JP6060297B2 - Anode-supported half cell and anode-supported cell using the same - Google Patents

Description

  The present invention relates to an anode-supported half cell, and more particularly to an anode-supported half cell with reduced peripheral edge warpage.

  Fuel cells are attracting attention as a source of clean energy, and their use is rapidly being studied for improvement and practical application mainly from household power generation to commercial power generation, and further to power generation for automobiles.

  A typical structure of a solid oxide fuel cell is basically a stack in which a large number of cells each provided with an anode electrode on one side and a cathode electrode on the other side are stacked in the vertical direction. Here, in order to improve the power generation performance of the solid oxide fuel cell, it is effective to make the solid electrolyte membrane dense and thin. This is because the solid electrolyte membrane is required to be dense enough to reliably prevent the mixing of fuel gas and air serving as a power generation source and to have excellent ionic conductivity capable of suppressing conduction loss as much as possible. However, as the thickness of the solid electrolyte membrane is reduced, there is a tendency that cracks are likely to occur due to the stacking load when a large number of cells are stacked. Therefore, in order to make the solid electrolyte membrane thinner, an anode support type cell in which an anode support substrate for supporting the anode electrode and the solid electrolyte membrane is provided on the anode electrode side of the solid electrolyte has been proposed.

Various techniques for improving the performance of such anode-supported cells have been studied. For example, Patent Document 1 has excellent characteristics in terms of stacking load resistance and printing suitability when forming electrode printing and solid electrolyte membranes by reducing the burr height at the peripheral edge of the anode support substrate. It is described that it is obtained (see Patent Document 1 (page 16, lines 10 to 19)). However, Patent Document 1 relates to the burr height of the single layer of the anode support substrate, and has not been studied for an anode support type half cell in which an anode layer or an electrolyte layer is formed on the anode support substrate.
Further, although not related to the anode support substrate, Patent Document 2 describes the performance of the fuel cell by setting the burr height at the peripheral edge of the ceramic sheet used for the solid electrolyte free-standing membrane to be ± 100 μm or less. (See Patent Document 2 (paragraph [0016])).

International Publication No. 2003/098724 JP 2001-10866 A

  Conventionally, in an anode-supported cell, battery performance has been improved by reducing the burr height at the peripheral edge of the anode support substrate on which the electrolyte layer and electrodes are printed. That is, it has been considered that the peripheral edge portion can be smoothed even in the finally obtained anode support type cell by reducing the burr height at the peripheral edge portion of the anode support substrate and smoothing the peripheral edge portion. This is because the anode support substrate that has been fired once has been sufficiently strengthened, so that it was considered that the anode support substrate would not be deformed in the subsequent steps. Therefore, conventionally, only the smoothness of the peripheral portion in the state of the single layer of the anode support substrate has been examined, and after the electrolyte layer is laminated thereon, the warpage of the peripheral portion has not been studied at all. .

  However, as a result of investigations by the present inventors, it was confirmed that even when the peripheral portion of the anode support substrate was smoothed, the peripheral portion of the anode support cell manufactured using the anode support substrate was warped. . The warpage of the peripheral edge of the anode-supporting cell is caused by the shrinkage of the electrolyte layer precursor when the anode support substrate or the laminate of the anode support substrate green sheet and the electrolyte layer precursor is fired. It has been found that the peripheral edge of the film is pulled to the electrolyte membrane side and warps up.

  In this way, if there is a warp at the periphery of the anode-supported cell, when the cell stack is multi-layered and subjected to a large stacking load, cracking or breakage due to local stress concentration caused by the warp may occur. In addition, there are joints between single cells and gas pipes when configuring a fuel cell, joints between single cells or interconnectors (separators) arranged between single cells and joints between single cells, etc. The sealing performance deteriorates and gas leakage may occur during operation. Further, if there is a warp at the peripheral edge at the stage of the anode-supporting half-cell, when the cathode layer is printed by screen printing, the contact between the anode-supporting half-cell and the printing plate becomes uneven, and the thickness of the cathode layer There was a problem of causing unevenness and missing prints.

  As a result of advancing research to solve the problems caused by the warping of the peripheral edge of the anode-supporting cell or the anode-supporting half-cell as described above, the present inventors have found that the anode-supporting cell having an anode-supporting substrate and an electrolyte layer. The inventors have found that by reducing the warpage of the peripheral portion of the half cell, the warpage of the peripheral portion of the finally obtained anode-supporting cell can be reduced, and the present invention has been completed.

  The present invention has been made in view of the above circumstances, and is an anode-supported half cell having an anode support substrate and an electrolyte layer, in which warpage of the peripheral portion thereof is reduced, and the cathode layer is stabilized by screen printing. It is an object to provide an anode-supported half cell that can be formed in this manner. It is another object of the present invention to provide an anode-supported cell that is unlikely to be cracked or damaged even when multilayered as a cell stack, and that has excellent peripheral edge sealing properties.

  The anode-supporting half cell of the present invention that has solved the above problems is an anode-supporting half-cell having an anode supporting substrate and an electrolyte layer laminated on the anode supporting substrate, and the electrolyte layer is the upper surface. The height of the peripheral edge of the electrolyte layer (h1) obtained by irradiating the surface of the electrolyte layer with laser light and analyzing the reflected light three-dimensionally using a laser optical three-dimensional shape measuring device ) And the height (h2) of the electrolyte layer at a position of 3 mm from the peripheral edge to the center of the half cell, the difference (Δh) is 100 μm or less. In the anode-supported half cell, if the curvature of the peripheral edge is reduced, the electrolyte layer and the printing plate come into uniform contact with each other when the cathode layer is formed by screen printing, improving the uniformity of the cathode layer thickness. In addition, printing omission is reduced. Furthermore, by reducing the warpage of the peripheral edge of the half cell, the warpage of the peripheral edge of the finally obtained anode-supporting cell can also be reduced. As a result, an anode-supported cell having excellent part sealing properties can be obtained.

