and the small-diameter ceria grains independently fixed to the surface of the porous nickel having the skeletal structure shown in the structure photograph were measured by an image analysis method.
- the samarium strontium cobaltite-based air electrode raw material powder prepared in the above (d) is mixed with an organic binder solution in which polybutyral and N-dioctyl phthalate are dissolved in a toluene-ethanol mixed solvent to form a slurry.
- the slurry was prepared and the slurry On the other side of the tangalate-based electrolyte, it is formed by screen printing to a thickness of 30 ⁇ m, dried, and then heated and maintained at 1100 ° C for 5 hours in air to form an air electrode.
- a power generation cell for a solid electrolyte fuel cell of the present invention (hereinafter, referred to as a power generation cell of the present invention) comprising a solid electrolyte, a fuel electrode, and an air electrode is manufactured.
- the anode current collector consisting of porous M with a thickness of lmm is laminated on the
- a 1.2 mm-thick porous Ag current collector is stacked on the air electrode, and separators are stacked on the fuel electrode current collector and the air electrode current collector, respectively.
- a solid oxide fuel cell of the present invention having the configuration shown in FIG. 4 was produced.
- a conventional solid oxide fuel cell was manufactured by the method described below. First, an aqueous solution of 1N-nickel nitrate, an aqueous solution of 1N-cerium nitrate and an aqueous solution of 1N-samarium nitrate were prepared and weighed so that the volume ratio of NiO and (Ce Sm) O was 60:40.
- a slurry is prepared by using the composite powder, and the slurry is applied to one surface of the lanthanum gallate-based solid electrolyte prepared in Example 1 and sintered to form a fuel electrode.
- the fuel electrode formed in this power generation cell has a network structure in which samarium-doped ceria (SDC) surrounds the porous nickel surface of the framework, as shown in Fig. 3! /
- SDC samarium-doped ceria
- Oxidant gas air
- the solid electrolyte fuel cell of the present invention and the conventional solid electrolyte fuel cell differ only in the configuration of the fuel electrode, and the other configurations are the same. It is clear that solid oxide fuel cells show superior values for load current density, fuel utilization, cell voltage, output, output density, and power generation efficiency compared to conventional solid oxide fuel cells. .
- the mixture was heated and maintained at 1350 ° C. for 3 hours in the air, and the obtained massive sintered body was coarsely pulverized with a Nommer mill and then finely pulverized with a ball mill to obtain an average particle size of 1 3 ⁇ m lanthanum gallate-based solid electrolyte raw material powder was produced.
- a 1 mol / L sodium hydroxide aqueous solution was added dropwise with stirring to a mixed aqueous solution of 8 parts of a 0.5 mol / L aqueous cerium nitrate solution and 2 parts of a 0.5 mol / L aqueous samarium nitrate solution. Cerium and samarium co-precipitated.
- the resulting powder was sedimented using a centrifuge, the supernatant was discarded, distilled water was added, and the mixture was stirred and washed, and sedimented again using a centrifuge, and this operation was repeated six times to wash.
- a 1 mol / L sodium hydroxide aqueous solution was added dropwise with stirring to a mixed aqueous solution of 8 parts of a 0.5 mol / L aqueous cerium nitrate solution and 2 parts of a 0.5 mol / L aqueous samarium nitrate solution.
- the mixture was washed with water by repeating stirring and filtration with pure water six times to produce co-precipitated powder of Seridium Cerium and Sidani Samarium.
- SDC powder having a composition of (C e Sm) 0 and an average particle size of about 0.8 Manufactured.
- a 1 mol / L sodium hydroxide aqueous solution was added dropwise to the 1 mol / L nickel nitrate aqueous solution with stirring, to precipitate the hydroxide sodium chloride, filtered, and then stirred and washed with pure water six times.
- the resultant was repeatedly washed with water, and heated and kept at 900 ° C. for 3 hours in the air to produce nickel oxide powder having an average particle size of 1.1 ⁇ m.
