WO2007091642A1 - Materiau pour electrode a air utilisee dans une pile a combustible a oxyde solide - Google Patents

Materiau pour electrode a air utilisee dans une pile a combustible a oxyde solide Download PDF

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Publication number
WO2007091642A1
WO2007091642A1 PCT/JP2007/052247 JP2007052247W WO2007091642A1 WO 2007091642 A1 WO2007091642 A1 WO 2007091642A1 JP 2007052247 W JP2007052247 W JP 2007052247W WO 2007091642 A1 WO2007091642 A1 WO 2007091642A1
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Prior art keywords
air electrode
particles
fuel cell
average particle
particle size
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PCT/JP2007/052247
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English (en)
Japanese (ja)
Inventor
Kazuo Hata
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Nippon Shokubai Co., Ltd.
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Priority to JP2007513500A priority Critical patent/JP5044392B2/ja
Publication of WO2007091642A1 publication Critical patent/WO2007091642A1/fr

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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
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
    • 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
    • H01M8/1253—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 the electrolyte containing zirconium oxide
    • 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
    • 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
    • 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 an air electrode material for a solid oxide fuel cell.
  • the present invention also relates to an air electrode formed from the air electrode material and a fuel cell having the air electrode.
  • Fuel cells have attracted attention as clean energy sources. Fuel cells are rapidly being studied for improvement and practical use mainly for household power generation, commercial power generation, and automobile power generation.
  • a cathode material for a solid oxide fuel cell a generalized bumskite oxide (ABO: A and B represent metal elements) is generally used. Among them, A site
  • Lanthanum with lanthanum and B-site manganese manganese are widely used. However, the electrode activity of this lanthanum-manganate material is low. Therefore, in order to increase the power generation efficiency, the operating temperature of the fuel cell power generation system must be raised to 900 ° C or higher.
  • Japanese Patent Application Laid-Open No. 7-226208 adds manganese having high activity to manganese.
  • Perovskite type oxides are disclosed.
  • Solid State Ionics, Vol. 118 (1999) p.241 shows that the crystal structure and thermal expansion of an air electrode material with praseodymium, strontium at the A site, and cobalt / manganese velobskite-type oxides. The rate has been reported.
  • the electrode activity at 750 ° C is inferior to that of an oxide containing cobalt.
  • a velovskite-type oxide containing iron is also used. It leaves and speaks. The ⁇ row shows Proceedings of the 3rd.International Symposium on bolid Oxide Fuel Cells p.241, 1993, Honolulu Hawaii.Perovskite-type oxides with lanthanum 'strontium at A site and cobalt' iron at B site Is described.
  • Japanese Patent Publication No. 11 242960 and Japanese Patent Application Laid-Open No. 2002-1510918 disclose perovskite-type oxides containing iron and Nikkenore.
  • US Pat. No. 6,946,213 describes an air electrode material using a perovskite oxide containing a transition element and magnesium, or a transition element and zinc.
  • the present invention has been made paying attention to the above situation. Its purpose is to maintain long-term electrode activity sustainability as a cathode material compared to conventional materials, and to withstand the heat history of repeated high temperatures exceeding 700 ° C at room temperature during operation and operation.
  • the object is to provide an air electrode material for a fuel cell having high durability.
  • Another object of the present invention is to provide a high-performance air electrode and fuel cell using the air electrode material.
  • perovskite oxides containing lanthanum and iron'cobalt have excellent electrode activity at 750 ° C or higher, and thus air. Used as an extreme material.
  • the present inventors based on iron-containing mouthbushite oxides, and their drawbacks.
  • the performance as an air electrode material was investigated by variously changing the constituent metal of the A site and B site in the iron-containing perovskite oxide, which should improve the performance further.
