KR101260856B1 - Dual layer interconnect for solid oxide fuel cell, solid oxide fuel cell therewith and preparation method thereof - Google Patents

Abstract

The present invention has a double layer structure of an n-type conductor layer and a p-type conductor layer, and is easy to manufacture thin and compact, and has a high electrical conductivity in both the reducing atmosphere of the anode and the oxidation atmosphere of the cathode. It relates to a solid oxide fuel cell comprising and a method of manufacturing the same.

Description

Dual layer connector for solid oxide fuel cell, solid oxide fuel cell comprising same and method for manufacturing same {DUAL LAYER INTERCONNECT FOR SOLID OXIDE FUEL CELL, SOLID OXIDE FUEL CELL THEREWITH AND PREPARATION METHOD THEREOF}

The present invention relates to a double layer connector for a solid oxide fuel cell, a solid oxide fuel cell including the same, and a method for manufacturing the same. More specifically, the n-type conductor layer and the p-type conductor layer are made of thin and dense connectors. The present invention relates to a double layer connector for a solid oxide fuel cell having high electrical conductivity in both a reduction atmosphere of an anode and an oxidation atmosphere of an anode, a solid oxide fuel cell including the same, and a manufacturing method thereof.

Solid Oxide Fuel Cell (SOFC) uses solid ceramic as an electrolyte to generate electricity by electrochemical reaction between fuel (H ₂ , CH _4, etc.) and air (oxygen) at high temperature of 600 ~ 1000 ℃. As a fuel cell to be produced, there is an advantage in generating power generation efficiency and excellent economic efficiency among the existing power generation technology.

SOFC can be manufactured in various types of cells such as flat, cylindrical, and flat tubes because the electrolyte and the electrode are in a solid state, and the anode support type, the cathode support type, and the electrolyte support according to the fuel cell support. Classified as

Flat type SOFCs have high power density, high productivity, and thin electrolyte, but require gas sealing using a separate sealant, and due to chromium volatilization, there is a problem of deteriorating electrode efficiency due to the use of metal connecting materials at high temperatures. However, it has a disadvantage of lacking reliability due to low resistance to thermal cycles. Moreover, since flat panel SOFCs are not only difficult to manufacture large-area cells but also easy to manufacture large-capacity stacks, solving these problems becomes a key to practical use.

In the case of cylindrical and flat SOFCs, gas sealing is not required, mechanical strength is excellent, and reliability has been verified in various test items. However, there is a disadvantage in that the output density is lower than the flat SOFC.

The above-described flat or cylindrical SOFC stack is manufactured by sequentially forming an anode, an electrolyte layer, an anode and a connector on the anode support.

In SOFCs, interconnects are a key component of flat and cylindrical SOFCs that electrically connect unit cells and separate fuel and air. Splicer materials for SOFCs must meet the requirements of high electronic conductivity, chemical stability in an oxidizing / reducing atmosphere, low reactivity with other materials and similar coefficients of thermal expansion, low gas permeability.

Conventional techniques as Korea Patent Registration No. No. 283 207 In the LaCrO ₃ as a Cr sintered alloy containing 5 to 25% by volume, solid-oxide, characterized by yirueojim the grain boundaries of the Cr particles with the metal microstructure of the dispersed type LaCrO ₃ particles Disclosed is a metal connecting material for a fuel cell.

The use of a ceramic connector has the advantage of suppressing cathode poisoning caused by chromium volatilization and increased contact resistance due to oxide film formation of existing metal materials. As a conventional ceramic connector material for a solid oxide fuel cell, a LaCrO ₃ based oxide doped with calcium (Ca) or strontium (Sr) is used. However, doped LaCrO ₃ has a disadvantage in that it is difficult to manufacture a thin and dense connector layer having a thickness of several tens to several tens of micrometers, and has a p-type conductor characteristic, and thus shows very low electrical conductivity in a reducing atmosphere in which the anode of the fuel cell is exposed.

The present inventors have made diligent efforts to develop a technology capable of overcoming the technical limitations of the conventional solid oxide fuel cell connector, and as a result, it is easy to manufacture a thin and dense connector, and the electric A high conductivity conductor, a solid oxide fuel cell using the same, and a manufacturing method thereof have been developed.

