WO2006101136A1 - 固体酸化物形燃料電池用燃料極材料およびそれを用いた燃料極、並びに燃料電池セル - Google Patents
固体酸化物形燃料電池用燃料極材料およびそれを用いた燃料極、並びに燃料電池セル Download PDFInfo
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- WO2006101136A1 WO2006101136A1 PCT/JP2006/305724 JP2006305724W WO2006101136A1 WO 2006101136 A1 WO2006101136 A1 WO 2006101136A1 JP 2006305724 W JP2006305724 W JP 2006305724W WO 2006101136 A1 WO2006101136 A1 WO 2006101136A1
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Definitions
- Fuel electrode material for solid oxide fuel cell fuel electrode using the same, and fuel cell
- the present invention relates to a fuel electrode material for a solid oxide fuel cell, a fuel electrode using the same, and a fuel cell, and more specifically, has good gas permeability and an electrochemical reaction.
- a material that provides a fuel electrode for a solid oxide fuel cell that excels in durability, conductivity, and durability, and that does not cause damage or destruction due to thermal stress with other members. And a fuel electrode using the same, and a fuel cell using the fuel electrode.
- a porous cermet in which ceramic particles are mixed with conductive metal particles, such as nickel / zirconia cermet, is used. This is because thermal stress is generated due to the difference in thermal expansion coefficient between the metal particles, which are the main conductive components, and the solid electrolyte or other members, which induces internal strain, which causes the fuel cell to break or be damaged. This is to prevent this.
- Japanese Patent Laid-Open No. 3-49156 discloses a method of using ceramic particles coated with nickel fine particles on the surface as a fuel electrode
- Japanese Patent Laid-Open No. 5-174833 discloses ceramic particles.
- a composite material having particles coated with a conductive metal on the surface and oxygen ion conductive ceramic particle force.
- these techniques require sophisticated and complex processing to coat and coat ceramic particles with metal, It cannot be denied that the cost will be high.
- a fuel electrode material prepared by adding a zirca powder having an average particle size smaller than that of acid nickel to a fuel electrode material powder containing acid nickel powder JP-A-4-192261
- electrode materials satisfying the relationship that the average particle size of the prepared particle group is “coarse zirconia particle group> acid-nickel particle group> fine zircoure particle group” Japanese Patent Laid-Open No. 8-306361
- Public information has also been proposed.
- the degradation rate of the cell voltage in the power generation durability test is at most 2.2% per 1000 hours, which is not enough for practical use of fuel cells. Reached.
- Japanese Patent Application Laid-Open No. 9-92294 discloses a means for preventing the occurrence of fine cracks in the fuel electrode due to volume contraction caused by reduction of nickel oxide to metallic nickel during power generation.
- the anode comprises a first anode layer formed on the surface of a solid electrolyte composed of nickel oxide particles and zirconia particles and Z or ceria particles; and nickel particles and zircoure particles and / or ceria particles; It has been proposed to have a two-layer structure consisting of a second fuel electrode layer formed on the surface of the first fuel electrode layer.
- the electrode reaction layer is a mixture of fine Ni and fine oxygen ion conductors with an average particle size of 0.5 m or less.
- the present invention has been made in order to improve the problems of the prior art as described above.
- the purpose of the present invention is to have good gas permeability, excellent electrochemical reactivity and conductivity, and easy use.
- the fuel electrode material for a fuel cell according to the present invention that has solved the above problems is a fuel electrode material for a nickel-zirco-ceria-based solid oxide fuel cell,
- the coarse ceria particles, fine zirconia particles, and acid-nickel particles are mixed, and the coarse ceria particles are ceria doped with at least one element selected from yttrium, samarium, and gadolina.
- the fine zirconia particle group is a zirconia particle group stabilized with ittria and Z or scandia, and the average particle diameter of each particle group is coarse ceria particle group> acid.
- Nickel particle group> It has a feature that satisfies the relationship of fine zirconia particle group! RU
- each particle group satisfies the above average particle size relationship
- the ceria particle group has an average particle size in the range of 2 to 50 ⁇ m
- the nickel oxide particle group has an average particle size.
- the particle size is preferably in the range of 0.5 to 5 ⁇ m
- the average particle size of the zirconia particles is preferably in the range of 0.1 to 1 ⁇ m.
