JP2006185697A - Interconnector material and solid oxide fuel cell equipped with it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid oxide fuel cell having output performance without being impaired even if the co-baking of at least one-side electrode and an interconnector is executed, by developing the interconnector having a high degree of sintering. <P>SOLUTION: This solid oxide fuel cell is provided with an air electrode formed of a group A, an electrolyte formed of a group B, a fuel electrode formed of a group C, and the interconnector formed of a perovskite type oxide containing La and Fe as main constituents and formed by replacing 50 mol% or less of Fe with Cr or Ti. The group A is represented by ABO<SB>3</SB>, where A is at least one kind selected from alkaline earth metals excluding Mg, lanthanoid excluding Ce, Sc and Y, and B is at least one kind selected from Cr, Mn, Fe, Co, Ni, Cu, Al and Mg. The group B is at least one kind selected from stabilized zirconia, a celia-based solid solution and lanthanum gallate. The group C is a complex of at least one kind selected from Ni, Co, Cu and Fe, and at least one kind selected from the group B. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a solid oxide fuel cell, and has developed a highly sinterable interconnector and does not impair output performance even when at least one electrode and the interconnector are co-fired. It is invention regarding.

A solid oxide fuel cell is composed of four members: an air electrode, an electrolyte, a fuel electrode, and an interconnector. When forming and forming each member, it is possible to shorten the production process if it is possible to sinter at least two kinds, preferably all members at once (called co-firing or integral sintering). However, each member has a different role, and the material used and its characteristics are also different, so that it is very difficult to achieve. Among them, the co-firing of the interconnector and other members is considered to be a very difficult technology, and the reason for this is that LaCrO ₃ having a very low sinterability compared to other members is used for the conventional interconnector material. is there. When firing at the sintering temperature (1700 ° C.) of LaCrO ₃ , the porosity of the electrode is lost, so a high output cannot be obtained. In addition, LaCrO ₃ originally has a low electronic conductivity. Therefore, reports have been made to improve the sinterability and conductivity by replacing part of La with Sr, Ca, etc. and part of Cr with transition metal.

In order to sinter (La, Sr) CrO _{3 in} which part of La is replaced with Sr, a high temperature of 1700 ° C. or higher is required. Therefore, the B site of (La, Sr) CrO ₃ is doped with various metals and fired. The temperature has been lowered. (For example, refer to Patent Document 1).
According to Patent Document 1, the metal doping amount that is preferable from the viewpoint of ionic conductivity and reduction stability is limited to 30 mol%, and the firing temperature necessary for sintering can be 1600 ° C. or lower. However, there was a problem that the firing temperature could not be lowered to around 1400 ° C., which is the co-firing temperature required for co-firing with other members in the solid oxide fuel cell. In the flat type fuel cell, the interconnector and the other member may be separately sintered and then mechanically laminated. However, it is preferable to be able to co-fire with the other member because the man-hour is reduced. On the other hand, since cylindrical, flat tube, and monolith fuel cells cannot be sintered separately, a low-productivity manufacturing method such as vapor deposition or thermal spraying must be employed.

(La, Ca) CrO _{3 in} which a part of La is substituted with Ca can be fired at a relatively low temperature as compared with (La, Sr) CrO ₃ (see, for example, Patent Document 2).
However, in (La, Ca) CrO ₃ , a liquid phase component called calcium chromate generated during firing improves the sinterability, but during co-firing, this liquid phase component moves to another member, and (La , Ca) CrO ₃ itself does not sinter. Therefore, by providing a dense layer called a precoat layer, the movement of the liquid phase component is suppressed and sinterability is ensured (for example, see Patent Document 3).
In such a case, it is necessary to form a dense layer separately by baking or the like, which causes a problem that man-hours increase.

JP-A-4-219364 (page 4, Table 1) JP-A-9-249419 (5th page, Table 1) Japanese Patent Laid-Open No. 5-121085 (5th page, Table 1)

  The present invention has been made to solve the above problems, and the object of the present invention is to develop an interconnector having high sinterability, and at least one of the electrodes and the interconnector can be co-fired. It is an object of the present invention to provide a solid oxide fuel cell that does not impair performance.

In order to achieve the above object, according to the first aspect of the present invention, an air electrode composed of a group A, an electrolyte composed of a group B, a fuel electrode composed of a group C, and 50 mol% of Fe containing La and Fe as main components. Solid oxide fuel cell group A having an interconnector made of perovskite oxide with less than Cr or Ti substituted: ABO ₃ (A: alkaline earth metal excluding Mg, lanthanoid excluding Ce, Sc, Y At least one selected, B: at least one selected from Cr, Mn, Fe, Co, Ni, Cu, Al, Mg)
Group B: Provided is a complex of at least one selected from stabilized zirconia, ceria-based solid solution, and lanthanum gallate, C group: at least one selected from Ni, Co, Cu, and Fe, and at least one selected from Group B .

  In order to achieve the above object, according to the invention described in claim 2, the solid oxide fuel cell according to claim 1 is any one of a cylindrical vertical stripe type, a cylindrical horizontal stripe type, a flat tube type, and a monolith type. A solid oxide fuel cell is provided.

According to the invention of claim 3, wherein in order to achieve the above object, the general formula _{(La 1-x Sr x)} (Fe 1-y Cr y) O 3 (0 ≦ x ≦ 0.1,0 <y The solid oxide fuel cell according to claim 1 or 2, comprising an interconnector material represented by <0.5).

According to the fourth aspect of the invention in order to achieve the above object, the general formula _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) O 3 (M: Mn, Co, Ni , Cu, 0 ≦ x ≦ 0.05, 0 <y <0.5, 0 <z ≦ 0.1) The solid oxide fuel according to claim 1, Provide batteries.

According to the invention of claim 5, wherein in order to achieve the above object, the general formula _{(La 1-x Sr x)} (Fe 1-y Ti y) O 3 (0 ≦ x ≦ 0.1,0 <y The solid oxide fuel cell according to claim 1 or 2, comprising an interconnector material represented by <0.5).

According to the invention of claim 6, wherein in order to achieve the above object, the general formula _{(La 1-x Sr x)} (Fe 1-y-z Ti y M z) O 3 (M: Mn, Co, Ni , Cu, 0 ≦ x ≦ 0.05, 0 <y <0.5, 0 <z ≦ 0.1) The solid oxide fuel according to claim 1, Battery.