  The anode support substrate includes at least one selected from the group consisting of nickel, cobalt, iron and oxides thereof, and at least one selected from the group consisting of stabilized zirconia, ceria and lanthanum gallate. Preferably, the electrolyte layer contains at least one selected from the group consisting of stabilized zirconia, ceria and lanthanum gallate. The ratio (T2 / T1) between the thickness (T1) of the anode support substrate and the thickness (T2) of the electrolyte layer is preferably 0.003 to 0.35.

  The present invention also includes an anode-supported cell in which a cathode layer is formed on the anode-supported half cell; and a solid oxide fuel cell having the anode-supported cell. The solid oxide fuel cell having the anode-supported cell is prevented from being deteriorated by cracking of the anode-supported cell, has a long life, and has excellent sealing performance at the periphery, and gas leakage during operation is suppressed. Power generation efficiency is improved.

  The anode-supporting half cell of the present invention has an anode support substrate and an electrolyte layer, and the warping of the peripheral edge portion is reduced. Therefore, the anode supported half cell of the present invention can stably form the cathode layer by screen printing. In addition, the anode-supported cell produced using the anode-supported half cell of the present invention has reduced warpage at the peripheral edge, and is less likely to crack or break even when multilayered as a cell stack. Excellent sealing performance.

It is a figure which shows the laser optical non-contact three-dimensional shape measurement result of the multilayer sintered body A. It is a figure which shows the laser optical non-contact three-dimensional shape measurement result of the anode support type half cell A. It is a figure which shows the laser optical non-contact three-dimensional shape measurement result of the multilayer sintered body B. It is a figure which shows the laser optical non-contact three-dimensional shape measurement result of the anode support type half cell B.

  The anode-supporting half cell of the present invention includes an anode support substrate and an electrolyte layer laminated on the anode support substrate, and the height (h1) of the electrolyte layer peripheral edge and the half cell from the peripheral edge. The difference (Δh) from the height (h2) of the electrolyte layer at a position of 3 mm in the center direction is 100 μm or less. The difference (Δh) is the absolute value of the difference between the height (h1) and the height (h2). The difference (Δh) is preferably 50 μm or less, more preferably 20 μm or less, still more preferably 10 μm or less, and particularly preferably 5 μm or less.

  Since the electrolyte layer changes its precursor into a dense layer by firing, the amount of shrinkage during firing becomes very large. Therefore, when the anode support substrate or its green sheet and the electrolyte layer precursor are laminated and fired, the peripheral edge portion of the anode support substrate is pulled by the shrinkage of the electrolyte layer and warps to the electrolyte layer side. The anode-supporting half cell of the present invention is obtained by reducing the warpage of the peripheral portion by removing the peripheral portion that has warped in this manner.

  In the anode-supporting half cell of the present invention, since the warpage of the peripheral portion is reduced, when the cathode layer is printed by screen printing, the anode-supporting half cell and the printing plate can be uniformly contacted. Therefore, a cathode layer with high uniformity in thickness can be formed by screen printing, and printing omission can be suppressed. When an anode-supported cell is produced using the anode-supported half cell of the present invention, a cathode layer precursor is formed on the electrolyte layer and fired. Here, since the amount of shrinkage at the time of firing the cathode layer precursor is small, the firing does not cause the anode support substrate or the electrolyte layer to warp to the cathode layer side. Therefore, when the anode-supported half cell of the present invention is used, an anode-supported cell with reduced peripheral edge warpage can be obtained.

  The ratio (Δh / T) of the difference (Δh) to the thickness (T) of the anode-supported half cell is preferably 0.5 or less, more preferably 0.35 or less, still more preferably 0.3 or less, particularly preferably. Is 0.2 or less. The smaller the ratio (Δh / T), the easier it is to produce an anode-supported cell that is less susceptible to cracking and breakage even when multilayered as a cell stack, and that has excellent peripheral edge sealing properties. The lower limit of the ratio (Δh / T) is naturally zero.

  The thickness (T) of the anode-supporting half cell is preferably 110 μm or more, more preferably 130 μm or more, further preferably 160 μm or more, preferably 3 mm or less, more preferably 1 mm or less, still more preferably 0.5 mm or less. It is. If the thickness of the anode-supporting half cell is within the above range, the anode-supporting cell has sufficient mechanical strength and good fuel gas diffusibility.

  In the anode-supporting half cell, the ratio (T2 / T1) between the thickness (T1) of the anode support substrate and the thickness (T2) of the electrolyte layer is preferably 0.003 or more, more preferably 0.01 or more. More preferably, it is 0.04 or more, 0.35 or less is preferable, More preferably, it is 0.2 or less, More preferably, it is 0.1 or less. As the thickness of the electrolyte layer with respect to the thickness of the anode support substrate is increased, the warpage due to firing shrinkage of the electrolyte layer is increased, and thus the effect of the present invention becomes more remarkable.

  The anode support substrate is mainly composed of a conductive component for imparting conductivity and a ceramic material which is a skeleton component of the support substrate.

  The conductive component is an essential component for imparting conductivity to the anode support substrate, and is a metal such as nickel, cobalt, iron, platinum, palladium, ruthenium; and fuel cell operation such as nickel oxide, cobalt oxide, and iron oxide. Metal oxides that change to conductive metals in the reducing atmosphere at the time; or composite metal oxides such as nickel ferrite and cobalt ferrite containing two or more of these oxides. These may be used alone or in combination of two or more as necessary. Among these, metallic nickel, metallic cobalt, metallic iron, or oxides thereof are preferable.