- the content ratio of each particle group in the fuel electrode material is The ceria particle group: 20 to 50% by mass, the nickel oxide particle group: 40 to 70% by mass, and the zirconia particle group: 5 to 25% by mass are preferable.
- the total content ratio of the ceria particle group and the zirconium oxide particle group is preferably 30 to 60% by mass.
- the fuel electrode for a solid oxide fuel cell of the present invention is a fuel electrode formed on one side of a solid electrolyte in a solid oxide fuel cell, and the fuel electrode satisfies the specified requirements. It is characterized in that it is formed of a fuel electrode material that fills, and further, a solid electrolyte Also included in the technical scope of the present invention is a solid oxide fuel cell in which a fuel electrode is formed on one side of the fuel electrode by the fuel electrode material and an air electrode is formed on the other side.
- coarse ceria particles doped with at least one selected from yttrium, samarium, and gadolinium having conductivity and ion conductivity as a constituent material of the fuel electrode for a fuel cell.
- a mixture of fine particles, nickel oxide particles, yttria and fine zirconia particles stabilized with Z or scandia, and the relationship between the average particle diameters of these particles is identified, and the coarse ceria particles
- a conductive path between electricity and ions is formed by dispersing the nickel oxide particles in between.
- the force also increases the contact point between the three types of particle groups by defining the relationship between the average particle sizes as described above, and as a result, the coarse ceria particle groups are firmly bonded.
- the fuel electrode formed from the uniform mixture of the above three kinds of particle groups exhibits excellent electrochemical characteristics, and also has a non-sinterable coarse ceria particle group and fine zirconia particles.
- the child skeleton forms a structural skeleton, which increases the structural strength of the fuel electrode and, in turn, forms such a strong structural skeleton, which suppresses the sintering that tends to occur when exposed to high temperatures for a long time.
- the fine-grained ceria particle skeleton is strengthened by interspersing the fine-grained zirconia particles between the coarse-grained ceria particles and sintering, the pores required on the anode side serving as the fuel electrode are blocked. It can sustain excellent gas permeability over a long period of time.
- the average particle diameter of each particle group satisfies the relationship of "coarse ceria particle group> acid-nickel particle group> fine-grained zirconium particle group". More preferably, while satisfying these relationships, the average particle size of each particle group is as follows: coarse ceria particles: 2 to 50 111, nickel oxide particles: 0.5 to 5 / ⁇ ⁇ , fine zirconia particles: 0.1 It is desirable that the range be ⁇ 1 ⁇ m.
- the coarse ceria particle group it is preferable to use those having an average particle diameter in the range of 2 ⁇ m to 50 ⁇ m.
- the average particle size of the ceria particle group is less than 2 m, the role as a coarse particle is reduced and the formation of the skeleton as an anode material becomes insufficient, so If it is difficult to obtain a satisfactory air permeability when it is difficult to form an appropriate gap, it is difficult to obtain force.
- the porosity of the fuel electrode is significantly reduced.
- the average particle size of the ceria particles exceeds 50 m and becomes too large, the gap between the particles is sufficiently secured and the decrease in porosity due to the progress of sintering can be sufficiently suppressed, but the fuel electrode.
- a large amount of fine zirconia particles must be blended as a bonding agent, and an acid for forming a conductive path in the fuel electrode. ⁇
- the amount of nickel particles is relatively short, and the conductivity is hindered.
- the average particle size of the more preferable coarse ceria particle group is 3 ⁇ m or more and 40 ⁇ m or less, more preferably 3 ⁇ m or more and 30 ⁇ m or less.
- the amount of extremely coarse particles is suppressed as much as possible to achieve a uniform fuel electrode layer. Therefore, more for even preferably 90 volume 0/0 diameter, 5 m or more, 80 m or less, more preferably 7 m or more, 70 m or less, more preferably 9 m or more, preferably set to less 50 m.
- the specific surface area is preferably in the range of 0.5 to 30 m 2 Zg. If the specific surface area is less than 0.5 m 2 Zg, the particles are very hard and streaks are likely to appear during printing. Conversely, if the specific surface area exceeds 30 m 2 Zg and the specific surface area becomes too large, the fuel electrode paste is printed. This is because when baking, the specific surface area is greatly reduced, the ceria particles are greatly shrunk, and cracks are likely to enter the fuel electrode, which may cause strength deterioration.
- ceria particles containing cerium oxide alone or ceria particles to which an appropriate amount of alumina or zirconia is added can be used.