In order to achieve the above object, according to the seventh aspect of the present invention, there is formed a solid oxide fuel cell comprising an air electrode comprising a group A, an electrolyte comprising a group B, a fuel electrode comprising a group C, and an interconnector. An interconnector material comprising a perovskite oxide in which La and Fe are the main components and less than 50 mol% of Fe is replaced by Cr or Ti. Group A: ABO ₃ (A: Alkali excluding Mg An earth metal, a lanthanoid excluding Ce, at least one selected from Sc and Y, and B: at least one selected from Cr, Mn, Fe, Co, Ni, Cu, Al, and Mg)
Group B: Provided is a complex of at least one selected from stabilized zirconia, ceria-based solid solution, and lanthanum gallate, C group: at least one selected from Ni, Co, Cu, and Fe, and at least one selected from Group B .

According to the invention of claim 8, wherein in order to achieve the above object, the general formula _{(La 1-x Sr x)} (Fe 1-y Cr y) O 3 (0 ≦ x ≦ 0.1,0 <y The interconnector material of Claim 7 represented by <0.5) is provided.

According to the invention of claim 9, wherein in order to achieve the above object, the general formula _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) O 3 (M: Mn, Co, Ni , Cu, 0 ≦ x ≦ 0.05, 0 <y <0.5, 0 <z ≦ 0.1).

According to the invention of claim 10, wherein in order to achieve the above object, the general formula _{(La 1-x Sr x)} (Fe 1-y Ti y) O 3 (0 ≦ x ≦ 0.1,0 <y The interconnector material according to claim 7, represented by <0.5).

In order to achieve the above object, according to the invention of claim 11, the general formula is (La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ (M: Mn, Co, Ni , Cu, 0 ≦ x ≦ 0.05, 0 <y <0.5, 0 <z ≦ 0.1).

According to the present invention, it is possible to co-fire at least one electrode and the interconnector in the production of the solid oxide fuel cell by the interconnector having high sinterability.

  Embodiments of the present invention will be described below.

  A solid oxide fuel cell is composed of four members: an air electrode, an electrolyte, a fuel electrode, and an interconnector.

Since the air electrode of a solid oxide fuel cell is required to have high temperature, stability in an oxidizing atmosphere and high electronic conductivity, the general formula ABO ₃ (A: alkaline earth metal excluding Mg, Ce A perovskite oxide represented by at least one selected from lanthanoids, Sc, and Y, and B: at least one selected from Cr, Mn, Fe, Co, Ni, Cu, Al, and Mg). Above all, based on LaMnO ₃ , LaCoO ₃ , LaFeO ₃ , each A site is substituted with at least one selected from alkaline earth metals excluding Mg, lanthanoids excluding La and Ce, Sc and Y, and each B site Are substituted with at least one selected from Cr, Mn, Fe, Co, Ni, Cu, Al, and Mg. The air electrode is required to have a porosity of 20 to 40% because gas diffusibility and high catalytic activity are required. When the air electrode material is molded or formed into a film by a firing method, the firing temperature is preferably 1000 ° C. or more and 1500 ° C. or less, and if it exceeds 1500 ° C., it is difficult for any material to maintain the porosity.

The electrolyte of the solid oxide fuel cell is required to have stability in both high temperature and redox atmospheres and high ionic conductivity, and therefore, stabilized zirconia, ceria-based solid solution, and lanthanum gallate are used. The stabilized zirconia in this specification is a general term for zirconia substituted with a metal having a valence different from that of zirconium. As the stabilizing material for stabilized zirconia, at least one of Ca, Mg and rare earth elements is used, and the amount of substitution is generally 2 to 20 mol% as an oxide with respect to 1 mol of stabilized zirconia. . Among these, stabilized zirconia substituted with Y and Sc is preferable because it has high ionic conductivity. The ceria-based solid solution in the present specification is a general term for ceria substituted with rare earth elements having different valences, like the stabilized zirconia. As the ceria-based solid solution dopant, at least one of lanthanoids excluding Ca, Mg, Zr, and Ce is used, and the substitution amount is generally 10 to 40 mol%. Among these, ceria substituted by 10 to 20 mol% with Gd, Sm, and Y is preferable because it has high ionic conductivity. As disclosed in JP-A-10-114520, lanthanum gallate in the present specification is a perovskite type based on LaGaO _{3, in} which a part of La is substituted with Sr and a part of Ga is substituted with Mg. A generic term for oxides. Formula is represented by _{(La 1-x Sr x)} (Ga 1-y Mg y) O 3 (0 <x ≦ 0.4,0 <y ≦ 0.4). Further, as disclosed in JP-A-11-335164, a part of the B site of lanthanum gallate may be substituted with any of Co, Fe, Ni, and Cu. General formula _{(La 1-x Sr x)} (Ga 1-y-z Mg y M z) O 3 (0.05 ≦ x ≦ 0.3,0.025 ≦ y ≦ 0.29,0.01 ≦ z ≦ 0.15, 0.025 ≦ y + z ≦ 0.3, M: Co, Fe, Ni, Cu). The electrolyte is required to have gas tightness, and the relative density is preferably 95% or more. When the electrolyte material is molded or formed into a film by a firing method, the firing temperature is required to be 1300 ° C. or higher, and if it exceeds 1500 ° C., the output performance is degraded due to the reaction with the electrode depending on the manufacturing process and the material used Cause.

  Since the fuel electrode of the solid oxide fuel cell is required to have stability in a high temperature, reducing atmosphere and high electronic conductivity, at least one selected from metals Ni, Co, Cu, and Fe A composite with the electrolyte material is used. Among these, Ni is preferable because it is difficult to be oxidized and the fuel utilization rate can be increased. It is said that making some or all of Ni Co effective in suppressing sulfur poisoning, and making some or all Ni Ni Cu or Fe is effective in suppressing carbon deposition. Since the fuel electrode is required to have gas diffusibility and high catalytic activity, a porosity of 20 to 40% is required. When the fuel electrode material is formed or formed by a firing method, an oxide of Ni, Co, Cu, or Fe is used as a metal source, and the firing temperature is preferably 1000 ° C. or more and 1500 ° C. or less, and preferably exceeds 1500 ° C. And it is difficult for any material to maintain the porosity.