The skeletal component is an important component in securing the lamination load strength and redox resistance of the anode layer and the anode support substrate. As the skeletal component, zirconia, alumina, magnesia, titania, aluminum nitride, mullite or the like is used alone or in combination. Among these, the most versatile is stabilized zirconia. As the stabilized zirconia, zirconia is used, and oxides of alkaline earth metals such as MgO, CaO, SrO, BaO as stabilizers; Y ₂ O ₃ , La ₂ O ₃ , CeO ₂ , Pr ₂ O ₃ , Nd ₂ O ₃ , Sm ₂ O ₃ , Eu ₂ O ₃ , Gd ₂ O ₃ , Tb ₂ O ₃ , Dy ₂ O ₃ , Er ₂ O ₃ , Oxides of rare earth elements such as Tm ₂ O ₃ and Yb ₂ O ₃ ; one or more oxides selected from Sc ₂ O ₃ , Bi ₂ O ₃ , In ₂ O _3, etc. Or, furthermore, dispersion strengthened zirconia or the like to which alumina, titania, Ta ₂ O ₅ , Nb ₂ O ₅ or the like is added as a dispersion strengthening agent is exemplified. Further, as the skeleton component, CeO ₂ and Bi ₂ O ₃ are added to CaO, SrO, BaO, Y ₂ O ₃ , La ₂ O ₃ , Ce ₂ O ₃ , Pr ₂ O ₃ , Nb ₂ O ₃ , Sm ₂ O ₃ , Eu ₂ O ₃ , Gd ₂ O ₃ , Tb ₂ O ₃ , Dr ₂ O ₃ , Ho ₂ O ₃ , Er ₂ O ₃ , YbO ₃ , PbO, WO ₃ , MoO ₃ , V ₂ O ₅ , Ta ₂ O ₅ Further, a ceria-based or bismuth-based ceramic added with one or more of Nb ₂ O _{5 and} a gallate-based ceramic such as LaGaO ₃ can also be used. These may be used alone or in combination of two or more. Among these, as the skeleton component, stabilized zirconia, ceria, and lanthanum gallate are preferable, stabilized zirconia is more preferable, and particularly preferable is zirconia stabilized with 2.5 to 12 mol% yttria, 3 to Zirconia stabilized with 15 mol% scandia.

  The ratio of the conductive component to the skeletal component is 30% by mass / 70% by mass or more and 80% by mass when the total of these components is 100% by mass. / 20 mass% or less is preferable, More preferably, it is 40 mass% / 60 mass% or more and 70 mass% / 30 mass% or less. The amount of the conductive component referred to here is an amount when the conductive component exists as an oxide, and is an amount converted to an oxide.

  The thickness (T1) of the anode support substrate is preferably 100 μm or more, more preferably 120 μm or more, further preferably 150 μm or more, preferably 3 mm or less, more preferably 2 mm or less, still more preferably 1 mm or less, particularly preferably. 500 μm or less. As long as the thickness of the anode support substrate is within the above range, the mechanical strength and gas permeability of the anode support substrate can be balanced.

  Further, the porosity of the anode support substrate is preferably 20% or more, more preferably 25% or more, further preferably 30% or more, preferably 50% or less, more preferably 45% or less, still more preferably 40%. It is as follows. If the porosity of the anode support substrate is within the above range, the mechanical strength and gas permeability of the anode support substrate can be achieved in a balanced manner.

An electrolyte layer is formed on the anode support substrate. At this time, an anode layer may be provided between the anode support substrate and the electrolyte layer. When the anode support substrate can act as an anode, the anode layer may not be provided.
Similar to the anode support substrate, the anode layer is mainly composed of a conductive component for providing conductivity and a ceramic material which is a skeleton component of the support substrate. Examples of the conductive component and the skeleton component are the same as those for the anode support substrate.

  The thickness of the anode layer is preferably 5 μm or more, more preferably 10 μm or more, further preferably 15 μm or more, preferably 100 μm or less, more preferably 50 μm or less, and further preferably 30 μm or less. When the thickness of the anode layer is within the above range, the electrode reaction is efficiently performed, and the power generation performance is better when the anode-supported cell is used.

  The electrolyte layer is mainly composed of a ceramic material. The ceramic material is not particularly limited as long as it is usually used as a material for the electrolyte layer. For example, zirconia stabilized with yttrium oxide, cerium oxide, scandium oxide, ytterbium oxide, etc .; yttria, samaria, gadolinia, etc. Doped ceria; lanthanum gallate and lanthanum gallate perovskite structure oxidation in which lanthanum or gallium part of lanthanum gallate is substituted with strontium, calcium, barium, magnesium, aluminum, indium, cobalt, iron, nickel, copper, etc. Things can be used. These may be used alone or in combination of two or more. Among these, zirconia stabilized with yttrium oxide, scandium oxide, ytterbium oxide, or the like is preferable.

  In particular, as a ceramic material, zirconia stabilized with 3 to 10 mol% yttrium oxide, 4 to 12 mol% zirconia stabilized with scandium oxide, 8 to 12 mol% It is preferable to use zirconia stabilized with 4 mol% or more and 15 mol% or less of ytterbium oxide. A material obtained by adding alumina, silica, titania or the like as a sintering aid or dispersion strengthening agent to these stabilized zirconia can also be suitably used.

  The thickness (T2) of the electrolyte layer is preferably 5 μm or more, more preferably 7 μm or more, further preferably 10 μm or more, preferably 50 μm or less, more preferably 30 μm or less, and still more preferably 20 μm or less. When the thickness of the electrolyte layer is within the above range, the power generation performance is better when an anode-supported cell is used.

  The porosity of the electrolyte layer is preferably 10% or less, more preferably 7% or less, and still more preferably 5% or less. If the porosity of the electrolyte layer is within the above range, the mechanical strength of the electrolyte layer will be sufficient, and the gas tightness of fuel gas and air will be good.

  The method for producing an anode-supported half cell of the present invention includes, for example, a step of producing a multilayer fired body (laminated body) including an anode support substrate and an electrolyte layer; and a step of cutting and removing a peripheral portion of the multilayer fired body. A method is mentioned. By cutting and removing the peripheral edge portion of the multilayer fired body, the warped portion is removed, and an anode-supporting half cell in which the peripheral edge warpage is reduced is obtained.

  Examples of a method for producing a laminate including the anode support substrate and the electrolyte layer include, for example, a method of forming a laminate in which an anode support substrate green sheet and an electrolyte layer precursor are laminated and then firing them together (mode) 1): A method of firing the anode supporting substrate green sheet, the anode layer green sheet, and the electrolyte layer precursor in this order and then firing them together (Aspect 2); firing the anode supporting substrate green sheet A method of producing an anode support substrate, laminating an electrolyte layer precursor thereon, and firing the laminate (Aspect 3); firing an anode support substrate green sheet, producing an anode support substrate, and Examples include a method of laminating an anode layer green sheet, further laminating an electrolyte layer precursor thereon, and firing the laminate (Aspect 4). Among these, aspect 2 is preferable. Hereinafter, the said aspect 2 is demonstrated as an example of the method of forming the said laminated body.