- the doping amount is not particularly limited, but is preferably in the range of 5 to 40 atomic%, more preferably 10 to 30 atomic% with respect to cerium.
- the acid / nickel nickel particles are reduced by being exposed to a fuel gas such as hydrogen when operating as a fuel cell, and change into metal nickel particles that form a conductive path. Because it shrinks by about 10-20% in diameter, it is related to the group of fine zirconia particles used together. In consideration of such change to nickel particles, the average particle size is preferably adjusted to be in the range of 0.5 to 5 / ⁇ ⁇ .
- a more preferable average particle diameter of the nickel oxide particle group is 0.7 ⁇ m or more and 4 ⁇ m or less, and more preferably 0.7 ⁇ m or more and 3 ⁇ m or less.
- the 90% by volume diameter is 0.8 ⁇ m or more and 10 ⁇ m or less, more preferably 1 ⁇ m or more and 5 ⁇ m or less, and even more preferably 2 / zm or more and 8 / zm or less.
- the specific surface area of nickel oxide, 0. 5 ⁇ : L0m is preferable in the range of 2 Zg.
- the specific surface area is less than 0.5 m 2 / g, the electrode activity decreases significantly.
- the specific surface area exceeds 10 m 2 / g, the initial electrode activity is high, but the deterioration of the activity with time increases, and the deterioration rate of the output density also increases. It is.
- the fine-grained zirconia particles act as an adhesive for joining the above-mentioned coarse-grained ceria particles to form a skeleton, and the average particle size is in the range of 0.1 to 1 / ⁇ ⁇ . It is better to adjust so that it is inside.
- the average particle size of the fine zirconia particles is less than 0.1 ⁇ m, a large amount of fine zircoure particles are required to bond the coarse ceria particles to form a strong skeleton, If it becomes difficult to secure the amount of nickel oxide necessary to form a conductive path in the fuel electrode layer, there is a risk of impeding conductivity.
- the average particle size of the fine zirconia particles exceeds 1 m, the contact point with the coarse ceria particles decreases and it becomes difficult to obtain sufficient conductivity.
- the average particle diameter of the fine zirconia particles is not less than 0.2 ⁇ m and not more than 0.8 m, more preferably not less than 0.2 ⁇ m and not more than 0.6 ⁇ m.
- the specific surface area of the zirconia particles is preferably in the range of 2 to 30 m 2 Zg. If the specific surface area is less than ⁇ m 2 Zg, the formation of the skeleton becomes difficult.If the specific surface area exceeds 30 m 2 Zg, the skeleton formation is improved, but the specific surface area decreases with time, causing shrinkage and This is because cracks tend to enter and the strength decreases.
- the average particle size (50% by volume) of each particle group is determined in distilled water using a laser diffraction type particle size distribution analyzer “LA-920” manufactured by HORIBA, Ltd.
- the 90 volume% diameter means the particle diameter at the position of 90 volume% in the particle size distribution of each sample particle measured by the same method.
- the amount of relatively coarse particles mixed in is suppressed as much as possible to further form a skeleton by joining the coarse ceria particles.
- the 90% by volume diameter is 0.5 ⁇ m or more and 5 m or less, more preferably ⁇ or more and less or less, and further preferably ⁇ or less or more and more than or equal to 2 m or less.
- the fine zircoure particles are effective as a bonding material for forming a skeleton by force coarse ceria particles which are zircouria stabilized with yttria and Z or scandia as described above.
- Tetragonal zirconia with superior toughness and strength is preferred over cubic zirconia.
- yttria-stabilized zirconium oxide it is stabilized with 3 to 6 mol% yttria, and in the case of scandia-stabilized zircoia, mainly composed of tetragonal crystals stabilized with 3 to 7 mol% scandia.
- the partially stable zirconia powder is particularly preferred.
- each of the above particles is 20 to 50% by mass of the coarse ceria particle group, 40 to 70% by mass of the nickel oxide particle group, and 5 to 25% by mass of the fine zirconia particle group, respectively. More preferable contents are in the range of 25 to 45% by mass for the coarse ceria particles, 45 to 65% by mass for the oxidized nickel particles, and 5 to 20% by mass for the fine zirconia particles.