Thus, in order to form and form each member excluding the interconnector by the firing method, it is desirable that the firing temperature is 1300 ° C to 1500 ° C. On the other hand, a LaCrO ₃ -based material, which is a conventional interconnector, cannot be sintered unless it is fired at 1600 ° C. or higher or a separate dense layer is not provided. In other words, it is not possible to co-fire the interconnector made of LaCrO ₃ system material and the porous electrode adjacent to the interconnector, but the interconnector made of LaCrO ₃ system material on the porous electrode. It is even impossible to sinter. So, I've looked for a material having a high reduction stability in addition to LaCrO _3-based material, LaFeO ₃ based material was appropriate.

LaFeO ₃ has high sinterability and can be easily sintered at 1400 ° C. or lower. Although not as good as LaCrO ₃ -based materials, the reduction stability is high, and we have confirmed that the oxygen partial pressure at 1000 ° C. is stable up to 1 × 10 ⁻¹⁷ (corresponding to 6% humidified H ₂ gas). If it is possible to widen the oxygen partial pressure 1 × ^(equivalent to ^2% humidified H ₂ gas) 10 ^-18 until a stable region at 1000 ° C. which is the lower limit of the production conditions, it can be used as the interconnector. Therefore, by substituting less than 50% of Fe of LaFeO ₃ with Cr or Ti, a stable material was found even at an oxygen partial pressure of 1 × 10 ⁻¹⁸ or less at 1000 ° C. As a result, even when co-firing with at least one of the electrodes and the electrolyte, an interconnector with high gas tightness and reduction stability can be formed, and a solid oxide fuel cell that does not impair output performance has been produced. When the substitution amount of Cr is 50% or more, in the case of Cr, the sinterability is lowered, and when co-firing with the electrode, a gastight interconnector cannot be produced, so that high output performance cannot be obtained. When the substitution amount of Ti is 50% or more, the electronic conductivity is greatly lowered, and high output performance cannot be obtained.

  The shape of the solid oxide fuel cell in the present invention is preferably a cylindrical vertical stripe type, a cylindrical horizontal stripe type, a flat tube type, or a monolith type. This is because, in any shape, it is difficult to fire only the interconnector and mechanically join it. Here, the shape of the solid oxide fuel cell will be described in detail with reference to the drawings.

  FIG. 1 shows an example of a cylindrical vertical stripe fuel cell 10. An air electrode 1 is used as a support tube, and an electrolyte 2 and a fuel electrode 3 are formed on the outer periphery thereof. The interconnector 4 for current collection is adjacent to the air electrode 1 and extends in the longitudinal direction of the cylinder without contacting the fuel electrode 3. As long as the gas tightness can be secured, the thickness of the interconnector is preferably as thin as possible from the viewpoint of electrical resistance, and is generally 200 μm or less, more preferably 100 μm or less. Since the thickness of the interconnector is thin, it is difficult to fire and interconnect mechanically only the interconnector. The same can be said even if the support tube of the cylindrical vertical stripe fuel cell shown in FIG. 1 is a fuel electrode.

  FIG. 2 shows a cross-sectional view of an example of the cylindrical horizontal stripe fuel cell 11. A fuel electrode 3, an electrolyte 2, and an air electrode 1 are formed on the outer periphery of a porous support tube 5 made of calcia-stabilized zirconia, which becomes a single cell. In single cells, the fuel electrode of the cell adjacent to the air electrode is electrically connected by the interconnector 4. Like the cylindrical vertical stripe type, the interconnector should be thin, and in addition, since the film formation surface is the entire circumference in the circumferential direction, mechanical joining is extremely difficult.

  FIG. 3 shows a cross-sectional view of an example of the flat tube fuel cell 12. The shape is flattened cylindrical vertical stripe fuel cell, and the structure is similar. An air electrode 1 is used as a support tube, and an electrolyte 2 and a fuel electrode 3 are formed on the outer periphery thereof. The interconnector 4 for current collection is adjacent to the air electrode 1 and extends toward the back of the paper without contacting the fuel electrode 3. The interconnector is preferably thin and difficult to mechanically join.

  FIG. 4 shows a cross-sectional view of an example of the monolith type fuel cell 13. Monolith is a generic term for an integral sintered stack. The green sheet in which the air electrode 1, the interconnector 4, and the fuel electrode 3 are laminated, and the green sheet in which the air electrode 1, the electrolyte 2 and the fuel electrode 3 are laminated are folded, and the laminated bodies are alternately stacked, and then integrally fired. Is produced. Similarly, it is preferable that the interconnector is thin, it is difficult to mechanically join, and it is contrary to the co-firing which is the original purpose.

  It should be noted that there is no problem even if the fuel cell described in this specification is a flat plate type fuel cell, and a reduction in man-hours can be expected by co-firing.

In the present invention, a part of La (Fe, Cr) O ₃ in which part of LaFeO ₃ Fe is replaced with Cr may be replaced with an alkaline earth metal such as Sr, or a lanthanoid excluding Sc, Y, and Ce. good. Of these, Sr having an ion radius close to La is most preferable. In the perovskite oxide represented by the general formula (La _1-x Sr _x ) (Fe _1-y Cr _y ) O ₃ , 0 ≦ x ≦ 0.1 and 0 <y <0.5 are preferable. By substituting part of La with Sr, the electronic conductivity can be improved.

Further, in order to improve the electronic conductivity, a part of the B site may be substituted with a transition metal such as Mn. Formula _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) O 3 (M: Mn, Co, Ni, Cu) in the perovskite type oxide represented by, 0 ≦ x ≦ 0 .05, 0 <y <0.5 and 0 <z ≦ 0.1 are preferred.

In the present invention, a part of La (Fe, Ti) O ₃ A site obtained by substituting a part of Fe of LaFeO ₃ with Ti is replaced with an alkaline earth metal such as Sr, and a lanthanoid excluding Sc, Y, and Ce. Also good. Of these, Sr having an ion radius close to La is most preferable. In the perovskite type oxide represented by the general formula (La _1-x Sr _x ) (Fe _1-y Ti _y ) O ₃ , 0 ≦ x ≦ 0.1 and 0 <y <0.5 are preferable. Substitution with Sr improves the electronic conductivity.