SUMMARY OF THE INVENTION The present invention provides a thin, dense, double layer connector for a solid oxide fuel cell having high electrical conductivity in both a reducing atmosphere of an anode and an oxidation atmosphere of an anode, a solid oxide fuel cell including the same, and a method of manufacturing the same.

In order to achieve the above object, the present invention is a solid oxide fuel cell comprising a fuel electrode support, an electrolyte, a cathode and a double layer connector,

The bilayer interconnector is a part of Sr is substituted with one or more elements selected from La, Y, Ce, Pr, Nd, Sm, Gd and Pm or a part of Ti is Co, Mn, Fe, Cr, Cu, V, Ni, Zn, An n-type conductor layer formed of SrTiO ₃ oxide of perovskite structure substituted with one or more elements selected from Ag, Au, Pt, Pd, Mo, W, and Si; And

A part of La is substituted with at least one element selected from Sr, Ca, Ba and Mg, or a part of Mn is Co, Mn, Fe, Cr, Cu, V, Ni, Zn, Ag, Au, Pt, Pd, Mo, W and Provided is a solid oxide fuel cell comprising a p-type conductor layer formed of a LaMnO ₃ oxide having a perovskite structure substituted with at least one element selected from Si.

In one embodiment of the present invention, the n-type conductor layer is formed to a thickness of 2 to 20 ㎛, the p-type conductor layer is formed to a thickness of 3 to 48 ㎛, the total thickness of the double layer connector is 5-50 ㎛ It is preferable to form.

In another aspect, the present invention comprises the steps of extruding the anode support, followed by drying and sintering; Coating and drying an electrolyte layer on the anode support; Coating and drying an n-type conductor layer of a double layer connector on a surface of the anode support; Coating and drying a p-type conductor layer of a double layer connector on the surface of the n-type conductor layer; Sintering the anode support coated with the electrolyte layer and the double layer connector; And it provides a method for producing a solid oxide fuel cell comprising the step of coating, drying and sintering the cathode.

In one embodiment of the present invention, the n-type conductor layer is a portion of Sr is substituted with one or more elements selected from La, Y, Ce, Pr, Nd, Sm, Gd and Pm or Ti portion of Co, Mn, Fe Pastes of perovskite-structured SrTiO ₃ oxides, binders and solvents substituted with at least one element selected from Cr, Cu, V, Ni, Zn, Ag, Au, Pt, Pd, Mo, W and Si It can be formed by coating.

In one embodiment of the present invention, the p-type conductor layer is a part of La is substituted with at least one element selected from Sr, Ca, Ba and Mg, or a part of Mn is Co, Mn, Fe, Cr, Cu, V, Ni , Zn, Ag, Au, Pt, Pd, Mo, W and Si may be formed by coating a paste of a mixture of LaMnO ₃ oxide, a binder and a solvent of the perovskite structure substituted with one or more elements selected from.

The binder may be mixed in an amount of 3 to 20 parts by weight based on 100 parts by weight of the oxide, and the solvent may be mixed in an amount of 40 to 120 parts by weight based on 100 parts by weight of the oxide.

As the binder, ethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, polyvinyl alcohol, polyvinyl butyral, and the like may be used. Can be used.

The solvent may include, but is not limited to, α-terpinol, ethyl alcohol, toluene, amyl alcohol, butyl alcohol, ethyl lactate, isopropyl alcohol, ethanol, acetone, ethylel glycol, and the like.

Unlike the conventional solid oxide fuel cell connector, the present invention can be manufactured thinly and densely with a thickness of several tens to several micrometers, and has a high electrical conductivity in both the reducing atmosphere of the anode and the oxidation atmosphere of the cathode, and the solid oxide fuel cell including the same. And it may provide a method for producing the same.

1 is a schematic conceptual view of a double layer connector for a solid oxide fuel cell of the present invention.
2 is a side cross-sectional view of a flat tube solid oxide fuel cell to which a double layer connector for a solid oxide fuel cell of the present invention is applied.
3 is a side cross-sectional view of a cylindrical solid oxide fuel cell to which a double layer connector for a solid oxide fuel cell of the present invention is applied.
Figure 4 is a scanning electron micrograph of the double layer connector prepared in the embodiment of the present invention.
FIG. 5 is a photograph of a planar solid oxide fuel cell manufactured in an embodiment of the present invention. FIG.