  • An air electrode material for a solid oxide fuel cell according to the present invention that has solved the above-mentioned problems is characterized by containing a velovskite oxide represented by the following general formula (I):
  • A represents at least one element selected from alkaline earth metal elements and rare earth elements; B represents at least one element selected from group 7a elements and group 8 element forces] ⁇ or 0.5 ⁇ x ⁇ l; y «0. Indicates 5 ⁇ y ⁇ l]
  • the air electrode for a solid oxide fuel cell of the present invention is an air electrode formed on one side of a solid electrolyte in a solid oxide fuel cell, and is formed of the air electrode material according to the present invention. It is characterized by that.
  • the solid oxide fuel cell of the present invention is a solid oxide fuel cell in which an air electrode is formed on one side of a solid electrolyte and a fuel electrode is formed on the other side.
  • the electrode is formed of the air electrode material according to the present invention.
  • FIG. 1 is a conceptual diagram showing a single cell power generation evaluation apparatus used in an experiment.
  • 1 indicates a heater
  • 2 indicates an alumina outer tube
  • 3 indicates an alumina inner tube
  • 4 indicates a platinum lead wire
  • 5 indicates a solid electrolyte sheet
  • 6 indicates a force sword
  • 7 indicates an anode 8 indicates a sealing material.
  • An air electrode material for a solid oxide fuel cell according to the present invention is characterized in that it includes a peculiar bskite oxide represented by the following general formula (I).
  • A represents at least one element selected from alkaline earth metal elements and rare earth elements; B represents at least one element selected from group 7a elements and group 8 element forces] ⁇ or 0.5 ⁇ x ⁇ l; y «0. Indicates 5 ⁇ y ⁇ l]
  • preferred alkaline earth metals used as the element A are Ca, Sr, Ba and the like.
  • Preferred rare earth elements include La, Ce, Sm, Gd and the like. These can be used alone, or two or more of them may be used in any combination as required. Of these, Sr and Ce are particularly preferable.
  • the 7a group element and the 8 group element used as the B element are described in “Science and Chemistry Dictionary” (issued by Iwanami Shoten, December 20, 2004, 5th edition, 20th edition, page 1525).
  • Group 7a and group 8 elements classified as “periodic rules of elements” are short-period type).
  • Preferred group 7a elements include Mn
  • preferred group 8 elements include Co, Ni, Cu and the like. These can be used alone, or two or more of them can be used in any combination as required. Of these, Ni and Cu are particularly preferred.
  • the values of X and y in the above formula are also important, and it is necessary to set the value of X in the range of 0.5 ⁇ x ⁇ l in order to exert the combined effect of the above elements effectively It is. More preferably, 0.5 5 ⁇ x ⁇ 0.95, even more preferably 0.660 ⁇ x ⁇ 0.90.
  • the force is less than 5, the difference in thermal expansion from the electrolyte is too large, so when the fuel cell is operated, it undergoes repeated thermal cycles between room temperature and operating temperature, so that the interface between the electrolyte membrane and the air electrode When stress is generated, the electrolyte membrane and the air electrode are easily separated or cracks are easily generated in the electrolyte membrane.
  • the value of y needs to be set in the range of 0.5 ⁇ y ⁇ 1. More preferably 0.
  • the y force is less than 0.05, it is difficult to exhibit the excellent electrode activity inherent in the iron-containing mouthbskite-type air electrode, and in particular, the stability of the electrode activity with time decreases.
  • the atomic ratio of oxygen in the perovskite-type acid complex is expressed as 3. ing.
  • the oxygen atomic ratio often takes a value smaller than 3. .
  • the atomic ratio of oxygen is represented as 3 for convenience.
  • a mixture of at least one of stable zirconium oxides stabilized by at least one of the selected elemental oxides is also an excellent air electrode material.
  • a preferable mixing ratio in this case is 5 to 30% by mass in total power of at least one of the doped silica and the stable zirconium oxide to 70 to 95% by mass of the above-mentioned brazeodymium iron-containing perovskite oxide. This is the range.
  • the doped ceria has electronic conductivity and ionic conductivity, and also has a characteristic of absorbing oxygen when the oxygen concentration is high and releasing the absorbed oxygen when the oxygen concentration is low.