Further, in order to improve the electronic conductivity, a part of the B site may be substituted with a transition metal such as Mn. Formula _{(La 1-x Sr x)} (Fe 1-y-z Ti y M z) O 3 (M: Mn, Co, Ni, Cu) in the perovskite type oxide represented by, 0 ≦ x ≦ 0 .05, 0 <y <0.5 and 0 <z ≦ 0.1 are preferred.

Even if La of the base composition LaFeO ₃ is replaced with a lanthanoid excluding Sc, Y, and Ce, reduction resistance comparable to that of LaFeO ₃ can be expected, but La is most preferable in view of material costs. Furthermore, it is conceivable that the same effect can be obtained even when two kinds of Cr and Ti that improve the reduction stability are substituted at the same time.

  Next, a production method and an evaluation method of an interconnector material according to the present invention, and a production method and an evaluation method of a solid oxide fuel cell including the interconnector will be described.

[Sinterability and conductivity evaluation by bulk material]
Various metal oxides other than lanthanum hydroxide and strontium carbonate were used as starting materials for the LaFeO ₃ -based material bulk material. Various starting materials were weighed according to the stoichiometric ratio, water was added and the wet-mixed slurry was dried, and then the powder was calcined at 1100 ° C. for 10 hours. The calcined powder is wet-pulverized until the average particle size is around 1 μm, and the dried powder is uniaxially pressed at a pressure of 200 kgf / cm ² to obtain a green body, which is fired at 1400 ° C. for 2 hours. went. The relative density of the obtained bulk body was calculated by the Archimedes method. The bulk body was exposed to an atmosphere of 1000 ° C. and an oxygen partial pressure of 10 ⁻¹⁸ overnight, and then the surface state was observed to evaluate the reduction stability. The bulk body was measured for conductivity by the direct current four-terminal method in an atmosphere of 1000 ° C., oxygen partial pressure 0.2 and 10 ⁻¹⁸ , and ½ of the sum of the reciprocals of the respective conductivity was calculated as the resistance value. For comparison, powders of La _0.8 Sr _0.2 CrO ₃ and La _0.8 Ca _0.2 CrO ₃ were prepared by spray pyrolysis, and the bulk data of each was described.

[Production of fuel cell and evaluation of power generation]
For the LaFeO ₃ -based material that was determined to have no problem in sinterability and reduction stability in the bulk investigation, a cylindrical vertical stripe type solid oxide fuel cell having the material in an interconnector was produced, A power generation test was conducted. The manufacturing method of the cell is as follows.

(1) Molding of air electrode current collecting layer (support tube) After producing Sr-doped lanthanum manganite represented by La _0.8 Sr _0.2 MnO ₃ by a solid phase method, heat treatment is performed to produce an air electrode. Raw material powder was obtained. The average particle size was 3 μm. The powder is mixed with 100 parts by weight, binder (methylcellulose) 10 parts by weight, solvent (water) 20 parts by weight to obtain a clay, and cylindrical shape so that the thickness after firing is 2 mm using an extrusion method. A molded body was produced.

(2) Film formation of interconnector Various interconnector materials having an average particle diameter of 1 μm were prepared by the solid phase method as described above. After mixing 100 parts by weight of the powder, 40 parts by weight of a solvent (α-terpineol), 10 parts by weight of a binder (polyvinyl butyral) and 1 part by weight of a dispersant (polycarboxylic acid amine), the mixture was sufficiently kneaded to prepare a paste. . An interconnector was formed on the air electrode so that the paste had a thickness of 20 μm after being baked by screen printing.

(3) Film formation of electrolyte Yttria-stabilized zirconia whose composition is represented by (ZrO ₂ ) _0.9 (Y ₂ O ₃ ) _0.1 (hereinafter referred to as YSZ) is prepared by a coprecipitation method and then heat-treated. An electrolyte raw material powder was obtained. The average particle size was 0.5 μm. 40 parts by weight of the powder, 100 parts by weight of a solvent (ethanol), 2 parts by weight of a binder (ethyl cellulose), 1 part by weight of a dispersant (polyoxyethylene alkyl phosphate ester), 1 part by weight of an antifoaming agent (sorbitan sesquiolate) After mixing, the slurry was prepared by sufficiently stirring. Using the slurry, a film was formed on the air electrode using a slurry coating method so that the film thickness after firing was 30 μm.

(4) Co-firing of air electrode / interconnector / electrolyte The air electrode supporting tube on which the interconnector and the electrolyte were formed was fired. The firing conditions were 1400 ° C. and 2 hours.

(5) Film Formation and Firing of Fuel Electrode A mixture of NiO powder and YSZ powder was prepared by a wet mixing method and then heat-treated to obtain a fuel electrode raw material powder. The mixing ratio of NiO and YSZ was 70:30 by weight. The average particle size was 3 μm. 100 parts by weight of the powder, 500 parts by weight of a solvent (ethanol), 20 parts by weight of a binder (ethyl cellulose), 5 parts by weight of a dispersant (polyoxyethylene alkyl phosphate ester), 1 part by weight of an antifoaming agent (sorbitan sesquiolate), plastic After mixing 5 parts by weight of the agent (dibutyl phthalate), the slurry was prepared by sufficiently stirring. The slurry was formed into a film on the fuel side electrode reaction layer by using a slurry coating method on the fuel side current collecting layer. Thereafter, baking was performed at 1350 ° C. for 2 hours. The film thickness after firing was 100 μm.

The power generation conditions of the produced fuel cell were 1000 ° C., 0.3 A / cm ² , FU 80%, fuel gas: 3% humidified hydrogen, and oxidizing gas: air. As a comparison, a fuel cell using La _0.8 Sr _0.2 CrO ₃ and La _0.8 Ca _0.2 CrO ₃ as an interconnector was prepared, and data was described. In either case, the film thickness was 20 μm.

With Example 1 from 12 and Comparative Examples 1 to 8, _was investigated proper range of the x and y values in the _{(La 1-x Sr x)} (Fe 1-y Cr y) O 3.