Hereinafter, the present invention will be described in detail with reference to the drawings.

The double layer connector 100 according to the present invention may be applied to a flat solid oxide fuel cell or a cylindrical solid oxide fuel cell.

Referring to FIG. 1, the double layer connector 100 according to the present invention is formed by sequentially coating an n-type conductor layer 101 and a p-type conductor layer 102 on a surface of an anode support.

As shown in FIGS. 2 and 3, a dual-layer interconnect according to the present invention is a flat-shaped solid oxide composed of an anode support, an electrolyte layer, a cathode, and a double layer interconnector. It can be applied to fuel cells or cylindrical solid oxide fuel cells.

Referring to FIG. 2, the flat tubular solid oxide fuel cell includes an electrolyte layer 220, an air electrode 230, and a double layer connector 200 formed on the anode support 210 having a plurality of flow paths 211.

In addition, referring to FIG. 3, the cylindrical solid oxide fuel cell includes an electrolyte layer 320, an air electrode 330, and a double layer connector 300 formed on the cylindrical anode support 310.

In the present invention, the double layer connectors 200 and 300 have a double layer structure in which n-type conductor layers 201 and 301 are formed on the anode support and p-type conductor layers 202 and 302 are formed on the air flow path side.

The double layer connectors 200 and 300 may have a portion of Sr substituted with at least one element selected from La, Y, Ce, Pr, Nd, Sm, Gd, and Pm, or Ti portion of Co, Mn, Fe, Cr, Cu, V. N-type conductor layer formed of SrTiO ₃ oxide of perovskite structure substituted with at least one element selected from Ni, Zn, Ag, Au, Pt, Pd, Mo, W and Si; And

A part of La is substituted with at least one element selected from Sr, Ca, Ba and Mg, or a part of Mn is Co, Mn, Fe, Cr, Cu, V, Ni, Zn, Ag, Au, Pt, Pd, Mo, W and It is composed of a p-type conductor layer formed of LaMnO ₃ oxide of perovskite structure substituted with one or more elements selected from Si.

In the present invention, the SrTiO ₃ oxide of the perovskite structure is represented by the following Chemical Formula 1 or Chemical Formula 2:

[Formula 1]

Sr _{1- x-δ} M1 _x Ti _{1 - y} M2 _y O ₃

[Formula 2]

(Sr _{1 - x} M1 _x ) _1-δ Ti _{1 - y} M2 _y O ₃

Here, M1 is at least one element selected from La, Y, Ce, Pr, Nd, Sm, Gd and Pm, and M2 is Co, Mn, Fe, Cr, Cu, V, Ni, Zn, Ag, Au, Pt , At least one element selected from Pd, Mo, W and Si, wherein 0.05 ≦ x ≦ 0.4, 0 ≦ δ ≦ 0.2, 0 ≦ y ≦ 0.2.

In addition, LaMnO ₃ oxide of the perovskite structure in the present invention is represented by the following formula (3) or (4):

(3)

La _{1- x-δ} M3 _x Mn _{1 - y} M4 _y O ₃

[Formula 4]

(La _{1 - x} M3 _x ) _1-δ Mn _{1 - y} M4 _y O _{3 ,}

Where M3 is at least one element selected from Sr, Ca, Ba and Mg, and M4 is Co, Mn, Fe, Cr, Cu, V, Ni, Zn, Ag, Au, Pt, Pd, Mo, W and Si At least one element selected from 0.05 ≦ x ≦ 0.4, 0 ≦ δ ≦ 0.2, and 0 ≦ y ≦ 0.2.

Because in the double-layer splice according to the present invention, the perovskite the electrical conductivity of the n-type conductor formed of SrTiO ₃ oxide in the tree structure layer perovskite structure of LaMnO than ₃ p-type conductor formed of an oxide layer relatively low n The type conductor layer should be thinner than the p type conductor layer. Therefore, the n-type conductor layer is preferably formed to a thickness of 2 to 20 ㎛, the p-type conductor layer is preferably formed to a thickness of 3 to 48 ㎛ and the total thickness of the double layer connector is formed of 5 to 50 ㎛. It is desirable to be.