- the skeleton formation becomes insufficient and the gas If the permeability is low, the porosity will be reduced significantly when used, and conversely if it exceeds 50% by mass, the skeletal strength will be low. Also, if the content of the nickel oxide particles is less than 40% by mass, the formation of the conductive path becomes insufficient, resulting in poor conductivity. Conversely, if the content exceeds 70% by mass, the nickel particles are sintered together. As this occurs easily, the conductive path is interrupted and the conductivity tends to be insufficient.
- the skeleton formation becomes difficult due to insufficient bonding material and gas permeability deteriorates. If it exceeds 25% by mass, the skeletal strength increases, but the skeletal strength increases. Occasionally, sintering proceeds at a high temperature, and porosity changes with time.
- the coarse ceria particle group is 20 to 50% by mass
- the nickel oxide particle group is 40 to 70% by mass.
- Fine particles Each raw material powder may be weighed so as to be in the range of 5 to 25% by mass and mixed uniformly with a mill or the like, but it is particularly preferable that a predetermined amount of coarse ceria particles and In this method, nickel oxide particles are mixed, and nickel oxide particles are adhered to the surface of coarse ceria particles, and then a predetermined amount of fine zirconia particles are collected and mixed uniformly.
- the type of mixing apparatus used in this case is not particularly limited, but a preferable mixing apparatus used by the present inventors is, for example, a multi-purpose mixer manufactured by Mitsui Mining Co., Ltd. Rotate the rotating blade at high speed to mix coarse ceria particles and nickel oxide particles first, then add fine zirconia powder to this, then rotate the rotating blade of the same device at low speed and mix. For example, make sure that the three types of particles can be mixed evenly and uniformly.
- the mixed powder material thus obtained is mixed with a binder such as ethyl cellulose, polyethylene glycol, polybutyl butyral resin; a solvent such as ethanol, toluene, OC terbinol, carbitol; glycerin, glycol, phthalic acid.
- a plasticizer such as dibutyl, as well as dispersants, antifoaming agents, surfactants, etc. that are blended as necessary, for example, a three-roll mill or planetary mill can be used to obtain a paste with an appropriate viscosity.
- a paste for the fuel electrode is obtained.
- noinder there is no particular limitation on the type as long as it has a fluidity suitable for printing and coating because it is easily decomposed by heat and has a fluidity suitable for printing and coating.
- a Neuder can be selected and used as appropriate.
- the organic binder include an ethylene copolymer, a styrene copolymer, an acrylate copolymer and a methacrylate copolymer, a butyl acetate copolymer, a maleic acid copolymer, a vinyl butyral resin, and a vinyl acetate.
- examples thereof include celluloses such as rubber based resins, vinyl formal based resins, vinyl alcohol based resins, and ethyl cellulose.
- methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, and cyclohexyl acrylate are preferable from the viewpoints of film formation of the fuel electrode layer and thermal decomposition during baking.
- Alkyl acrylates having an alkyl group with 10 or less carbon atoms such as 2-ethylhexyl acrylate, and the like; and methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, octyl methacrylate
- Alkyl metatalates having an alkyl group having 20 or less carbon atoms such as rate, 2-ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate Hydroxyethyl acrylate, hydroxypropyl phthalate Hydroxyalkyl acrylates or hydroxyalkyl methacrylates having a hydroxyalkyl group such as acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc .; aminoalkyls such as dimethylaminoethy
- the solvent those having low volatility at room temperature are preferred in order to reduce the viscosity change during printing.
- those having low volatility at room temperature are preferred in order to reduce the viscosity change during printing.
- high boiling solvents with low boiling organic solvents such as acetone, methyl ethyl ketone, methanol, ethanol, isopropanol, butanols, denatured alcohol, ethyl acetate, toluene, xylene.
- I can.
- polyhydric alcohol esters such as glycerin and sorbitan, polyether (polyol) based amines, polyacrylic acid, polyacrylic acid ammonia
- polyether (polyol) based amines polyacrylic acid, polyacrylic acid ammonia
- Polymer electrolytes such as humic acid, organic acids such as citrate and tartaric acid, copolymers of isobutylene or styrene and maleic anhydride and their ammonium salts and diamine salts, and copolymerization of butadiene and maleic anhydride
- sorbitan triol is particularly preferred.
- plasticizer polyethylene glycol derivatives and phthalic acid esters are preferred, with dibutyl phthalate and dioctyl phthalate being particularly preferred.
- the fuel electrode paste is prepared by kneading a solvent and a binder into the acid oxide powder with a ball mill or the like by a known method. At this time, a bonding aid or a defoaming agent is used as necessary. Agents, leveling improvers, rheology modifiers and the like may be added.