- Powders of reagent grades of samarium oxide, strontium carbonate, and cobalt oxide were prepared, weighed to have a composition represented by (Sm Sr) CoO, mixed with a ball mill, and then mixed in air.
- the obtained powder was heated and maintained at 1000 ° C. for 3 hours, and the obtained powder was finely pulverized with a ball mill to produce a samarium strontium cobaltite-based air electrode raw material powder having an average particle diameter of 1.1 m.
- the lanthanum gallate-based solid electrolyte raw material powder was mixed with an organic binder solution obtained by dissolving polyvinyl butyral and N-dioctyl phthalate in a mixed solvent of toluene and ethanol to form a slurry, formed into a thin plate by a doctor blade method, and cut into a circle. After that, it was heated and maintained at 1450 ° C for 4 hours in the air and sintered to produce a disc-shaped lanthanum gallate-based solid electrolyte having a thickness of 200 m and a diameter of 120 mm.
- the above-mentioned oxidized nickel powder and the SDC powder are mixed at a volume ratio of 10:90, and mixed with a toluene-ethanol mixed solvent with an organic binder solution in which polybutyral and N-dioctyl phthalate are dissolved to form a slurry,
- the slurry was applied to one surface of the lanthanum gallate-based solid electrolyte so as to have an average thickness of 1 ⁇ m by a screen printing method, and dried to form a first green layer.
- an ethanol solution containing the above-mentioned nickel powder and the ultrafine powder of SDC was mixed so that the volume ratio of silica gel and SDC was 60:40, and polybutylene was added to a toluene-ethanol mixed solvent.
- a slurry was prepared by mixing a petalal and an organic binder solution in which N-dioctyl phthalate was dissolved, and this slurry was screen-printed on the dried first green layer so as to have a thickness of 30 ⁇ m. And dry to form a second green layer. It was.
- the lanthanum gallate-based solid electrolyte is formed by forming a plurality of green layers having a first green layer and a second green layer on one surface of the lanthanum gallate-based solid electrolyte in air at 1250 ° C for 3 hours.
- a fuel electrode composed of the innermost layer and the outermost layer shown in Fig. 5 was formed by baking on one surface of the solid electrolyte.
- the powder obtained by wet (coprecipitation) is a dispersed ultrafine powder. However, since the powder is agglomerated immediately after drying, it is mixed with the nickel oxide as fine powder while avoiding agglomeration. An ethanol solution containing ultrafine SDC powder is used for the slurry. After molding, when dried, SDC agglomerates on the surface of the nickel powder, forming an independent ceria state. When it is fired, the fuel electrode of the present invention is obtained. A part of the microstructure of the fuel electrode of the present invention thus obtained was observed with a scanning electron microscope, and a micrograph of the structure with the scanning electron microscope is shown in FIG.
- the diameters of the large-diameter ceria grains and the small-diameter ceria grains independently fixed to the surface of the porous nickel having the skeletal structure shown in the structure photograph were measured by an image analysis method.
- the samarium strontium cobaltite-based air electrode raw material powder is mixed with an organic binder solution obtained by dissolving polybutyral and N-dioctyl phthalate in a mixed solvent of toluene and ethanol to prepare a slurry.
- the other surface was formed by screen printing to a thickness of 30 m and dried, then heated and maintained at 1100 ° C for 5 hours in air to form and burn the air electrode shown in Fig. 5. .
- a power generation cell 1 (hereinafter, referred to as the power generation cell of the present invention) 1 for a solid electrolyte fuel cell of the present invention comprising the solid electrolyte, the fuel electrode, and the air electrode shown in FIG.
- a lmm-thick porous nickel current collector is stacked on the fuel electrode of the power generation cell 1 of the present invention, while a 1.2-mm-thick porous electrode is formed on the air electrode of the power generation cell of the present invention.
- the solid electrolyte fuel cell of the present invention having the structure shown in FIG. 4 is obtained by laminating an air electrode current collector that also provides high quality silver, and further laminating a separator on the fuel electrode current collector and the air electrode current collector. 1 Produced.