  • the characteristics of the perovskite type oxide as an air electrode are further improved.
  • the above stable zirconium oxide has an effect of further increasing the consistency of the thermal expansion coefficient with the electrolyte, and contributes to the improvement of the binding property with the electrolyte.
  • the effect of the doped ceria and Z or stable zirconium oxide is effectively exerted by blending 5% by mass or more with respect to praseodymium / iron-containing perovskite oxide: 70 to 95% by mass.
  • the total amount exceeds 30% by mass, the absolute amount of the electrode active ingredient, the velobskite-type acid oxide, becomes dull and the activity decreases, and the volume mixing ratio becomes 60% or less. Therefore, the conductivity is also lowered, and the original object of the present invention cannot be achieved.
  • the more preferable blending ratio of doped ceria and Z or stable zirconia is 10% by mass or more and 25% by mass or less, and more preferably 20% by mass or less.
  • An embodiment in which coarse particles and fine particles of doped ceria are collected is also suitable.
  • Doped ceria The blending amount of the coarse particles and fine particles is preferably 5% by mass or more and 30% by mass or less, more preferably 10% by mass or more and 25% by mass or less, and further preferably 20% by mass or less.
  • the average particle size of each component is "doped ceria coarse particles> praseodymium iron-based perovskite"
  • the particle size should be adjusted to satisfy the relationship of “type oxide particles> stable Zircoyu particles”.
  • the average particle size of the doped ceria coarse particles is 1 to 30 111, the perovskite type
  • the average particle diameter of the oxide particles is preferably in the range of 0.3 to 3 ⁇ m, and the average particle diameter of the stabilized zirconia particles is preferably in the range of 0.1 to m.
  • the average particle diameter of the doped ceria coarse particles is 1 to 30 ⁇ m and the perovskite oxide particles are satisfied after satisfying the above-mentioned relationship of the average particle sizes of the respective particles. It is preferable that the average particle size is 0.3 to 3 ⁇ m, and the average particle size of the doped ceria fine particles is 0.1 to 1 ⁇ m.
  • the average particle diameter refers to the particle diameter at 50 volume% in the cumulative graph after measuring the particle size distribution of the particles.
  • the average particle size of the bottom buxite oxide particles is 0.3-3.
  • m means an aggregate of the same particles whose 50 volume% diameter is in the range of 0.3-3 / ⁇ ⁇ .
  • the functions of the doped ceria particles having an average particle size of 1 to 30 m are the formation and maintenance of pores in the air layer and the prevention of aggregation of the mouth bumskite type oxide particles as the electrode catalyst.
  • the stabilized zirconia particles or doped ceria fine particles having an average particle diameter of 0.1 to 1 / ⁇ ⁇ increase the adhesion between the doped ceria particles and the velovskite-type oxide particles and reliably form a conductive path. It exhibits the function of enhancing the bondability with the electrolyte.
  • the doped ceria coarse particles are mixed, if the average particle size is less than 1 ⁇ m, there is a possibility that an appropriate gap is not formed between the particles and the air permeability is insufficient. In addition, sintering is likely to proceed when exposed to high temperatures, and the porosity may tend to decrease over time. On the other hand, if the average particle size of the doped ceria particles becomes too large exceeding 30 m, the gaps between the particles are sufficiently secured and the decrease in porosity due to the progress of sintering is suppressed, but the strength as the air electrode layer May feel down.
  • the more preferable average particle diameter of the doped ceria coarse particles is 1.5 ⁇ m or more and 25 ⁇ m or less, more preferably 2 ⁇ m or more and 20 ⁇ m or less.
  • the 90% by volume diameter is 3 ⁇ m or more and 60 ⁇ m. In the following, it is more preferably 5 ⁇ m or more and 50 / zm or less, and further preferably 7 m or more and 40 m or less. This is because the amount of mixing of extremely coarse particles is suppressed as much as possible to achieve a homogeneous air electrode layer.
  • the doped ceria coarse particles particles of cerium oxide alone, cerium oxide / aluminum oxide mixed particles, and acid / cerium / acid / zirconium mixed particles can be used.