  The anode layer green sheet and the anode support substrate green sheet are prepared by uniformly mixing a conductive component powder, a skeletal component powder, and a pore forming agent together with a binder, a solvent, and, if necessary, a dispersant, a plasticizer, and the like. Then, the prepared slurry is spread on a smooth sheet (for example, a polyester sheet) at an appropriate thickness by an arbitrary method such as a doctor blade method, a calender roll method, or an extrusion method, and dried to volatilize and remove the solvent. can get.

The conductive component powder preferably has an average particle diameter (D ₅₀ ) of 0.2 μm or more and 5 μm or less and a 90 volume% diameter (D ₉₀ ) of 15 μm or less, more preferably an average particle diameter of 0.3 μm or more and 3 μm or less. The 90 volume% diameter is 10 μm or less, more preferably the average particle diameter is 0.4 μm or more and 2 μm or less, and the 90 volume% diameter is 8 μm or less. Incidentally, the average particle diameter in the present invention, the median diameter determined from the particle size distribution, that is, shall refer to 50 volume% diameter (D _50). These average particle diameter and 90 volume% diameter were obtained from a particle size distribution measured using a 0.2% by mass sodium metaphosphate aqueous solution as a dispersion medium using a laser diffraction / scattering particle size distribution measuring apparatus such as LA-920 manufactured by Horiba Seisakusho. Can be sought.

The skeletal component powder preferably has an average particle diameter (D ₅₀ ) of 0.1 μm or more and 3 μm or less and a 90 volume% diameter (D ₉₀ ) of 6 μm or less, more preferably an average particle diameter of 0.1 μm or more. 5 μm or less and 90% by volume of 3 μm or less, more preferably 0.2 μm or more and 1 μm or less and 90% by volume of 2 μm or less are preferable.

  The pore-forming agent is not particularly limited as long as it burns down when the green sheet is fired, and is an aggregate of crosslinked fine particles made of an acrylic resin or the like; wheat flour, corn starch (corn starch), sweet potato starch, potato starch, tapioca starch Natural organic powders such as: thermally decomposable or sublimable resin powders such as melamine cyanurate; carbonaceous powders such as carbon black and activated carbon. These may be used alone or in combination of two or more.

  The average particle diameter of the pore forming agent is preferably 0.5 μm or more and 100 μm or less, more preferably 3 μm or more and 50 μm or less. Also. The 10% by volume diameter of the pore forming agent is preferably 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less.

  The amount of the pore-forming agent used is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and preferably 40 parts by mass or less with respect to 100 parts by mass in total of the conductive component powder and the skeleton component powder. More preferably, it is 30 parts by mass or less. By setting the use amount of the pore forming agent within the above range, pores are appropriately formed by thermal decomposition during firing, and the gas permeability and physical strength of the anode support substrate and the anode layer become better.

  The binder is not particularly limited, and a conventionally known organic binder can be appropriately selected and used. Examples of organic binders include ethylene copolymers, styrene copolymers, acrylate and methacrylate copolymers, vinyl acetate copolymers, maleic acid copolymers, vinyl butyral resins, and vinyl acetal series. Examples thereof include resins, vinyl formal resins, vinyl alcohol resins, waxes, and celluloses such as ethyl cellulose. These may be used alone or in combination of two or more.

  The solvent is not particularly limited, and various organic solvents such as alcohols, glycol ethers, aliphatic hydrocarbons, ketones, and esters can be used. Specific examples of the organic solvent include α-terpineol, dihydroterpineol, alcohols such as methanol, ethanol, isopropyl alcohol, 1-butanol, 1-hexanol, glycerin, and polyethylene glycol; butyl carbitol acetate, butyl carbitol Glycol ethers such as pentane, hexane, heptane, kerosene, cyclohexane, etc .; ketones such as acetone, 2-butanone, etc .; ethyl acetate, methyl acetate, butyl acetate, terpineol acetate, dihydroterpineol acetate, etc. Esters such as toluene and xylene. These may be used alone or in combination of two or more. Of these, ethyl acetate, methyl acetate, butyl acetate, methanol, ethanol, acetone, xylene, pentane, hexane, heptane and the like are preferable in order to accelerate drying after coating.

  The dispersant promotes peptization and dispersion of the ceramic powder. Examples of the dispersant include polyelectrolytes such as polyacrylic acid and ammonium polyacrylate; organic acids such as citric acid and tartaric acid; copolymers of isobutylene or styrene and maleic anhydride and ammonium salts or amine salts thereof. A copolymer of butadiene and maleic anhydride, and an ammonium salt thereof;

  The plasticizer imparts flexibility to the electrolyte layer. Examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, dioctyl phthalate and ditridecyl phthalate; glycols and glycol ethers such as propylene glycol; phthalic acid polyester, adipic acid polyester, sebacic acid polyester, and the like. Polyesters.

  In addition, what is necessary is just to prepare suitably the compounding quantity of each raw material of the slurry for anode layers, and the slurry for anode support substrates according to a desired physical property. Moreover, the drying conditions of the sheet | seat obtained from the slurry should just be a grade which can evaporate a solvent, for example, what is necessary is just to heat for about 1 hour or more and 10 hours or less at about 70 degreeC or more and 120 degrees C or less.

  And as a method of producing a laminate of the anode layer green sheet and the anode support substrate green sheet, the anode layer green sheet and the anode support substrate green sheet are separately produced, laminated, and heated and pressed to obtain a laminate. And a method of forming an anode layer green sheet by screen printing on the anode supporting substrate green sheet. The conditions for the heat press are not particularly limited, and may be, for example, about 30 ° C. or higher and 100 ° C. or lower, and 0.2 MPa or higher and 2 MPa or lower for 10 seconds or longer and 5 minutes or shorter. As for the anode support substrate, a plurality of green sheets may be laminated and used in order to ensure a desired strength. In the screen printing, an anode layer paste is screen-printed on an anode supporting substrate green sheet or a laminate in which a plurality of anode supporting substrate green sheets are laminated.