- a conventional solid oxide fuel cell was manufactured by the following method. First, an aqueous solution of 1N-nickel nitrate, an aqueous solution of 1N-cerium nitrate, and an aqueous solution of 1N-samarium nitrate were prepared and weighed so that the volume ratio of NiO and (Ce Sm) O was 60:40.
- a powder was obtained.
- a slurry is prepared by using the oxidized compound composite powder, and the slurry is applied to one surface of the lanthanum gallate-based solid electrolyte prepared in the example and sintered to form a fuel electrode, and further, an air electrode.
- the fuel electrode formed in this power generation cell had a network structure in which the SDC surrounded the nickel surface having a porous skeleton structure.
- Oxidant gas air
- the solid electrolyte fuel cell 1 of the present invention and the conventional solid electrolyte fuel cell differ only in the configuration of the fuel electrode, and the other configurations are the same. It can be seen that the electrolyte fuel cell 1 shows superior values in load current density, fuel utilization, cell voltage, output, output density, and power generation efficiency as compared with the conventional solid electrolyte fuel cell.
- the nickel powder and the SDC powder prepared in Example 2 were mixed at a volume ratio of 10:90, and mixed with an organic binder solution obtained by dissolving polybutyral and dioctyl phthalate in a mixed solvent of toluene and ethanol.
- an organic binder solution obtained by dissolving polybutyral and dioctyl phthalate in a mixed solvent of toluene and ethanol.
- a slurry was applied to one surface of the lanthanum gallate-based solid electrolyte so as to have an average thickness of 1 ⁇ m, and dried to form a first green layer.
- an ethanol solution containing the above-mentioned nickel powder and the ultrafine powder of SDC was mixed so that the volume ratio of silicon dioxide and SDC became 35:65, and polybutylene was added to a toluene-ethanol mixed solvent.
- a slurry was prepared by mixing a petalal and an organic binder solution in which N-dioctyl phthalate was dissolved, and this slurry was screen-printed on the dried first green layer so as to have a thickness of 1 ⁇ m. And dried to form an intermediate green layer.
- an ethanol solution containing the above-mentioned nickel powder and the ultrafine powder of SDC was mixed so that the volume ratio of silica gel and SDC was 60:40, and polybutylene was added to a toluene-ethanol mixed solvent.
- a slurry is prepared by mixing a petalal and an organic binder solution in which N-dioctyl phthalate is dissolved, and the slurry is formed on the dried intermediate green layer by a screen printing method so as to have a thickness of 20 ⁇ m. Was formed and dried to form a second green layer.
- the lanthanum gallate-based solid electrolyte having a plurality of green layers formed of a first green layer, an intermediate dullin layer and a second green layer on one surface is heated and maintained at 1250 ° C for 3 hours in air.
- the fuel electrode shown in FIG. 6, comprising the innermost layer of the fuel electrode, the intermediate layer of the fuel electrode, and the outermost layer of the fuel electrode, was formed by baking on one surface of the lanthanum gallate-based solid electrolyte.
- the fuel electrode obtained by baking has a mean diameter of samarium-doped samarium: 0.4 ⁇ m, and a mean diameter of samarium-doped interstices between the large-diameter ceria grains: 0.05 / zm. It was a component that the small diameter ceria grains had a structure in which they were fixed independently.
- a solid electrolyte and an air electrode were formed by baking in exactly the same manner as in Example 2 except that the fuel electrode was formed by baking in this manner, thereby producing a power generation cell 2 of the present invention comprising the solid electrolyte, the fuel electrode and the air electrode. Then, a fuel electrode current collector made of porous nickel having a thickness of lmm was laminated on the obtained fuel electrode of the power generation cell 2 of the present invention, while a thickness of 1.2 mm was formed on the air electrode of the power generation cell 2 of the present invention.