  • Particularly preferably used in the present invention is a ceria particle doped with at least one element selected from yttrium, samarium, and gadolinium forces to give mixed conductivity.
  • Doping amount is not particularly limited, 5 to 40 atoms relative to preferred cerium 0/0, more preferably from 10 to 30 atomic%.
  • Doped ceria fine particles have the same composition. Can be used.
  • a product heat-treated at 1300 ° C or higher for 5 hours or longer is pulverized with a bead mill or ball mill within the above average particle size range and 90 volumes.
  • Doped silica coarse particles and fine particles adjusted within the% diameter range are preferably used.
  • a more preferable heat treatment temperature condition is 1350 ° C. or more, more preferably 1400 ° C. or more, and a more preferred heat treatment time condition is 10 hours or more, more preferably 20 hours or more.
  • the perovskite type oxide used in the present invention is preferably adjusted so that the average particle diameter is within a range of 0.3 to 3 ⁇ m in order to form a conductive path. .
  • the average particle size of the perovskite-type oxide is less than 0.3 ⁇ m, sintering is likely to proceed when exposed to a high temperature for a long time, and the conductive path is blocked. There is a risk of impeding conductivity.
  • the average particle size of the perovskite type oxide exceeds 3 ⁇ m, the sintering does not easily proceed even when exposed to high temperatures, but the electrode activity tends to decrease.
  • the average particle size of the perovskite type oxide is more preferably not less than 0.4 m and not more than 2. More preferably not less than 0.5 m and not more than 2 m.
  • the volume% diameter may be 1 ⁇ m or more and 15 m or less, more preferably 2 ⁇ m or more and 10 ⁇ m or less, and even more preferably 2 / zm or more and 8 / zm or less.
  • a product heat-treated at 1300 ° C or higher for 5 hours or longer is pulverized with a bead mill or ball mill within the above average particle size range.
  • Perovskite-type oxides adjusted within the volume% diameter range are preferably used.
  • a more preferable heat treatment temperature condition is 1350 ° C. or more, more preferably 1400 ° C. or more, and a more preferred heat treatment time condition is 10 hours or more, more preferably 20 hours or more.
  • Stable Zirconia particles and doped ceria fine particles increase the consistency of thermal expansion with the electrolyte and increase the strength of the air electrode due to its easy sinterability to prevent segregation from the electrolyte. Demonstrate the effect.
  • These average particle diameters should be adjusted to be in the range of 0.1 to 1 m.
  • the average particle size of the stabilized zircoure particles and the doped ceria fine particles is less than 0.1 m, the cohesive force of the zircoure particles and the like becomes large, and the above effect is not sufficiently exhibited.
  • the average particle size exceeds 1 m, the sinterability decreases, and it becomes difficult to sufficiently exert the action of increasing the strength of the air electrode and the ability to suppress the powder separation from the electrolyte.
  • the average particle size of the stabilized zirconia particles and doped ceria fine particles is preferably 0.2 ⁇ m or more and 0.8 m or less, more preferably 0.2 ⁇ m or more, and 0.2 ⁇ m or more. It is less than 6 m.
  • the 90 volume% diameter is 0.5 m or more and 5 m or less, more preferably 0.8 m or more and 3 m or less, and still more preferably 0.8 m or more and 2 m or less.
  • the average particle diameter (50 volume% diameter) of each particle is measured as follows. That is, using a laser diffraction particle size distribution analyzer “LA-920” manufactured by HORIBA, Ltd., an aqueous solution in which 0.2% by mass of sodium metaphosphate as a dispersant is added to distilled water is used as a dispersion medium. Each particle is added in an amount of 0.01 to 0.5% by mass in about 100 cm 3 of the dispersion medium, and dispersed by sonication for 3 minutes, and then the particle size distribution is measured. The average particle size is the particle size at 50% by volume in the cumulative graph in the measurement result of particle size distribution.