  Next, the electrolyte paste is screen-printed on the anode layer green sheet of the obtained laminate. The electrolyte paste is prepared by mixing at least ceramic powder as a ceramic raw material and a solvent.

The ceramic powder preferably has a fine average particle diameter of 0.3 μm or more and 0.7 μm or less. Further, as the ceramic powder, those having a small particle size distribution are suitable. Specifically, those having an average particle diameter of 0.3 μm or more and 0.7 μm or less and a 90 volume% diameter (D ₉₀ ) of 1.2 μm or less are preferable, and more preferably the average particle diameter is 0. .4 μm or more and 0.6 μm or less, and 90% by volume diameter is 1.0 μm or less.

  It does not specifically limit as said solvent, It can select and use from what was mentioned as a material of the said slurry for anode layers. A solvent may be used independently and may use 2 or more types together. In addition, when forming the electrolyte layer precursor by screen printing, the solvent is not particularly limited, and various organic solvents such as alcohols, glycol ethers, aliphatic hydrocarbons, ketones, esters may be used. it can. Specific examples of the organic solvent include α-terpineol, dihydroterpineol, terpineol acetate, dihydroterpineol acetate, kerosene, 1-butanol, 1-hexanol, 2-butanone, isopropyl alcohol, polyethylene glycol, glycerin, butyl carbitol acetate, Butyl carbitol, toluene, cyclohexane, methyl ethyl ketone and the like are preferable. The amount of the solvent used is not particularly limited, and may be appropriately adjusted in consideration of the viscosity of the electrolyte paste during screen printing.

  In addition to the ceramic particles and the solvent, a binder, a dispersant, a plasticizer, a surfactant, an antifoaming agent, and the like may be added to the electrolyte paste. The binder, dispersant, and plasticizer can be selected from those listed as materials for the anode layer slurry according to the material of the electrolyte precursor to be formed. The electrolyte paste is prepared by mixing an appropriate amount of the above components. At that time, in order to make each particle fine or to make the particle diameter uniform, the particles may be mixed while being pulverized using a ball mill or the like. Moreover, the order of addition of each component is not particularly limited, and may be according to a conventional method.

  Screen printing when forming the electrolyte paste on the anode layer green sheet may be performed in the same manner as a conventional method. The electrolyte paste coated on the anode layer green sheet is dried to volatilize and remove the solvent. The drying condition of the electrolyte paste may be such that the solvent can be evaporated, and for example, it may be heated at 70 ° C. or higher and 120 ° C. or lower for 15 minutes or longer and 10 hours or shorter.

  The firing temperature of the laminate in which the anode support substrate green sheet, the anode layer green sheet, and the electrolyte layer precursor are laminated in this order is preferably 1100 ° C. or higher, more preferably 1200 ° C. or higher, and still more preferably 1290 ° C. or higher. 1500 degrees C or less is preferable, More preferably, it is 1400 degrees C or less, More preferably, it is 1330 degrees C or less. The firing time during firing is preferably 0.1 hour or longer, more preferably 0.5 hour or longer, further preferably 1 hour or longer, preferably 10 hours or shorter, more preferably 7 hours or shorter, still more preferably. Is 5 hours or less.

  Examples of the method for cutting the peripheral edge of the multilayer fired body include a method using a laser cutting device and a diamond cutter. Among these, it is preferable to use a laser cutting device. By using a laser cutting device, generation of microcracks in the cross section after cutting can be suppressed, and curved surface processing can be easily performed. In the case of using a laser cutting device, warping due to a difference in thermal expansion between the anode support substrate and the electrolyte layer may occur due to local heating by the laser. However, by adjusting the porosity of the anode support substrate and the electrolyte layer, it is possible to reduce the occurrence of warping due to this difference in thermal expansion.

  In cutting and removal, when the total length of the fired multilayer fired body is 100%, the distance from the peripheral edge to the cut portion is preferably 5% or more, more preferably 7% or more, and still more preferably 9 % Or more, preferably 20% or less, more preferably 17% or less, and still more preferably 15% or less. If the distance from the peripheral edge part to the cut part is within the above range, warping can be sufficiently reduced and waste of the multilayer fired body can be suppressed.

  Although the peripheral portion is cut and removed for the entire circumference of the multilayer fired body, it is preferable that the distance from the peripheral edge portion to the cut portion is unified for the entire periphery. The fired multilayer fired body has the same degree of warpage over its entire periphery. Therefore, by cutting and removing the entire circumference to the same degree, the peripheral edge of the anode-supporting half cell after the cutting process also has the same degree of warpage over the entire circumference. Thus, if the warpage of the entire peripheral edge is approximately the same, it is possible to further suppress cracking and breakage when multilayered as a cell stack. In addition, when a part of the peripheral part is removed or divided at the center part of the multilayer fired body, the anode-supported half cell after the cutting treatment is biased in the warp of the peripheral part, and a multilayer is formed as a cell stack. When laminated and subjected to a large lamination load, cracks or breakage due to local stress concentration caused by warping may occur.

Anode-supported cell In the anode-supported cell of the present invention, in the anode-supported half cell, a cathode layer is formed on the surface opposite to the surface on which the anode layer of the electrolyte is laminated. As described above, in the anode-supporting half cell, the warpage of the peripheral portion is reduced, so that the cathode layer can be stably formed by screen printing. Therefore, in the anode-supported cell of the present invention, the cathode layer has a uniform thickness, and defects due to printing failure are reduced. Further, the anode-supported cell of the present invention has a reduced warp at the peripheral edge, and even when multilayered as a cell stack, it does not easily crack or break, and has excellent sealing performance at the peripheral edge.

  The cathode layer is prepared by uniformly mixing a cathode layer material with a binder, a solvent, and, if necessary, a dispersant, a plasticizer, and the like to prepare a paste, and coating the prepared paste on the electrolyte layer by screen printing or the like. It can be formed by drying and baking.