In the present invention, when the thickness of the double layer connector is formed to be less than 5 μm, it is difficult to secure gas permeability, and thus the performance of the fuel cell may be degraded. When the thickness of the double layer connector is formed to exceed 50 μm, there is no problem in gas permeability. Increasing the resistance may reduce the performance of the fuel cell.

In general, the n-type conductors exhibit high electrical conductivity in the reducing atmosphere because of the electrical conductivity caused by electrons, and the p-type conductors exhibit high electrical conductivity in the oxidizing atmosphere because of the electrical conductivity caused by the holes. Since the connector made of the conventional LaCrO ₃ material is a p-type conductor, it exhibits high conductivity in the oxidation atmosphere of the cathode, but has a disadvantage in that the conductivity is drastically lowered in the reduction atmosphere of the anode.

However, as described in the present invention, when manufacturing a double-layer connector composed of an n-type conductor layer on the anode side exposed to the reducing atmosphere and a p-type conductor layer on the cathode side exposed to the oxidation atmosphere, high electrical conductivity in both reducing / oxidizing atmospheres is obtained. Can be seen.

When the splicer is manufactured from a conventional LaCrO ₃ material, sintering is caused by Cr evaporation and condensation rather than mass transfer / diffusion, so that sintering is difficult at low temperatures, and liquid materials (such as CaCrO ₄ or SrCrO ₄ ) formed during sintering It migrates into the porous support and forms dense porous connectors after sintering. Since SrTiO ₃ and LaMnO ₃ based materials used in the present invention are sintered by mass transfer / diffusion, low-temperature sintering is easy, and since no liquid substance is formed during sintering, a thin and dense connector can be manufactured on the porous anode support. .

Hereinafter, a method of manufacturing a solid oxide fuel cell according to the present invention will be described.

First, the anode support is extruded, and then dried and calcined.

The anode support, the electrolyte layer, and the cathode may be manufactured by a method for producing a flat or cylindrical support known in the art.

In one embodiment of the present invention, the anode support is a mixture of nickel oxide, yttria stabilized zirconia, and a pore-forming agent ball milling and drying to prepare a compressed powder; Preparing a paste by mixing the compressed powder, an organic binder, a plasticizer, a lubricant, and distilled water; It can be prepared by extruding the paste into a flat or cylindrical support using an extruder and drying and calcining the support.

In one embodiment of the present invention, the electrolyte may be formed by ball milling a mixture of yttria stabilized zirconia, a dispersant and a solvent to coat the electrolyte slurry on the outer surface of the anode support, which is known in the art An oxygen ion conductive electrolyte can be used without limitation. In the electrolyte coating, in order to form the double layer connector directly on the anode support, a portion of the plasticized body of the anode support is masked and then the electrolyte is coated.

In the process of coating the electrolyte on the anode support, a part of the anode support is masked to leave a portion where the electrolyte is not formed, in which a double layer connector is formed directly on the anode support. Next, the cathode is coated on a portion other than the double layer connector is coated.

Subsequently, in order to form a double layer connector according to the present invention, the n-type conductor layer is pasted and coated on a plastic body of the anode support by a coating method such as screen printing to a certain thickness and then dried.

The paste of the n-type conductor layer is a part of Sr is substituted with one or more elements selected from La, Y, Ce, Pr, Nd, Sm, Gd and Pm or a part of Ti is Co, Mn, Fe, Cr, Cu, V, It can be prepared by mixing SrTiO ₃ oxide, a binder and a solvent of perovskite structure substituted with one or more elements selected from Ni, Zn, Ag, Au, Pt, Pd, Mo, W and Si.

Thereafter, the p-type conductor layer is paste-coated to a constant thickness on the n-type conductor layer by a coating method such as screen printing and then dried.