  • the 90 volume% diameter means the particle diameter at a position of 90 volume% in the particle size distribution of each sample particle measured by the same method.
  • the stable zirconium oxide particles are stabilized with at least one kind of oxide selected from yttrium, scandium, and ittenorium force, and the total amount of these oxides is 3 to 15 mol%. It is a certain Zircoyu. In order to effectively exhibit the composite action with the doped ceria particles, tetragonal zircoure having better toughness and strength than cubic zirconia is preferred.
  • each raw material powder is weighed so as to have the above-mentioned preferred blending ratio and uniformly mixed by a mill or the like.
  • the type of the mixing apparatus used in this case is not particularly limited, but a preferable mixing apparatus used by the present inventors is, for example, a multipurpose mixer manufactured by Mitsui Mining Co., Ltd.
  • a preferable mixing apparatus used by the present inventors is, for example, a multipurpose mixer manufactured by Mitsui Mining Co., Ltd.
  • the stable zirconium oxide particles are added thereto, Rotate the rotating blades at low speed to mix. If a powerful method is adopted, it is confirmed that the three kinds of particles can be mixed evenly and uniformly.
  • the mixed powder material thus obtained is mixed with a paste component.
  • Components for pastes include binders such as ethyl cellulose, polyethylene glycol, polybutyral resin; solvents such as ethanol, toluene, a terpineol, carbitol; plasticizers such as glycerin, glycol, dibutyl phthalate; Can include dispersants, antifoaming agents, surfactants, and the like, which are blended as necessary.
  • the mixing means include a three roll mill and a planetary mill. If the viscosity is appropriately adjusted using such a mixing means, a paste for an air electrode can be obtained.
  • a noinder there is no particular limitation on the type as long as it is easily decomposed by heat and dissolves in a solvent and exhibits fluidity suitable for printing and coating. It can be appropriately selected and used.
  • the organic binder include an ethylene copolymer, a styrene copolymer, an acrylate copolymer and a metatarylate copolymer, a vinyl acetate copolymer, a maleic acid copolymer, and a bull petital resin.
  • examples thereof include celluloses such as buracetal resin, burformal resin, butyl alcohol resin, waxes, and cellulose.
  • methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, and cyclohexyl acrylate are preferable from the viewpoints of film formation of the air electrode layer and thermal decomposability during baking.
  • Alkyl acrylates having an alkyl group having 10 or less carbon atoms such as 2-ethylhexyl acrylate, and the like; Tylmetatalylate, butylmetatalylate, isobutylmethacrylate, octylmethacrylate, 2-ethylhexylmethacrylate, decylmethacrylate, dodecylmethacrylate, laurylmethacrylate, cyclohexylmeta
  • the solvent those having low volatility at room temperature are preferred in order to reduce the viscosity change during printing.
  • polyhydric alcohol ester type such as glycerin and sorbitan
  • polyether (polyol) type namine type polyacrylic acid, polyacrylic acid ammonium
  • polyacrylic acid, polyacrylic acid ammonium Polyelectrolytes such as: organic acids such as citrate and tartaric acid; copolymers of isobutylene or styrene and maleic anhydride and their ammonium salts; amine salts; copolymers of butadiene and maleic anhydride and The power with which the ammonium salt is used Particularly preferred is sorbitan triol.
  • the air electrode paste is prepared by adding a solvent or a binder to the raw material powder and kneading with a ball mill or the like by a known method. At this time, a bonding aid, an antifoaming agent, a leveling improver, a rheology modifier, etc. may be added as necessary.
  • the leveling improver mainly has an action of suppressing the generation of pinholes in the air electrode layer, and exhibits the same effect as a so-called lubricant.
  • examples include hydrocarbon-based polyethylene wax, urethane-modified polyether, alcohol-based polyglycerol, polyhydric alcohol, fatty acid-based higher fatty acid, and oxyacid.
  • Particularly preferred are fatty acid systems such as stearic acid and hydroxystearic acid.
  • a binder or a solvent is added to the raw material powder described above, and then kneaded with a machine, a ball mill, a three-roll mill or the like and mixed uniformly to obtain a paste.