As the cathode layer material, a material made of a perovskite oxide which is excellent in electronic conductivity and stable even in an oxidizing atmosphere is generally used. Specifically, La _0.8 Sr _0.2 MnO ₃ , La _0.6 Sr _0.4 CoO ₃ , La _0.6 Sr _0.4 FeO ₃ , La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O _3, etc., lanthanum manganite in which part of lanthanum is substituted with strontium Lanthanum ferrite, lanthanum cobaltite and the like are preferable as the cathode layer material. In addition, in order to impart oxygen ion conductivity to the cathode layer, ceria doped with a rare earth element or the like may be appropriately mixed.

  The binder, solvent, dispersant, plasticizer and the like used for the cathode layer paste may be the same as those used for the electrolyte paste. In addition, what is necessary is just to prepare the compounding quantity of each raw material suitably according to a desired physical property. A method for coating the obtained paste on the electrolyte layer is not particularly limited, but screen printing is preferable. Screen printing may be performed in the same manner as a conventional method.

  The cathode layer paste applied on the electrolyte layer is dried and fired to form the cathode layer. The drying condition of the cathode paste may be such that the solvent can be evaporated, and for example, it may be heated at about 70 ° C. to 120 ° C. for about 15 minutes to about 10 hours. The cathode layer precursor firing conditions may be appropriately adjusted according to the raw material and thickness thereof. For example, the cathode layer precursor may be fired at about 700 ° C. to 1300 ° C. for about 2 hours to 10 hours. The thickness of the cathode layer formed on the electrolyte is preferably 10 μm or more and 80 μm or less.

Solid oxide fuel cell The solid oxide fuel cell of the present invention is characterized by having the anode-supported cell. The anode-supported cell has a reduced warp at its peripheral edge. For this reason, the solid oxide fuel cell having the anode-supported cell is prevented from being deteriorated by cracking of the anode-supported cell, has a long life, has excellent sealing performance at the periphery, and suppresses gas leakage during operation. As a result, power generation efficiency is improved.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples, and may be appropriately modified and implemented within a range that can meet the purpose described above and below. All of which are within the scope of the present invention.

1. Peripheral warpage Place the anode-supported half cell so that the electrolyte layer is on top, and use a laser optical non-contact three-dimensional shape measuring device (trade name “UBM1-14”, Micro Focus Expert, manufactured by UBM) Then, by irradiating the surface of the electrolyte layer with laser light and analyzing the reflected light in a three-dimensional manner, the height (h1) of the peripheral edge of the electrolyte layer and the position of 3 mm from the peripheral edge to the center of the half cell The height (h2) of the electrolyte layer was measured and the difference (Δh) was determined.
The specifications of the measuring apparatus were: light source: semiconductor laser (780 nm), spot diameter: 1 μm, vertical separation power: 0.01 μm, and scan pitch was 0.2 mm.

2. Anode support substrate, porosity of electrolyte The anode support half-cell produced in the production example was cut, and a 10,000 times magnified photograph of the cross section was taken using a scanning electron microscope. An arbitrary area of 5 μm in the thickness direction × 10 μm in the planar direction in the enlarged cross-sectional photograph obtained was applied to a paint (registered trademark) Ver. It was imported into 5.1 and converted to black and white display. In such an image, the void portion is displayed in black and the filled portion is displayed in white. The obtained image was scanned with a scanning probe image processor Ver., Which is image analysis software manufactured by Image Metrology. Using 4.5.1.0 (hereinafter referred to as “SPIP”), the ratio of the void portion in the image was obtained. In the image before processing, there is a gray portion that is intermediate between black and white, but in order to reduce the error, by setting the gray scale of 0 to 20,000 in SPIP to 8,000, The contrast with the white part was clarified.

3. Load cracking test It was installed in a state where a half cell was sandwiched between two alumina plates ("SSA-S" manufactured by Nikkato Co., Ltd.) whose surfaces were smooth and kept parallel. A compressive load was applied from above the upper alumina plate using a material tester (Instron, “4301 type”), and the compressive load when the half cell was cracked was measured. The maximum compressive load was 2.0 kN (200 kgf), and “no cracking” was evaluated when no cracking occurred even at a compressive load of 2.0 kN.

4). Cathode electrode formation stability by screen printing and anode-supporting cell sealing performance Cathode layer paste is screen-printed on a square of 60 mm on a square on a 75 mm square anode-supporting half-cell obtained in the production example. A cathode layer green sheet was formed.
Here, the cathode paste was prepared as follows. 60 parts by mass of La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O ₃ particles (manufactured by Seimi Chemical Co., Ltd.) as the cathode powder, 5 parts by mass of ethyl cellulose (manufactured by Wako Pure Chemical Industries, Ltd.) as the binder, and α-terpineol (Wako Pure Chemical Industries, Ltd.) as the solvent 40 parts by mass, 6 parts by mass of dibutyl phthalate (manufactured by Wako Pure Chemical Industries, Ltd.) as a plasticizer, and a sorbitan acid-based surfactant (manufactured by Sanyo Kasei Co., Ltd., trade name “IONET (registered trademark) S-80” as a dispersant. “) 5 parts by mass were mixed using a mortar, and then pulverized using a three-roll mill (EXAKT technologies, model“ M-80S ”, roll material: alumina).

  After film formation, the thickness of the cathode layer green sheet after drying at 100 ° C. for 30 minutes was measured with a micrometer. In the measurement, the cathode layer was divided into square grids each having a size of 1 cm, and a total of 25 points were measured on each grid point. In the measurement, the total thickness of the anode-supporting half cell and the cathode layer green sheet was measured, and the thickness of the anode-supporting half cell was subtracted from that value to obtain the thickness of the cathode layer green sheet. The stability of the cathode layer formation was evaluated by obtaining the standard deviation of the measured thickness.

  Further, this cathode layer was baked at 1000 ° C. for 2 hours to produce an anode-supported cell. In order to evaluate the sealing performance of the cell, a glass paste was applied as a sealing material to a 3 mm peripheral portion of the cell, and was sandwiched between interconnectors and set in a cell electrical performance evaluation apparatus. Thereafter, the cell was heated to 800 ° C., 3% humidified hydrogen was introduced into the anode side, and the open circuit electromotive voltage (OCV) was measured. The theoretical electromotive voltage is about 1.10V. When the OCV is significantly lower than the theoretical electromotive voltage, the fuel gas leaks because the seal portion does not function sufficiently. Therefore, it can be determined that the smaller the OCV, the worse the sealing performance.