- the leveling improver mainly has an action of suppressing unevenness on the surface of the fuel electrode and exhibits the same effect as a so-called lubricant.
- a hydrocarbon-based polyethylene wax examples include urethane-modified polyethers, alcohol-based polyglycerols, polyhydric alcohols, fatty acid-based higher fatty acids, and oxyacids, with fatty acid systems such as stearic acid and hydroxystearic acid being particularly preferred.
- a binder or a solvent is added to the above-described oxide powder, and then kneaded with a machine, a ball mill, a three-roll mill, or the like, and mixed uniformly to obtain a paste.
- a machine a ball mill, a three-roll mill, or the like
- the slurry viscosity is 50,000 to 2,000,000 mPa's, more preferably 80,000 to l, 000,000 mPa's, more preferably 100,000 to 500,000 mPa's in a Brookfields viscometer, when the anode is formed by screen printing. Range.
- the viscosity is adjusted, for example, it is coated on the solid electrolyte by a bar coater, spin coater, dating device 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 fuel 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 fuel electrode layer is suitably about 10 to 300 ⁇ m, preferably 15 to: LOO ⁇ m, particularly preferably 20 to 50 ⁇ m.
- the solid electrolyte material of the solid oxide fuel cell according to the present invention includes, for example, zirconium oxide, alkaline earth metal oxides such as MgO, CaO, SrO, BaO, Y 2 O 3, La 2 O 3, CeO 2,
- Alkaline earth metal oxides Y 2 O, La 2 O, CeO, Pr 2 O, Nd 2 O, Sm 2 O, Eu 2 O
- Alkaline earth metal oxides such as SrO and BaO, Y O
- Transition metal oxides such as O, Nb O, and WO, Al O
- Examples include gallate ceramics that are doped or dispersion strengthened with 2 3 typical metal oxides such as 2 3 and BiO, and indium ceramics such as Ba In O having a brown millite structure. These secs
- It may contain Ta N, Nb ⁇ and the like.
- solid electrolytes having zirconate acid strength stabilized by one or more of soot, Ce, Sm, Pr, Yb, and Sc.
- a compound containing 0.05 to 5% by mass of at least one selected from the group strength consisting of na, titer, silica and ceria is also preferred and recommended.
- YSZ stabilized Jirukoyua based solid electrolyte yttria 3-10 mole 0/0
- ScSZ Sukanjia - ⁇ based solid electrolyte
- these solid electrolytes are zirconium oxide based solid electrolytes in which about 0.1 to 2 mass% of alumina and titaure are added.
- the shape of the electrolyte is , Flat plate shape, corrugated plate shape, corrugated shape, honeycomb shape, cylindrical shape, cylindrical flat plate shape or the like.
- the preferable thickness of the electrolyte is 5 to 500 / ⁇ ⁇ , more preferably 10 to 300 111, and still more preferably 20 to 200 ⁇ m.
- the powder mixture for the fuel electrode material is placed on one side of the electrolyte membrane with a binder, a solvent, and a plastic.
- a film is formed by screen printing or coating using paste or slurry obtained by uniformly kneading with an agent, dispersant, etc., and baked at a temperature of 1000 to 1400 ° C, preferably 1150 to 1350 ° C.
- the fuel electrode is formed.
- the air electrode material the composition of La, Sr, Co, Fe, etc., which is a complex oxide force such as La Sr Co Fe O, etc.
- a paste for an air electrode is formed, and this is formed on the opposite side of the electrolyte membrane by screen printing or the like, and baked at a temperature of, for example, 900 to 1200 ° C, preferably 1000 to 1150 ° C.
- a solid electrolyte fuel cell having a three-layer membrane structure is obtained.
- a perovskite type complex oxide or a mixture of a perovskite type oxide and a solid electrolyte oxide is preferably used as the air electrode material.
- belobskite type oxides include La Sr Co Fe O (0.2 0.2 ⁇ x ⁇ 0.6, 0.6 l -x l -y y 3
- the atomic ratio of oxygen in the perovskite-type acid oxide yarn-forming formula is expressed as 3.
- the atomic ratio x (y) is not 0, oxygen vacancies are generated. Therefore, the atomic ratio of oxygen is actually smaller than 3 and often takes a value.
- the atomic ratio of oxygen is represented as 3 for convenience.