The paste of the p-type conductor layer is a part of La is substituted with at least one element selected from Sr, Ca, Ba and Mg, or a part of Mn is Co, Mn, Fe, Cr, Cu, V, Ni, Zn, Ag, Au, It can be prepared by mixing a LaMnO ₃ oxide, a binder and a solvent having a perovskite structure substituted with one or more elements selected from Pt, Pd, Mo, W and Si.

In preparing the paste of the n-type conductor layer and the p-type conductor layer, the binder is preferably added in an amount of 3 to 20 parts by weight based on 100 parts by weight of the oxide. When the binder is included in more than 20 parts by weight based on 100 parts by weight of the oxide may be difficult to form a dense film due to the pores formed during the thermal decomposition of the binder, when the binder is included in less than 3 parts by weight based on 100 parts by weight of oxide, Coating the paste can be difficult to coat to a constant thickness.

In addition, in preparing the paste of the n-type conductor layer and the p-type conductor layer, the solvent is preferably added in an amount of 40 to 120 parts by weight based on 100 parts by weight of the oxide. When the solvent is included in excess of 120 parts by weight based on 100 parts by weight of oxide, the thickness of the layer may be too thin. When the solvent is included by less than 40 parts by weight based on 100 parts by weight of oxide, it is difficult to prepare a uniform paste. Can lose.

As the binder, ethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, polyvinyl alcohol, polyvinyl butyral, and the like may be used. Can be used, but is not necessarily limited thereto.

The solvent may include, but is not limited to, α-terpinol, ethyl alcohol, toluene, amyl alcohol, butyl alcohol, ethyl lactate, isopropyl alcohol, ethanol, acetone, ethylel glycol, and the like.

After the coating of the n-type conductor layer and the p-type conductor layer is completed, it is charged into a furnace and sintered by heat treatment at 1300 to 1400 ° C.

After the double layer connector manufacturing process, the cathode is coated and sintered by heat treatment at a temperature of 1400 ℃ or less. In one embodiment of the present invention, as the cathode, a multilayer structure cathode membrane in which an LSM-YSZ layer, an LSM layer, and an LSCF layer are sequentially formed may be used.

Hereinafter, preferred embodiments and test examples of the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and should be construed in accordance with the technical meanings and concepts of the present invention.

The embodiments, test examples, and drawings described in this specification are preferred embodiments of the present invention and do not represent all the technical ideas of the present invention, so that there are various equivalents and modifications that can be substituted at the time of the present application .

Example  One

Activated carbon was weighed and mixed with NiO (JT Baker Co.), 8 mol% Y ₂ O ₃ stabilized ZrO ₂ (TZ-8YS, Tosoh Co.), and pore-forming agent, respectively. After adding ethanol as a solvent, the mixed powder was wet ball milled for 2 weeks using high purity zirconia balls, dried in a dryer at 70 ° C., and sieved to prepare a compressed powder. 20 wt% of distilled water, 13 wt% of organic binder (MP3000), 8 wt% of plasticizer (glycerol), and 3 wt% of lubricant (cellosol) were added to the compressed powder to prepare a paste. At this time, the mixing process was first mixed the powder and the organic binder in powder form for 10 minutes, and then mixed evenly by adding a liquid solution mixed with a plasticizer and lubricant with distilled water to the kneader, so that the additive does not solidify during the kneading process Cooling water was supplied inside the apparatus to lower the temperature of the apparatus. After low temperature aging for 24 hours to evenly distribute the moisture, extrusion was carried out. The extruded molded body was packaged and stored in a linear low density polyethylene (linear low density polyethylene) film to prevent warpage and cracking due to evaporation of the solvent during drying, and was rolled to dry at a speed of 70 rpm at room temperature. Thereafter, the flat tubular support was subjected to plastic sintering at 1100 ° C.

Thereafter, 8 mol% Y ₂ O ₃ -stabilized-ZrO _{2 in the} electrolyte slurry. The concentration of the powder was 3% by weight, and the dispersant and the solvent were each weighed and added, followed by ball milling. After masking a portion of the sintered body of the anode support, the inside was vacuumed using the opening of the flat cathode support using a vacuum slurry coating method, and the inside was vacuum coated and immersed in an electrolyte slurry, followed by drying. After sintering at 1400 ° C. for 5 hours, an electrolyte was formed on the outer surface of the flat tubular anode support.