[Example 1]
Prepared in _{(La 1-x Sr x)} (Fe 1-y Cr y) x in _{O 3} = 0, y = 0.1 and powder said method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 2]
Prepared in _{(La 1-x Sr x)} (Fe 1-y Cr y) x in _{O 3} = 0, y = 0.2 and powder said method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 3]
Prepared in _{(La 1-x Sr x)} (Fe 1-y Cr y) x in _{O 3} = 0, y = 0.3 and powder said method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 4]
Prepared in _{(La 1-x Sr x)} (Fe 1-y Cr y) x in _{O 3} = 0, y = 0.4 and powder said method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 5]
_{(La 1-x Sr x)} (Fe 1-y Cr y) O 3 in x = 0.05, the powder was y = 0.1 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 6]
_{(La 1-x Sr x)} (Fe 1-y Cr y) O 3 in x = 0.05, the powder was y = 0.2 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 7]
_{(La 1-x Sr x)} (Fe 1-y Cr y) O 3 in x = 0.05, the powder was y = 0.3 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 8]
_{(La 1-x Sr x)} (Fe 1-y Cr y) O 3 in x = 0.05, the powder was y = 0.4 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 9]
_{(La 1-x Sr x)} (Fe 1-y Cr y) O 3 in x = 0.1, the powder was y = 0.1 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 10]
_{(La 1-x Sr x)} (Fe 1-y Cr y) x in _{O 3} = 0.1, the powder was y = 0.2 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 11]
_{(La 1-x Sr x)} (Fe 1-y Cr y) x in _{O 3} = 0.1, the powder was y = 0.3 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 12]
_{(La 1-x Sr x)} (Fe 1-y Cr y) x in _{O 3} = 0.1, the powder was y = 0.4 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Comparative Example 1]
(La _0.8 Sr _0.2 ) CrO ₃ powder was prepared by the above method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Comparative Example 2]
(La _0.8 Ca _0.2 ) CrO ₃ powder was prepared by the above method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Comparative Example 3]
Prepared in _{(La 1-x Sr x)} (Fe 1-y Cr y) x in _{O 3} = 0, y = 0 and powder said method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Comparative Example 4]
Prepared in _{(La 1-x Sr x)} (Fe 1-y Cr y) x in _{O 3} = 0, y = 0.5 and powder said method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Comparative Example 5]
_{(La 1-x Sr x)} (Fe 1-y Cr y) O 3 in x = 0.05, the powder with y = 0 was made by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Comparative Example 6]
_{(La 1-x Sr x)} (Fe 1-y Cr y) O 3 in x = 0.05, the powder was y = 0.5 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Comparative Example 7]
_{(La 1-x Sr x)} (Fe 1-y Cr y) x in _{O 3} = 0.1, the powder was y = 0 was made by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Comparative Example 8]
_{(La 1-x Sr x)} (Fe 1-y Cr y) x in _{O 3} = 0.1, the powder was y = 0.5 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

  The survey results of Examples 1 to 12 and Comparative Examples 1 to 8 are summarized in Table 1.

Table 1 _shows the relative density and reducing the stability of the _{(La 1-x Sr x)} (Fe 1-y Cr y) O 3 bulk. A relative density of 95% or more was secured up to a Cr content of 0.4. In addition, reduction stability could be ensured by replacing with Cr. (La _1-x Sr _x ) FeO ₃ not substituted with Cr was powdered after exposure to a reducing atmosphere overnight, and reduction stability could not be ensured. On the other hand, La _0.8 Ca _0.2 CrO ₃ which is an existing material can secure a relative density of 95%, but La _0.8 Sr _0.2 CrO ₃ hardly undergoes sintering. Of the present invention _{(La 1-x Sr x)} (Fe 1-y Cr y) O 3 was shown to be excellent in sinterability than _La 0.8 _Sr 0.2 CrO ₃ in bulk.

Table 1 shows the resistivity calculated from the conductivity. When the amount of Cr increases, the resistivity tends to increase slightly, which is considered to be due to the difference in porosity. In addition, the resistivity tends to decrease as the amount of Sr increases. _{(La 1-x Sr x)} (Fe 1-y Cr y) resistivity of _{O 3} of the present invention was about 1～2Omucm. The resistivity of La _0.8 Ca _0.2 CrO ₃ which is an existing material is _0.2 Ωcm, which is smaller than (La _1-x Sr _x ) (Fe _1-y Cr _y ) O _{3 of} the present invention. there were. When the influence of the cell potential drop is calculated from the calculated difference in resistivity, when the interconnector film thickness is 20 μm, the difference in potential drop of the cylindrical cell when a current of 0.3 A / cm ² is passed is 4 to 8 mV. From this, it is presumed that the output performance is not greatly affected.

Table 1 _shows the potential at the power generation condition of _{(La 1-x Sr x)} (Fe 1-y Cr y) fuel cell of _{O 3} was interconnector. Good results of 0.6 V or more could be obtained until the Cr amount was 0.4, but the potential was greatly reduced when the Cr amount was 0.5. This is due to a decrease in gas tightness due to a decrease in sinterability. On the other hand, in the fuel cell using the existing materials La _0.8 Sr _0.2 CrO ₃ and La _0.8 Sr _0.2 CrO ₃ as an interconnector, it was not possible to generate power under the power generation conditions. This is because a gastight interconnector could not be produced. It than, the present invention _{(La 1-x Sr x)} (Fe 1-y Cr y) O 3 even in any composition, is a good material for the interconnector for co-firing and than the existing material electrode or Is clear. Also in _{(La 1-x Sr x)} (Fe 1-y Cr y) O 3, the value of the more preferred x and y is 0 ≦ x ≦ 0.1,0.1 ≦ y ≦ 0.4.

With Example 16 from 30, and Comparative Examples 1,2,3,5,7 and 9 to _11, appropriateness of x and y values in the _{(La 1-x Sr x)} (Fe 1-y Ti y) O 3 The range was investigated.