5. Anode Support Substrate, Anode Layer, and Electrolyte Layer Thickness The anode supported half cell obtained in the production example was cut in the thickness direction, and the cut surface was observed with a scanning electron microscope (SEM) to determine the thickness of each layer. It was measured.

Production Example 1
1-1. Production of anode support substrate green sheet 60 parts by mass of nickel oxide (manufactured by Shodo Chemical Co., Ltd., average particle diameter 0.7 μm, 90 vol% diameter 1.2 μm) as conductive component, 3 mol% yttria stabilized zirconia as skeletal component 40 parts by mass of powder (manufactured by Daiichi Rare Element Co., Ltd., trade name “HSY-3.0”, average particle diameter 0.7 μm, 90 volume% diameter 1.9 μm), carbon black as a pore forming agent (manufactured by SEC Carbon Co., Ltd.) , SGP-3, average particle diameter 3.3 μm, 10 volume% diameter 1.5 μm) 10 parts by mass, mixed solvent of 60 parts by mass of toluene and 40 parts by mass of ethanol, butyral resin as a binder (manufactured by Sekisui Chemical Co., Ltd.) , Product name “BM-S”) 10 parts by mass, 3 parts by mass of dibutyl phthalate as a plasticizer (manufactured by Wako Pure Chemical Industries, Ltd.), sorbitan fatty acid ester based surface activity as a dispersant A slurry was prepared by mixing 2 parts by mass of a sex agent with a ball mill.
Using the obtained slurry, a sheet was formed by a doctor blade method and dried at 70 ° C. for 5 hours to prepare a 300 μm thick anode supporting substrate green sheet.

1-2. Preparation of Anode Layer Green Sheet 60 parts by mass of nickel oxide (made by Kishida Chemical Co., Ltd., average particle diameter of 0.75 μm, 90 vol% diameter of 1.4 μm) as a conductive component, 3 mol% yttria-stabilized zirconia powder as a skeletal component ( Product name “HSY-3.0” manufactured by Daiichi Rare Element Co., Ltd., 40 parts by mass of average particle diameter 0.7 μm, 90 volume% diameter 1.9 μm, carbon black as a pore forming agent (manufactured by SEC Carbon, SGP -3, 6 parts by mass of an average particle size of 3.3 μm, 10% by volume of 1.5 μm), a mixed solvent of 60 parts by mass of toluene as a solvent and 40 parts by mass of ethanol, butyral resin as a binder (manufactured by Sekisui Chemical Co., Ltd., product name) "BM-S") 10 parts by weight, 3 parts by weight of dibutyl phthalate (manufactured by Wako Pure Chemical Industries, Ltd.) as a plasticizer, sorbitan fatty acid ester surfactant as a dispersant Two parts by mass were mixed by a ball mill to prepare a slurry.
Using the obtained slurry, a sheet was formed by a doctor blade method and dried at 100 ° C. for 1 hour to prepare an anode layer green sheet having a thickness of 20 μm.

  1-3. Production of Laminate of Anode Layer Green Sheet and Anode Support Substrate Green Sheet The anode layer green sheet obtained above was laminated on the anode support substrate green sheet obtained above. A laminate of the anode support substrate green sheet and the anode layer green sheet was hot-pressed at 60 ° C. and 0.5 MPa for 30 seconds using a hot press machine.

1-4. Formation of Electrolyte Film As ceramic powder, scandia-stabilized zirconia unsintered powder (trade name “10Sc1CeSZ”, average particle diameter 0.60 μm, manufactured by Daiichi Rare Element Co., Ltd.) 60 parts by mass, ethyl cellulose (manufactured by Wako Pure Chemical Industries, Ltd.) as a binder ) 5 parts by mass, α-terpineol (manufactured by Wako Pure Chemical Industries) as a solvent, 40 parts by mass, 6 parts by mass of dibutyl phthalate (manufactured by Wako Pure Chemical Industries) as a plasticizer, and sorbitan acid ester-based interface as a dispersant After mixing 5 parts by mass of an activator (manufactured by Sanyo Kasei Co., Ltd., trade name “Ionet S-80”) using a mortar, a three-roll mill (manufactured by EXAKT technologies, model “M-80S”, roll material: alumina ).

  The pulverized electrolyte paste was printed on the anode layer green sheet of the laminate obtained above by screen printing so as to have a thickness of 15 μm, and dried at 100 ° C. for 30 minutes. After drying, the substrate was punched into a square shape with a side of 100 mm to prepare a laminate of an anode support substrate green sheet, an anode layer precursor, and an electrolyte layer precursor. The laminate was fired at 1300 ° C. for 2 hours to produce a multilayer fired body. The fired multilayer fired body had a square shape with a side of 85 mm. The anode support substrate had a thickness of 250 μm, the anode layer had a thickness of 15 μm, and the electrolyte layer had a thickness of 10 μm. The ratio (T2 / T1) between the thickness (T1) of the anode support substrate and the thickness (T2) of the electrolyte layer was 0.04. Further, the porosity of the anode support substrate was 32%, and the porosity of the electrolyte layer was 5%. The warpage of the peripheral part was measured for two of the produced multilayer fired bodies (referred to as multilayer fired body A and multilayer fired body B, respectively). The results are shown in FIGS.

  Using a laser cutting device (YAG laser device manufactured by Sumitomo Heavy Industries Mechatronics, model “JK702H”), the peripheral portion of the fired multilayer fired body was cut and removed to obtain an anode-supported half cell. Specifically, all the 10 mm portions from the peripheral edge of the fired anode-supported half cell were removed. For the anode-supported half cell A from which the peripheral edge of the multilayer fired body A was removed and the anode-supported half cell B from which the peripheral edge of the multilayer fired body B was removed, the warpage of the peripheral edge was measured. The results are shown in FIGS.