Sr _{0 .7} an n-type conductor La _{0 .2} TiO _2, were mixed by weighing the solvent in α-terpinol, the binder of ethyl cellulose to form a dual-layer splice. The Sr _{0 .7} La _{0 .2} TiO ₂ sol-gel method was prepared using Fe-based and pitched (Pechini) method, Sr _{0 .7} La _{0 .2} TiO _2, a binder, a solvent, a weight ratio of 1: 0.15: 1.1 The paste was prepared by mixing. Thereafter, the film was coated on the plasticizer of the anode support by screen printing and then dried at 80 ° C. for about 20 minutes. The coating and drying process was carried out twice.

After the process, the p type conductor La _{0 .8} Sr _{0 .2} MnO _3, the solvent were mixed by weighing the α-terpinol, the binder is ethyl cellulose. La _{0 .8} Sr _{0 .2} MnO ₃ sol-was prepared using the Pechini method of gel process based, La _0.8 Sr _0.2 MnO _3, a binder, a solvent, a weight ratio of 1: 0.47 was prepared by mixing a paste: 0.0375. Thereafter, the film was coated on the n-type conductor layer by screen printing and then dried at 80 ° C. for about 20 minutes. The coating and drying process was carried out seven times. Scanning electron micrographs were taken of the double layer connectors formed by coating the paste as shown in FIG. 4.

After the process, the air electrode on the electrolyte _{LSM ((La 0 .85 Sr 0} .15) 0.9 MnO 3) / YSZ and _{LSM ((La 0 .85 Sr 0} .15) 0.9 MnO 3), and the LSCF (La _{0. 6 Sr 0 .4 Co 0 .2 Fe} 0 .8 O 3) was coated with, and then dried at room temperature, was formed for 3 hours and sintered at 1150 ℃ shown in Figure 5, the final shot formed of flat tubular solid oxide fuel cell It was.

Referring to Figure 4 it can be seen that the bilayer splicer prepared in accordance with the present invention is a dense double layer splicer without pores.

Description of the Related Art [0002]
100, 200, 300: Double layer splicer
101, 201, 301: n-type conductor layer
102, 202, 302: p-type conductor layer
211: Euro
210, 310: anode support
220, 320: electrolyte layer
230, 330: air cathode

Claims (16)