[Example 13]
Prepared in _{(La 1-x Sr x)} (Fe 1-y Ti y) x in _{O 3} = 0, y = 0.1 and powder said method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 14]
Prepared in _{(La 1-x Sr x)} (Fe 1-y Ti y) x in _{O 3} = 0, y = 0.2 and powder said method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 15]
Prepared in _{(La 1-x Sr x)} (Fe 1-y Ti y) x in _{O 3} = 0, y = 0.3 and powder said method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 16]
Prepared in _{(La 1-x Sr x)} (Fe 1-y Ti y) x in _{O 3} = 0, y = 0.4 and powder said method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 17]
_{(La 1-x Sr x)} (Fe 1-y Ti y) O 3 in x = 0.05, the powder was y = 0.1 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 18]
_{(La 1-x Sr x)} (Fe 1-y Ti y) O 3 in x = 0.05, the powder was y = 0.2 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 19]
_{(La 1-x Sr x)} (Fe 1-y Ti y) O 3 in x = 0.05, the powder was y = 0.3 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 20]
_{(La 1-x Sr x)} (Fe 1-y Ti y) O 3 in x = 0.05, the powder was y = 0.4 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 21]
_{(La 1-x Sr x)} (Fe 1-y Ti y) O 3 in x = 0.1, the powder was y = 0.1 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 22]
_{(La 1-x Sr x)} (Fe 1-y Ti y) x in _{O 3} = 0.1, the powder was y = 0.2 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 23]
_{(La 1-x Sr x)} (Fe 1-y Ti y) x in _{O 3} = 0.1, the powder was y = 0.3 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 24]
_{(La 1-x Sr x)} (Fe 1-y Ti y) x in _{O 3} = 0.1, the powder was y = 0.4 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Comparative Example 9]
Prepared in _{(La 1-x Sr x)} (Fe 1-y Ti y) x in _{O 3} = 0, y = 0.5 and powder said method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Comparative Example 10]
_{(La 1-x Sr x)} (Fe 1-y Ti y) O 3 in x = 0.05, the powder was y = 0.5 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Comparative Example 11]
_{(La 1-x Sr x)} (Fe 1-y Ti y) x in _{O 3} = 0.1, the powder was y = 0.5 was prepared by the method. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

  The survey results of Examples 16 to 30 and Comparative Examples 1, 2, 3, 5, 7, and 9 to 11 are summarized in Table 2.

Table 2 _shows the relative density and reducing the stability of the _{(La 1-x Sr x)} (Fe 1-y Ti y) O 3 bulk. Regardless of the amount of Ti, a relative density of 95% or more could be secured, and reduction stability could be secured. Of the present invention _{((La 1-x Sr x} ) (Fe 1-y Ti y) O 3 was shown to be excellent in sinterability than _La 0.8 _Sr 0.2 CrO ₃ in bulk.

Table 2 shows the resistivity calculated from the conductivity. It can be seen that the resistivity increases as the amount of Ti increases. It can also be seen that the resistivity decreases as the amount of Sr increases. _{(La 1-x Sr x)} (Fe 1-y Cr y) resistivity of _{O 3} of the present invention was about 1～5Omucm. The resistivity of La _0.8 Ca _0.2 CrO ₃ which is an existing material is _0.2 Ωcm, which is smaller than (La _1-x Sr _x ) (Fe _1-y Cr _y ) O _{3 of} the present invention. there were. When the influence of the cell potential drop is calculated from the calculated difference in resistivity, when the interconnector film thickness is 20 μm, the difference in potential drop of the cylindrical cell when a current of 0.3 A / cm ² is passed is 4 to 20 mV. From this, it is presumed that the output performance is not greatly affected. On the other hand, when the amount of Ti is 0.5, the resistivity is 20 to 30 Ωcm, and the potential drop is calculated to be 120 mV at the maximum.

Table 2 shows the potentials of the fuel cells using (La _1-x Sr _x ) (Fe _1-y Ti _y ) O ₃ as interconnectors under the above power generation conditions. A good result of 0.6 V or more could be obtained until the Ti amount was 0.4, but when the Ti amount was 0.5, the potential was greatly reduced. This is due to a decrease in electronic conductivity. From the above, the present invention _{(La 1-x Sr x)} (Fe 1-y Ti y) O 3 is found to be good materials for interconnector than existing materials in any of the composition. Also in _{(La 1-x Sr x)} (Fe 1-y Cr y) O 3, the value of the more preferred x and y is 0 ≦ x ≦ 0.1,0.1 ≦ y ≦ 0.4.

With 62 from Example _31, was examined _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) type M at _{O 3} and x, y, a proper range of z values.

[Example 25]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ M = Mn, x = 0, y = 0.1, z = 0.05 was produced by the above method. did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 26]
Prepared in _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) M in _{O 3 = Mn, x = 0} , y = 0.1, z = 0.1 and powder said method did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 27]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ M = Co, x = 0, y = 0.1, z = 0.05 was produced by the above method. did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 28]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ powder with M = Co, x = 0, y = 0.1, z = 0.1 was prepared by the above method. did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 29]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ M = Ni, x = 0, y = 0.1, z = 0.05 was produced by the above method. did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 30]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ powder with M = Ni, x = 0, y = 0.1, z = 0.1 was prepared by the above method. did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 31]
Prepared in _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) M in _{O 3 = Cu, x = 0} , y = 0.1, z = 0.05 and powder said method did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 32]
Prepared in _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) M in _{O 3 = Cu, x = 0} , y = 0.1, z = 0.1 and powder said method did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 33]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ M = Mn, x = 0.05, y = 0.1, z = 0.05 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 34]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ M = Mn, x = 0.05, y = 0.1, z = 0.1 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 35]
_{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) M = Co in _{O 3, x = 0.05, y} = 0.1, the method powder with z = 0.05 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 36]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ M = Co, x = 0.05, y = 0.1, z = 0.1 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 37]
_{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) M = Ni in _{O 3, x = 0.05, y} = 0.1, the method powder with z = 0.05 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 38]
_{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) M in _{O 3 = Ni, x = 0.05} , y = 0.1, the method powder with z = 0.1 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 39]
_{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) M = Cu in _{O 3, x = 0.05, y} = 0.1, the method powder with z = 0.05 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 40]
_{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) M = Cu in _{O 3, x = 0.05, y} = 0.1, the method powder with z = 0.1 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 41]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ M = Mn, x = 0, y = 0.4, z = 0.05 was produced by the above method. did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 42]
Prepared in _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) M in _{O 3 = Mn, x = 0} , y = 0.4, z = 0.1 and powder said method did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 43]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ powder with M = Co, x = 0, y = 0.4, z = 0.05 was prepared by the above method. did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 44]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ M = Co, x = 0, y = 0.4, z = 0.1 did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 45]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ M = Ni, x = 0, y = 0.4, z = 0.05 was produced by the above method. did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 46]
Prepared in _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) M in _{O 3 = Ni, x = 0} , y = 0.4, z = 0.1 and powder said method did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 47]
Prepared in _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) M in _{O 3 = Cu, x = 0} , y = 0.4, z = 0.05 and powder said method did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 48]
Prepared in _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) M in _{O 3 = Cu, x = 0} , y = 0.4, z = 0.1 and powder said method did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 49]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ M = Mn, x = 0.05, y = 0.4, z = 0.05 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 50]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ M = Mn, x = 0.05, y = 0.4, z = 0.1 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 51]
_{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) M = Co in _{O 3, x = 0.05, y} = 0.4, the method powder with z = 0.05 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 52]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ M = Co, x = 0.05, y = 0.4, z = 0.1 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 53]
_{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) M = Ni in _{O 3, x = 0.05, y} = 0.4, the method powder with z = 0.05 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 54]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ M = Ni, x = 0.05, y = 0.4, z = 0.1 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 55]
_{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) M = Cu in _{O 3, x = 0.05, y} = 0.4, the method powder with z = 0.05 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 56]
(La _1-x Sr _x ) (Fe _1-yz Cr _y M _z ) O ₃ M = Cu, x = 0.05, y = 0.4, z = 0.1 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