- the solid electrolyte fuel cell 2 of the present invention is produced by laminating the air electrode current collector made of porous silver color, and further laminating a separator on the fuel electrode current collector and the air electrode current collector. did. Using the solid oxide fuel cell 2 of the present invention thus obtained, a power generation test under the following conditions was performed.
- Oxidant gas air
- the intermediate layer formed on the fuel electrode of the power generation cell 2 of the present invention is a single layer.
- This intermediate layer is composed of two or more layers, and extends from the innermost layer to the outermost layer.
- the fuel electrode can be manufactured by stacking so that the nickel content ratio increases continuously or intermittently, and by further increasing the number of intermediate layers, the nickel content composition becomes the innermost.
- Surface Force The fuel electrode according to the above (1) having a gradient composition in which the nickel content ratio increases in the thickness direction toward the outermost surface can be formed.
- FIG. 1 is an explanatory view showing the structure of a fuel electrode according to the present invention.
- FIG. 2 is a scanning electron micrograph of a fuel electrode of the present invention.
- FIG. 3 is an explanatory view showing the structure of a conventional fuel electrode.
- FIG. 4 is an explanatory view of a solid oxide fuel cell.
- FIG. 5 is an explanatory view of a power generation cell of the present invention of a solid oxide fuel cell.
- FIG. 6 is an explanatory view of a power generation cell of the present invention of a solid oxide fuel cell.
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Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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US10/595,769 US20090098436A1 (en) | 2003-11-10 | 2004-11-10 | Power generation cell for solid electrolyte fuel cell |
EP04799564A EP1689012A1 (en) | 2003-11-10 | 2004-11-10 | Generation cell for solid electrolyte fuel cell |
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JP2003379477 | 2003-11-10 | ||
JP2003-379477 | 2003-11-10 | ||
JP2003379791 | 2003-11-10 | ||
JP2003-379791 | 2003-11-10 | ||
JP2004169532 | 2004-06-08 | ||
JP2004-169532 | 2004-06-08 | ||
JP2004303860A JP2005166640A (ja) | 2003-11-10 | 2004-10-19 | 固体電解質型燃料電池用発電セル |
JP2004-303860 | 2004-10-19 | ||
JP2004-322303 | 2004-11-05 | ||
JP2004322303A JP2006024545A (ja) | 2003-11-10 | 2004-11-05 | 固体電解質型燃料電池用発電セル |
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Cited By (2)
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WO2006088133A1 (ja) | 2005-02-18 | 2006-08-24 | Mitsubishi Materials Corporation | 固体電解質形燃料電池用発電セルおよびその燃料極の構造 |
US20110200910A1 (en) * | 2008-10-14 | 2011-08-18 | University Of Florida Research Foundation Inc. | Advanced materials and design for low temperature sofcs |
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FR2940857B1 (fr) * | 2009-01-07 | 2011-02-11 | Commissariat Energie Atomique | Procede de fabrication d'un electrolyseur haute temperature ou d'une pile a combustible haute temperature comprenant un empilement de cellules elementaires |
GB2535338B (en) * | 2015-02-06 | 2017-01-25 | Ceres Ip Co Ltd | Electrolyte forming process |
GB2524638B (en) | 2015-02-06 | 2016-04-06 | Ceres Ip Co Ltd | Electrolyte forming process |
CN107925097B (zh) * | 2015-08-22 | 2021-06-01 | 京瓷株式会社 | 单体、单体堆装置、模块及模块收纳装置 |
US20200099062A1 (en) * | 2016-12-20 | 2020-03-26 | Kyocera Corporation | Cell, cell stack device, module, and module housing device |
KR20200114511A (ko) * | 2019-03-29 | 2020-10-07 | 현대자동차주식회사 | 연료전지용 산화방지제 및 이를 포함하는 연료전지 |
WO2023193062A1 (en) * | 2022-04-06 | 2023-10-12 | Commonwealth Scientific And Industrial Research Organisation | Electrode compositions |
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EP1689012A1 (en) | 2006-08-09 |
US20090098436A1 (en) | 2009-04-16 |
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