  • the viscosity should be adjusted to 1 to 50 mPa's, more preferably 2 to 20 mPa ⁇ s with a B-type viscometer.
  • the preferable slurry viscosity when forming the air electrode by screen printing is 50, 000 to 2,000, OOOmPa-s, more preferably 80,000 to 1,000, OOOmPa-s, more preferably, with a Brookfields viscometer. The range is from 1 00, 000 to 500, OOOmPa, s.
  • the viscosity is adjusted, for example, it is coated on the solid electrolyte by a bar coater, spin coater, dating apparatus or the like, or formed into a thin film by a screen printing method, and then a temperature of 40 to 150 ° C, for example,
  • the air electrode layer is formed by heating at a constant temperature such as 50 ° C, 80 ° C, 120 ° C, or successively by heating.
  • the thickness of the air electrode layer is suitably about 10 to 300 ⁇ m, preferably 15 to: LOO ⁇ m, particularly preferably 20 to 50 ⁇ m.
  • oxides used for forming the solid electrolyte membrane include zirconia, alkaline earth metal oxides such as MgO, CaO, SrO, and BaO, YO, LaO, CeO, PrO, NdO, SmO,
  • Rare earth metal oxides such as EuO, GdO, TbO, DyO, HoO, ErO, YbO
  • Zircoure ceramics containing one or more of ScO, BiO, InO, etc.
  • CeO or BiO alkaline earth metal oxides such as MgO, CaO, ScO, BaO,
  • Rare earth metal oxides such as O, ErO, YbO, ScO, InO, PbO, WO, MoO, V
  • AZrO with a perovskite structure (A: alkaline earth elements such as Sr) and In
  • metal oxides such as AlO, SiO, InO, SbO, and BiO
  • Dust-reinforced gallate ceramics Indium such as Ba In O with brown millelite structure
  • Ceramics examples include ceramics. These ceramics may further contain other oxides such as Si 2 O 3, Al 2 O 3, GeO 2, SnO 2, Sb 2, PbO, Ta 2, Nb 2, and the like.
  • a solid electrolyte having a zirconate-acid power stabilized by one or more acids selected from yttrium, scandium, and itumbumka as described above.
  • these solid electrolytes contain 0.1 to 2% by mass of at least one selected from the group consisting of alumina, titer and silica.
  • the shape of the electrolyte may be any of a flat plate shape, a corrugated plate shape, a corrugated shape, a Hercam shape, a cylindrical shape, a cylindrical flat plate shape, and the like.
  • the thickness of the electrolyte is 5 to 500 / ⁇ ⁇ , preferably 30 to 300 ⁇ m, more preferably 50 to 200 ⁇ m.
  • the fuel electrode paste is applied to one side of the electrolyte membrane by screen printing or the like.
  • the fuel electrode paste include NiO, ceria doped with at least one element selected from yttrium, samarium, and gadolinium power, and at least one oxide selected from Z or yttrium, scandium, and ytterbium power.
  • zirconia stabilized with seeds there may be mentioned those with the addition of zirconia stabilized with seeds.
  • more specific fuel electrode materials ? ⁇ 0: 50-70% by mass, 10 mol% scandia, 1 mol% ceria, stable zirconia: 30-50% by mass, etc.
  • the fuel electrode paste is dried, for example, it is baked at 1100 to 1400 ° C. to form a fuel electrode to form a half cell.
  • the powder for the air electrode material is mixed with binder, solvent, plastic It is applied by screen printing or coating using a paste or slurry obtained by kneading uniformly with an agent, dispersant and the like.
  • baking is performed at a temperature of 900 to 1300 ° C, preferably 950 to 1250 ° C, more preferably 1000 to 1200 ° C to form an air electrode, and a solid electrolyte fuel cell having a three-layer membrane structure
  • the solid electrolyte material and the air electrode material are exposed to a high temperature for a long time to cause a solid-phase reaction and an insulating material may be generated at the interface between them, the solid electrolyte layer and the air electrode layer An intermediate layer may be provided between them.