- the solid electrolyte oxide in the case of a mixture of a perovskite oxide and a solid electrolyte oxide is specifically 8 to 10 mol%, preferably 8 to 9 mol% of ⁇ O.
- Mole 0/0 preferably from 15 to 30 mole 0/0, more preferably ceria solid containing 20 to 30 mole 0/0 Solution (hereinafter referred to as “GDC” for ceria solid solution containing GdO, and ceria solid solution containing Y ⁇
- YDC ceria-based solid solution containing Sm 2 O
- the air electrode paste is prepared in the same manner as the above-described fuel electrode paste.
- the solid electrolyte layer and the air electrode layer 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 is preferably provided between them.
- the intermediate layer material for this purpose, the GDC, YDC, and SDC can be preferably used as materials that have oxygen ion conductivity and electronic conductivity and are less likely to cause a solid phase reaction with an electrolyte material or an air electrode material. Then, paste the intermediate layer using these materials in the same way, and form it as an intermediate layer film on the opposite electrolyte surface where the fuel electrode film is formed.
- the solid electrolyte membrane, the intermediate layer, the material constituting the air electrode, the film forming method and the like are not limited at all.
- the above is only an example.
- the fuel electrode material of the present invention can be used to manufacture a cylindrical solid oxide fuel cell. The same applies to the above. Further, the fuel electrode material of the present invention is applied to an electrode-supported 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 fuel cells.
- mol 0/0 On one side of 4 mol 0/0 consists stabilized Jirukoyua in Sukanjia 4ScSZ electrolyte membrane (thickness 15 O / zm X diameter 30 mm), Sani ⁇ nickel particles as described in the following Table 1, 2, coarse Seri A fuel electrode is formed by pasting and screen printing a fuel electrode material that also has fine particles and fine zirconia particles.
- a total of 300 g of the acid nickel particles and coarse ceria particles are put in a combined processing tank of a multi-purpose mixer (Mitsui Mining Co., Ltd.) and processed at a high speed for 1 minute at 7,000 rpm. Therefore, a mixed particle of coarse ceria particles and acid nickel particles was used. Next, the fine zirconia particles were collected at a predetermined ratio and treated at lOOOrpm for 1 minute to obtain a fuel electrode material.
- the fuel electrode paste was prepared by using 2 g of ethyl cellulose 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.) with respect to 50 g of the fuel electrode material. ) Prepared by adding 0.5 g and milling 5 times with a 3 roll mill. For screen printing, a 200 mesh SUS wire mesh printing plate was used, and it was applied and dried to form a fuel electrode film with a predetermined thickness.
- La Sr Co Fe O powder manufactured by Seimi Chemical Co., Ltd.
- the air electrode material consisting of 20 wt% one company made 10YS Zeta powder Toso Paste and screen print to form the air electrode.
- This air electrode paste was prepared in the same manner as the above fuel electrode paste, and then screen-printed using the same SUS wire mesh printing plate and baked at 1000 ° C for 3 hours. An air electrode having a thickness of about 30 m was formed, and a fuel cell having a diameter of 30 mm and a four-layer structure was obtained. [0065] Using this cell, a power generation test was performed at 800 ° C using a small single cell power generation test apparatus, and the maximum power density was measured. The fuel gas used was 3% steam-humidified hydrogen at room temperature, and the oxidant was air. The product name “R8240” manufactured by Advantest was used as the current measuring device, and the product name “R 6240” manufactured by Advantest was used as the current-voltage generator.
- Nickel oxide powder manufactured by Seimi Chemical Co., Ltd.
- TZ- 8YS Tosoh 8 mole made of one company 0/0 yttria-stabilized I ⁇ Jirukoyua powder
- SDC-30 coarse-grained product 30 atomic% samarium-doped ceria coarse-grained product manufactured by Daiichi Rare Element Chemicals
- SDC-20 coarse-grained product 20 atomic% samarium-doped ceria coarse-grained product manufactured by Daiichi Rare Element Chemicals,
- SDC- 20 0. 3 m Seimi Chemical Co., 20 atom 0/0 samarium-doped ceria of 0. 3 ⁇ m particles
- GDC-20 calcined product a calcined product of 20 atomic% gadolinium doped ceria particles manufactured by Daiichi Rare Elemental Chemical Co., Ltd.
- YDC-20 calcined product A calcined product of 20 atomic% yttrium-doped ceria powder manufactured by Daiichi Rare Element Chemicals.