  The survey results of Examples 31 to 62 are summarized in Table 3.

Table 3 _shows the _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) relative density and reducing the stability of the _{O 3} bulk. Regardless of the amount of Cr, amount of M, and type of M, a relative density of 95% or more could be secured, and reduction stability could be secured. Moreover, the improvement of sinterability was also seen by adding Co and Cu.

Table 3 shows the resistivity calculated from the conductivity. Regardless of the amount of Sr and the amount of Cr, it can be seen that the resistivity decreases by adding the transition metal M. _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) resistivity of _{O 3} of the present invention was about 0.5～1.1Omucm.

Table 3 _shows the potential at the power generation condition of _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) fuel cell of _{O 3} was interconnector. By adding the transition metal M, the potential of the fuel cell was generally improved. It is thought that the improvement in electronic conductivity is affecting. Exceptions include (La _0.95 Sr _0.05 ) (Fe _0.8 Cr _0.1 Cu _0.1 ) O ₃ and (La _0.95 Sr _0.05 ) (Fe _0.8 Cr _0.1 Ni _{In 0.1} ) O ₃ , the potential decreased compared to that without substitution, but the electromotive force of the sample was slightly lower than the others, but the cause was that the ionic conductivity was slightly higher. I guess. It is clear that a good material as the interconnector over existing material even in _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) O 3 is any composition of the above, the present invention . Further, more preferable values of x, y, and z are 0 ≦ x ≦ 0.05, 0.1 ≦ y ≦ 0.4, 0 ≦ z ≦ 0.1 (M: Mn), and 0 ≦ z ≦ 0.05. (M: Co, Ni, Cu).

With 94 from Example _63, was examined _{(La 1-x Sr x)} (Fe 1-y-z Ti y M z) type M at _{O 3} and x, y, a proper range of z values.

[Example 57]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Mn, x = 0, y = 0.1, z = 0.05 was produced by the above method. did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 58]
Prepared in _{(La 1-x Sr x)} (Fe 1-y-z Ti y M z) M in _{O 3 = Mn, x = 0} , y = 0.1, z = 0.1 and powder said method did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 59]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Co, x = 0, y = 0.1, z = 0.05 was produced by the above method. did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 60]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Co, x = 0, y = 0.1, z = 0.1 Powder produced by the above method did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 61]
Prepared in _{(La 1-x Sr x)} (Fe 1-y-z Ti y M z) M in _{O 3 = Ni, x = 0} , y = 0.1, z = 0.05 and powder said method did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 62]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Ni, x = 0, y = 0.1, z = 0.1 did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 63]
Prepared in _{(La 1-x Sr x)} (Fe 1-y-z Ti y M z) M in _{O 3 = Cu, x = 0} , y = 0.1, z = 0.05 and powder said method did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 64]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Cu, x = 0, y = 0.1, z = 0.1 Powder produced by the above method did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 65]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Mn, x = 0.05, y = 0.1, z = 0.05 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 66]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Mn, x = 0.05, y = 0.1, z = 0.1 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 67]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Co, x = 0.05, y = 0.1, z = 0.05 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 68]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Co, x = 0.05, y = 0.1, z = 0.1 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 69]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Ni, x = 0.05, y = 0.1, z = 0.05 It was produced with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 70]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Ni, x = 0.05, y = 0.1, z = 0.1 It was made with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 71]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Cu, x = 0.05, y = 0.1, z = 0.05 It was made with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 72]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Cu, x = 0.05, y = 0.1, z = 0.1 It was made with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 73]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Mn, x = 0, y = 0.4, z = 0.05 was produced by the above method. did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 74]
Prepared in _{(La 1-x Sr x)} (Fe 1-y-z Ti y M z) M in _{O 3 = Mn, x = 0} , y = 0.4, z = 0.1 and powder said method did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 75]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Co, x = 0, y = 0.4, z = 0.05 was produced by the above method. did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 76]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Co, x = 0, y = 0.4, z = 0.1 did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 77]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Ni, x = 0, y = 0.4, z = 0.05 was produced by the above method. did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 78]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Ni, x = 0, y = 0.4, z = 0.1 did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 79]
Prepared in _{(La 1-x Sr x)} (Fe 1-y-z Ti y M z) M in _{O 3 = Cu, x = 0} , y = 0.4, z = 0.05 and powder said method did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 80]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Cu, x = 0, y = 0.4, z = 0.1 did. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 81]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Mn, x = 0.05, y = 0.4, z = 0.05 It was made with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 82]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Mn, x = 0.05, y = 0.4, z = 0.1 It was made with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 83]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Co, x = 0.05, y = 0.4, z = 0.05 It was made with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 84]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Co, x = 0.05, y = 0.4, z = 0.1 It was made with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 85]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Ni, x = 0.05, y = 0.4, z = 0.05 It was made with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 86]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Ni, x = 0.05, y = 0.4, z = 0.1 It was made with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 87]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Cu, x = 0.05, y = 0.4, z = 0.05 It was made with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

[Example 88]
(La _1-x Sr _x ) (Fe _1-yz Ti _y M _z ) O ₃ M = Cu, x = 0.05, y = 0.4, z = 0.1 It was made with. According to the said method, evaluation of the bulk body and evaluation of the fuel cell were performed.