  • the yttria-doped ceria, samariado pud ceria, and gadria-doped ceria are materials having oxygen ion conductivity and electron conductivity and functioning as a barrier layer of the air electrode material. It can be used preferably.
  • an intermediate layer paste using these materials may be prepared in the same manner and formed as an intermediate layer film on the opposite electrolyte surface where the fuel electrode film is formed.
  • the material constituting the solid electrolyte membrane, the intermediate layer, the fuel electrode, and the film forming method there is no limitation on the material constituting the solid electrolyte membrane, the intermediate layer, the fuel electrode, and the film forming method.
  • the above is only an example.
  • the air electrode material of the present invention may be an electrode-supported fuel cell or a cylindrical solid electrolyte fuel cell. The same applies to the manufacture of fuel cells. Further, the air electrode material of the present invention is applied to a solid electrolyte fuel cell having a structure in which a fuel electrode, a solid electrolyte, and an air electrode are formed on the surface of a porous support tube or a support plate. Of course, it is possible to fabricate a cell.
  • the air electrode material of the present invention has excellent long-term sustainability of electrode activity and good sintering resistance, and also has a severe heat history due to repetition of room temperature and high operating temperature when the fuel cell is stopped. High performance that can withstand Further, by using the air electrode material of the present invention, it is possible to provide a high-performance and durable air electrode, and further a fuel cell.
  • Perovskite type oxide powder which is a raw material, is commercially available with a purity of 99.9% Pr 2 O 3 La
  • Ethanol was added to the mixture and pulverized and mixed with a bead mill for 1 hour. Next, it was dried and calcined at 800 ° C for 1 hour. Further, ethanol was added and pulverized and mixed in a bead mill for 1 hour, followed by drying. Thereafter, a solid phase reaction was carried out at 1100-1300 ° C. for 5 hours.
  • Ethanol was added to the obtained powder, which was further pulverized and mixed with a ball mill for 16 hours and then dried to obtain powders having an average particle diameter shown in Tables 1 to 3.
  • the obtained powder was confirmed to be a single phase composed of perovskite by X-ray diffraction.
  • the perovskite powder was further heat-treated at 1400 ° C for 10 hours and then pulverized with a planetary ball mill while adjusting the rotation speed and rotation time. The average particle size and 90% by volume were set.
  • the doped ceria particles that are raw materials include commercially available CeO, GdO having a purity of 99.9% or more.
  • the stable zircoure powder a commercial product manufactured by Daiichi Rare Element Co., Ltd. was used except for ytterbia stable zircoure.
  • a powder prepared as follows was used.
  • Zircoyu powder (trade name “OZC-OY”) manufactured by Sumitomo Osaka Cement Co., Ltd. was impregnated with an aqueous solution of ytterbium nitrate. The impregnated product was dried and then calcined at 1000 ° C. Then obtained The powder was ground in a bead mill in ethanol. After drying, when a mortar and pestle were further attached, or by pulverizing with a machine, 11 mol% ytterbia stable zircoure powder having an average particle size shown in Table 2 was obtained.
  • the obtained powders were prepared so as to have the composition ratios shown in Tables 1 to 3.
  • 2 g of ethylcellulose as a binder, 38 g of tervineol as a solvent, and sorbitan acid ester as a dispersant (trade name “IONET S-80” manufactured by Sanyo Chemical Co., Ltd.) 0 Added 5 g.
  • the mixture was stirred and mixed with a mortar and pestle, and then milled using a three-roll mill to prepare an air electrode paste.
  • Test example 1 Power generation test
  • a power generation test was conducted on the cell produced above, and the cell output density was measured.
  • the fuel gas used was 3% steam-humidified hydrogen at 800 ° C, and air was used as the oxidant.
  • the product name “R8240” manufactured by Advantest was used as the current measuring device, and the product name “R6240” manufactured by Advantest was used as the current-voltage generator. The results are shown in Tables 1-3.