Production Example 2
In the same manner as in Production Example 1, a laminate of an anode support substrate green sheet, an anode layer precursor, and an electrolyte layer precursor was produced. However, the punching size was a square shape with a side of 77 mm. Then, like the manufacture example 1, this laminated body was baked at 1300 degreeC for 2 hours, and the multilayer baked body was produced. The fired multilayer fired body had a square shape with a side of 65 mm. The anode support substrate had a thickness of 250 μm, the anode layer had a thickness of 15 μm, and the electrolyte layer had a thickness of 10 μm.

  A plurality of anode-supported half cells were produced by the method described in Production Example 1, and a plurality of multilayer fired bodies were produced by the method described in Production Example 2. The obtained anode-supported half cell and multilayer fired body were evaluated for the warpage of the peripheral edge and the results are shown in Tables 1 to 3.

  As shown in Table 1, none of the anode-supported half cells obtained in Production Example 1 having Δh of 100 μm or less was cracked even at a compression load of 2.0 kN. On the other hand, in the multilayer fired body of Production Example 2 in which Δh exceeds 100 μm, it was cracked at 1.5 kN and 1.7 kN. From these results, it can be seen that by setting Δh to 100 μm or less, it is possible to suppress the occurrence of cracks, breakage, and the like even when the cell stack is multi-layered and receives a large stacking load.

  As shown in Table 2, the anode-supported half cell obtained in Production Example 1 in which Δh is 100 μm or less has a standard deviation of the cathode layer thickness of 3 μm or less, and is excellent in thickness uniformity. I understand. In contrast, in the multilayer fired body of Production Example 2 in which Δh exceeds 100 μm, the standard deviation of the cathode layer thickness exceeds 5 μm, and it can be seen that the thickness varies greatly. From these results, it can be seen that by setting Δh to 100 μm or less, the cathode layer can be stably formed by screen printing.

  As shown in Table 3, it can be seen that all of the anode-supported half cells obtained in Production Example 1 having Δh of 100 μm or less have an OCV of 1 V or more and have excellent sealing properties. On the other hand, in the multilayer fired body of Production Example 2 in which Δh exceeds 100 μm, the OCV is as small as less than 0.8, indicating that the sealing performance is poor. From these results, it can be seen that by setting Δh to 100 μm or less, it is possible to obtain an anode-supported cell having excellent peripheral edge sealing performance.

Claims (12)

An anode-supported half cell having an anode support substrate, an anode layer, and an electrolyte layer in this order,
The anode support substrate and the anode layer include a conductive component and a skeleton component,
The conductive component is one or more selected from the group consisting of metallic nickel, metallic cobalt, metallic iron, and oxides thereof,
The skeletal component of the anode support substrate is stabilized zirconia,
The skeletal component of the anode layer is stabilized zirconia (except for zirconia stabilized with 2.5-12 mol% yttria and zirconia stabilized with 3-15 mol% scandia). ,
The ratio of the conductive component and the skeletal component is such that the ratio of the conductive component to the skeletal component (conductive component / skeleton component) is 30% by mass, where the total of the conductive component and the skeletal component is 100% by mass. 70% by mass or more and 80% by mass / 20% by mass or less,
The electrolyte layer includes a ceramic as a main component,
The ceramic material is zirconia stabilized with at least one selected from the group consisting of yttrium oxide, scandium oxide, and ytterbium oxide,
Place the anode-supported half cell so that the electrolyte layer is on the top surface, and use a laser optical three-dimensional shape measuring device to irradiate the electrolyte layer surface with laser light and analyze the reflected light in three dimensions. The difference (Δh) between the height (h1) of the peripheral edge of the electrolyte layer obtained by the above and the height (h2) of the electrolyte layer at a position of 3 mm from the peripheral edge to the center of the half cell is 100 μm or less. An anode-supported half-cell characterized by The stabilized zirconia of the skeletal component of the anode support substrate and the stabilized zirconia of the skeletal component of the anode layer include an alkaline earth metal oxide, a rare earth element oxide, Sc ₂ O ₃ , Bi _2. O _3, and in ₂ anode supported half-cell according to claim 1 O ₃ at least one selected from the group consisting of is zirconia in solid solution.   3. The anode-supported half cell according to claim 2, wherein the alkaline earth metal oxide is at least one selected from the group consisting of MgO, CaO, SrO, and BaO. The rare earth oxides are Y ₂ O ₃ , La ₂ O ₃ , CeO ₂ , Pr ₂ O ₃ , Nd ₂ O ₃ , Sm ₂ O ₃ , Eu ₂ O ₃ , Gd ₂ O ₃ , Tb ₂ O _{3. 3.} The anode-supported half cell according to claim 2, which is at least one selected from the group consisting of Dy ₂ O ₃ , Er ₂ O ₃ , Tm ₂ O ₃ , and Yb ₂ O ₃ . The anode support substrate has a thickness of 100 μm or more and 3 mm or less,
The anode layer has a thickness of 5 μm or more and 100 μm or less,
The thickness of the electrolyte layer is 5 μm or more and 50 μm or less,
The anode-supported half cell according to any one of claims 1 to 4.   6. The ratio (T 2 / T 1) between the thickness (T 1) of the anode support substrate and the thickness (T 2) of the electrolyte layer is 0.003 to 0.35, 6. Anode supported half-cell.   An anode-supported cell, wherein a cathode layer is formed on the anode-supported half cell according to any one of claims 1 to 6.   The anode-supported cell according to claim 7, wherein the standard deviation of the thickness of the cathode layer is 3 μm or less.   A solid oxide fuel cell comprising the anode-supported cell according to claim 7. It is a manufacturing method of the anode support type half cell according to any one of claims 1 to 6,
Producing a multilayer fired body including the anode support substrate and the electrolyte layer;
Cutting and removing the peripheral edge of the multilayer fired body;
A process for producing an anode-supported half cell, comprising:   The method for producing an anode-supported half cell according to claim 10, wherein the step of cutting and removing the peripheral portion is performed by cutting and removing using a laser cutting device.   The manufacturing method of the anode support type cell which forms a cathode layer by screen printing in the anode support type half cell manufactured by the manufacturing method of Claim 10 or 11.

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