The survey results of Examples 63 to 94 are summarized in Table 4.

Table 4 _shows the _{(La 1-x Sr x)} (Fe 1-y-z Ti y M z) relative density and reducing the stability of the _{O 3} bulk. Regardless of the amount of Ti, amount of M, and type of M, a relative density of 95% or more could be secured, and reduction stability could be secured. Moreover, the improvement of sinterability was also seen by substituting Co and Cu.

Table 4 shows the resistivity calculated from the conductivity. Regardless of the amount of Sr and the amount of Ti, it can be seen that the resistivity decreases by adding the transition metal M. _{(La 1-x Sr x)} (Fe 1-y-z Ti y M z) resistivity of _{O 3} of the present invention was about 0.5～1.3Omucm.

Table 4 _shows the potential at the power generation condition of _{(La 1-x Sr x)} (Fe 1-y-z Ti y M z) fuel cell of _{O 3} was interconnector. By adding the transition metal M, the potential of all the fuel cells was improved. It is thought that the improvement in electronic conductivity is affecting. It is clear that a good material as the interconnector over existing material even in _{(La 1-x Sr x)} (Fe 1-y-z Ti y M z) O 3 is any composition of the above, the present invention . Further, more preferable values of x, y, and z are 0 ≦ x ≦ 0.05, 0.1 ≦ y ≦ 0.4, 0 ≦ z ≦ 0.1 (M: Mn), and 0 ≦ z ≦ 0.05. (M: Co, Ni, Cu).

It is a figure which shows the cylindrical vertical stripe fuel cell which concerns on one example of this invention. It is a figure which shows the cylindrical horizontal stripe type fuel cell which concerns on one example of this invention. It is a figure which shows the flat tube type fuel cell which concerns on one example of this invention. It is a figure which shows the monolith type fuel cell which concerns on one example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Air electrode 2 ... Electrolyte 3 ... Fuel electrode 4 ... Interconnector 5 ... Porous base tube 10 ... Cylindrical vertical stripe type fuel cell 11 ... Cylindrical horizontal stripe type fuel cell 12 ... Flat tube type fuel cell 13 ... Monolith type fuel cell

Claims (11)

An air electrode composed of Group A, an electrolyte composed of Group B, a fuel electrode composed of Group C, and an interconnector composed of a perovskite oxide in which La and Fe are the main components and less than 50 mol% of Fe is replaced with Cr or Ti. A solid oxide fuel cell provided.
Group A: ABO ₃ (A: alkaline earth metal excluding Mg, lanthanoid excluding Ce, Sc, Y, B: selected from Cr, Mn, Fe, Co, Ni, Cu, Al, Mg At least one)
Group B: at least one selected from stabilized zirconia, ceria-based solid solution, lanthanum gallate C group: a composite of at least one selected from Ni, Co, Cu, Fe and at least one selected from Group B 2. The solid oxide fuel cell according to claim 1, wherein the solid oxide fuel cell is any one of a cylindrical vertical stripe type, a cylindrical horizontal stripe type, a flat tube type, and a monolith type. Claim comprising the general formula of _{(La 1-x Sr x)} (Fe 1-y Cr y) O 3 (0 ≦ x ≦ 0.1,0 <y <0.5) interconnector material expressed by 3. The solid oxide fuel cell according to 1 or 2. General formula _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) O 3 (M: Mn, Co, Ni, Cu, 0 ≦ x ≦ 0.05,0 <y <0. The solid oxide fuel cell according to claim 1, further comprising an interconnector material represented by 5, 0 <z ≦ 0.1). Claim comprising the general formula of _{(La 1-x Sr x)} (Fe 1-y Ti y) O 3 (0 ≦ x ≦ 0.1,0 <y <0.5) interconnector material expressed by 3. The solid oxide fuel cell according to 1 or 2. General formula _{(La 1-x Sr x)} (Fe 1-y-z Ti y M z) O 3 (M: Mn, Co, Ni, Cu, 0 ≦ x ≦ 0.05,0 <y <0. The solid oxide fuel cell according to claim 1, further comprising an interconnector material represented by 5, 0 <z ≦ 0.1). An interconnector material for forming a solid oxide fuel cell composed of an air electrode composed of a group A, an electrolyte composed of a group B, a fuel electrode composed of a group C, and an interconnector, comprising La and Fe as main components An interconnector material comprising a perovskite oxide in which less than 50 mol% of Fe is replaced by Cr or Ti.
Group A: ABO ₃ (A: alkaline earth metal excluding Mg, lanthanoid excluding Ce, Sc, Y, B: selected from Cr, Mn, Fe, Co, Ni, Cu, Al, Mg At least one)
Group B: at least one selected from stabilized zirconia, ceria-based solid solution, and lanthanum gallate C group: a composite of at least one selected from Ni, Co, Cu, and Fe and at least one selected from Group B Interconnector of claim 7 of the general formula expressed by _{(La 1-x Sr x)} (Fe 1-y Cr y) O 3 (0 ≦ x ≦ 0.1,0 <y <0.5) material. General formula _{(La 1-x Sr x)} (Fe 1-y-z Cr y M z) O 3 (M: Mn, Co, Ni, Cu, 0 ≦ x ≦ 0.05,0 <y <0. The interconnector material according to claim 7, represented by 5, 0 <z ≦ 0.1). The general formula _{(La 1-x Sr x)} (Fe 1-y Ti y) O 3 (0 ≦ x ≦ 0.1,0 <y <0.5) according to claim 7 represented by represented by The interconnector material described. General formula _{(La 1-x Sr x)} (Fe 1-y-z Ti y M z) O 3 (M: Mn, Co, Ni, Cu, 0 ≦ x ≦ 0.05,0 <y <0. The interconnector material according to claim 7, represented by 5, 0 <z ≦ 0.1).

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