  • the cell terminal voltage was measured by supplying a current of 300 mAZcm 2 , and the deterioration rate after 200 hours, 500 hours, and 1000 hours from the initial stage was measured.
  • the results are shown in Tables 1-3.
  • the cell terminal voltage drop rate was obtained as follows. In Comparative Examples 1 to 4, 6 and 7, the initial output density measured in Test Example 1 was low, so the measurement was strong. Also, Examples 5, 6, and 20 according to the present invention In order to shorten the experimental time, measurements after 500 hours or 1000 hours were omitted in and.
  • the initial power density is 0.2 WZcm 2 or less and the electrode activity is poor.
  • the air electrode material of the present invention is used, an initial output density of approximately 0.3 WZcm 2 or more is obtained. Therefore, it can be seen that the fuel battery cell according to the present invention has excellent electrode activity.
  • the perovskite type oxide is used.
  • the initial output density and the cell terminal voltage drop rate after 500 hours are the same as in the case of a single object, and the superiority of the present invention can be confirmed.
  • the blending ratio of the perovskite type oxide and the doped silica or stable zirconium oxide is outside the specified range of the present invention, the initial output density is greatly reduced, and the electrode activity is remarkably deteriorated.

Abstract

La présente invention concerne un matériau d'électrode à air pour pile à combustible, ledit matériau offrant une persistance de l'activité d'électrode supérieure à celle des matériaux traditionnels et une durabilité suffisamment élevée pour supporter des cycles répétés de température entre la température ambiante (à l'arrêt) et une température dépassant 700 ºC (en fonctionnement). Le matériau d'électrode à air de l'invention est caractérisé en ce qu'il contient un oxyde pérovskite de formule générale (I) : (PrxA1-x)(FeyB1-y)O3 ······ (I), dans laquelle A représente un métal alcalino-terreux ou un élément similaire ; B représente un élément du groupe 7a ou un élément similaire ; x va de 0,5 à 1 ; et y va de 0,5 à 1.
PCT/JP2007/052247 2006-02-10 2007-02-08 Materiau pour electrode a air utilisee dans une pile a combustible a oxyde solide WO2007091642A1 (fr)

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JP2016501435A (ja) * 2012-12-18 2016-01-18 サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド 固体酸化物燃料電池における層のための粉末混合物
CN112204780A (zh) * 2018-03-29 2021-01-08 堺化学工业株式会社 固体氧化物型燃料电池的空气极材料粉体
JP2022028167A (ja) * 2020-08-03 2022-02-16 森村Ｓｏｆｃテクノロジー株式会社 電気化学反応単セル

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JP2011514644A (ja) * 2008-03-18 2011-05-06 テクニカル ユニヴァーシティー オブ デンマーク 全セラミックス固体酸化物形電池
JP2009259568A (ja) * 2008-04-16 2009-11-05 Nippon Telegr & Teleph Corp <Ntt> 固体酸化物形燃料電池
JP2010277877A (ja) * 2009-05-29 2010-12-09 Nippon Telegr & Teleph Corp <Ntt> 固体酸化物形燃料電池
JP2011228009A (ja) * 2010-04-15 2011-11-10 Dowa Electronics Materials Co Ltd 固体電解質型燃料電池用複合酸化物、固体電解質型燃料電池セル用接合剤、固体電解質型燃料電池用電極、固体電解質型燃料電池用集電部材、固体電解質型燃料電池、固体電解質型燃料電池セルスタック、及び固体電解質型燃料電池用複合酸化物混合物の製造方法
JP2012043774A (ja) * 2010-07-21 2012-03-01 Ngk Insulators Ltd 電極材料及びそれを含む固体酸化物型燃料電池セル
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JP2016501435A (ja) * 2012-12-18 2016-01-18 サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド 固体酸化物燃料電池における層のための粉末混合物
JP2013101965A (ja) * 2013-01-24 2013-05-23 Nippon Telegr & Teleph Corp <Ntt> 固体酸化物形燃料電池
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