- Experiment No. 16 in Table 1 is an example that satisfies the stipulated requirements of the present invention, and includes the acid-nickel nickel particle group, the fine zirconium oxide particle group, and the coarse ceria particle group that constitute the fuel electrode. It can be seen that since the relationship between the average particle diameters meets the specified requirements of the present invention, sufficient power generation efficiency can be maintained even during long-term operation with little deterioration in power density and porosity over time.
- Experiment Nos. 7 and 8 in Table 2 show that the acid-nickel nickel particles are used as the material constituting the fuel electrode. Although the three types of particles, fine zirconia particles and coarse ceria particles are included, the relationship between their average particle sizes is outside the requirements of the present invention. Experiments No. 9 and 10 do not contain fine zirconia particles or coarse ceria particles as a material constituting the fuel electrode, so the power density and porosity are high. It cannot withstand long-term operation with a high rate of deterioration. Industrial applicability
- the fuel electrode material is composed of a mixture of a specific coarse-grained ceria particle group, a specific fine-grained zirconium oxide particle group, and a nickel oxide particle group, and the average particle size of each particle group
- gas permeability is good, electrochemical reactivity and conductivity, and further superior to their durability, and between other members.
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Abstract
Description
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EP06729691A EP1870950B1 (en) | 2005-03-23 | 2006-03-22 | Fuel electrode material for solid oxide fuel cell, fuel electrode using same, fuel-cell cell |
US11/886,850 US20090023027A1 (en) | 2005-03-23 | 2006-03-22 | Fuel Electrode Material for Solid Oxide Fuel Cell, Fuel Electrode Using the Same, and Fuel Cell |
JP2006520619A JP4795949B2 (ja) | 2005-03-23 | 2006-03-22 | 固体酸化物形燃料電池用燃料極材料およびそれを用いた燃料極、並びに燃料電池セル |
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JP2008258064A (ja) * | 2007-04-06 | 2008-10-23 | Honda Motor Co Ltd | 電解質・電極接合体及びその製造方法 |
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US8557471B2 (en) | 2007-11-05 | 2013-10-15 | Sumitomo Metal Mining Co., Ltd. | Nickel oxide powder comprising zirconium hydroxide coating layer or zirconium oxide coating layer, SOFC anode material and method of producing the same |
JP5218419B2 (ja) * | 2007-11-05 | 2013-06-26 | 住友金属鉱山株式会社 | 固体酸化物形燃料電池用の酸化ニッケル粉末材料とその製造方法、並びにそれを用いた燃料極材料、燃料極、及び固体酸化物形燃料電池 |
WO2009060752A1 (ja) * | 2007-11-05 | 2009-05-14 | Sumitomo Metal Mining Co., Ltd. | 固体酸化物形燃料電池用の酸化ニッケル粉末材料とその製造方法、並びにそれを用いた燃料極材料、燃料極、及び固体酸化物形燃料電池 |
US8741502B2 (en) | 2007-11-05 | 2014-06-03 | Sumitomo Metal Mining Co., Ltd. | Nickel oxide powder material for solid oxide type fuel cell and method for producing the same, and anode material, anode and solid oxide type fuel cell using the same |
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JP4868557B2 (ja) * | 2009-09-25 | 2012-02-01 | 日本碍子株式会社 | 固体酸化物形燃料電池のセル |
JP2013101965A (ja) * | 2013-01-24 | 2013-05-23 | Nippon Telegr & Teleph Corp <Ntt> | 固体酸化物形燃料電池 |
US11411245B2 (en) | 2014-10-16 | 2022-08-09 | Corning Incorporated | Electrolyte for a solid-state battery |
JP2017076520A (ja) * | 2015-10-14 | 2017-04-20 | 株式会社ノリタケカンパニーリミテド | 固体酸化物形燃料電池用の電極材料とこれを用いた固体酸化物形燃料電池 |
Also Published As
Publication number | Publication date |
---|---|
EP1870950B1 (en) | 2011-08-17 |
CN101147285A (zh) | 2008-03-19 |
JPWO2006101136A1 (ja) | 2008-09-04 |
EP1870950A1 (en) | 2007-12-26 |
US20090023027A1 (en) | 2009-01-22 |
EP1870950A4 (en) | 2009-09-09 |
JP4795949B2 (ja) | 2011-10-19 |
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