A part of Sr is substituted with at least one element selected from La, Y, Ce, Pr, Nd, Sm, Gd and Pm, or a part of Ti is Co, Mn, Fe, Cr, Cu, V, Ni, Zn, Ag, Au, An n-type conductor layer formed of an SrTiO ₃ oxide having a perovskite structure substituted with one or more elements selected from Pt, Pd, Mo, W, and Si; And
A part of La is substituted with at least one element selected from Sr, Ca, Ba and Mg, or a part of Mn is Co, Mn, Fe, Cr, Cu, V, Ni, Zn, Ag, Au, Pt, Pd, Mo, W and A double layer connector for a solid oxide fuel cell comprising a p-type conductor layer formed of a LaMnO ₃ oxide having a perovskite structure substituted with at least one element selected from Si.
The method according to claim 1,
SrTiO ₃ oxide of the perovskite structure is a double layer connector for a solid oxide fuel cell, characterized in that represented by the following formula (1) or (2):
[Formula 1]
Sr _1-x-δ M1 _x Ti _1-y M2 _y O ₃
(2)
(Sr _1-x M1 _x ) _1-δ Ti _1-y M2 _y O ₃
Here, M1 is at least one element selected from La, Y, Ce, Pr, Nd, Sm, Gd and Pm, and M2 is Co, Mn, Fe, Cr, Cu, V, Ni, Zn, Ag, Au, Pt , At least one element selected from Pd, Mo, W and Si, wherein 0.05 ≦ x ≦ 0.4, 0 ≦ δ ≦ 0.2, 0 ≦ y ≦ 0.2.
The method according to claim 1,
LaMnO ₃ oxide of the perovskite structure is a double layer connector for a solid oxide fuel cell, characterized in that represented by the formula (3) or (4):
(3)
La _1-x-δ M3 _x Mn _1-y M4 _y O ₃
[Chemical Formula 4]
(La _1-x M3 _x ) _1-δ Mn _1-y M4 _y O _3,
Where M3 is at least one element selected from Sr, Ca, Ba and Mg, and M4 is Co, Mn, Fe, Cr, Cu, V, Ni, Zn, Ag, Au, Pt, Pd, Mo, W and Si At least one element selected from 0.05 ≦ x ≦ 0.4, 0 ≦ δ ≦ 0.2, and 0 ≦ y ≦ 0.2.
A solid oxide fuel cell comprising an anode support, an electrolyte, an anode, and a double layer connector,
The bilayer interconnector is a part of Sr is substituted with one or more elements selected from La, Y, Ce, Pr, Nd, Sm, Gd and Pm or a part of Ti is Co, Mn, Fe, Cr, Cu, V, Ni, Zn, An n-type conductor layer formed of SrTiO ₃ oxide of perovskite structure substituted with one or more elements selected from Ag, Au, Pt, Pd, Mo, W, and Si; And
A part of La is substituted with at least one element selected from Sr, Ca, Ba and Mg, or a part of Mn is Co, Mn, Fe, Cr, Cu, V, Ni, Zn, Ag, Au, Pt, Pd, Mo, W and A solid oxide fuel cell comprising a p-type conductor layer formed of a LaMnO ₃ oxide having a perovskite structure substituted with at least one element selected from Si.
The method of claim 4,
SrTiO ₃ oxide of the perovskite structure is a solid oxide fuel cell, characterized in that represented by the formula (1) or formula (2):
[Formula 1]
Sr _1-x-δ M1 _x Ti _1-y M2 _y O ₃
(2)
(Sr _1-x M1 _x ) _1-δ Ti _1-y M2 _y O ₃
Here, M1 is at least one element selected from La, Y, Ce, Pr, Nd, Sm, Gd and Pm, and M2 is Co, Mn, Fe, Cr, Cu, V, Ni, Zn, Ag, Au, Pt , At least one element selected from Pd, Mo, W and Si, wherein 0.05 ≦ x ≦ 0.4, 0 ≦ δ ≦ 0.2, 0 ≦ y ≦ 0.2.
The method of claim 4,
LaMnO ₃ oxide of the perovskite structure is a solid oxide fuel cell, characterized in that represented by the following formula (3) or (4):
(3)
La _{1- x-δ} M3 _x Mn _{1 - y} M4 _y O ₃
[Chemical Formula 4]
(La _{1 - x} M3 _x ) _1-δ Mn _{1 - y} M4 _y O _{3 ,}
Where M3 is at least one element selected from Sr, Ca, Ba and Mg, and M4 is Co, Mn, Fe, Cr, Cu, V, Ni, Zn, Ag, Au, Pt, Pd, Mo, W and Si At least one element selected from 0.05 ≦ x ≦ 0.4, 0 ≦ δ ≦ 0.2, and 0 ≦ y ≦ 0.2.
The method of claim 4,
The double layer connector is a solid oxide fuel cell, characterized in that formed to a thickness of 5 to 50 ㎛.
The method of claim 4,
The n-type conductor layer is formed to a thickness of 2 to 20 ㎛, the p-type conductor layer is a solid oxide fuel cell, characterized in that formed to a thickness of 3 ~ 48 ㎛.
The method of claim 4,
A solid oxide fuel cell, characterized in that a flat tube solid oxide fuel cell or a cylindrical solid oxide fuel cell.
Extruding the anode support, followed by drying and sintering;
Coating and drying an electrolyte layer on the anode support;
Coating and drying an n-type conductor layer of a double layer connector on a surface of the anode support;
Coating and drying a p-type conductor layer of a double layer connector on the surface of the n-type conductor layer;
Sintering the anode support coated with the electrolyte layer and the double layer connector; And
Coating, drying and sintering the cathode;
The p-type conductor layer is a part of La is substituted with at least one element selected from Sr, Ca, Ba and Mg or a part of Mn is Co, Mn, Fe, Cr, Cu, V, Ni, Zn, Ag, Au, Pt, A method of manufacturing a solid oxide fuel cell, characterized in that it is formed by coating a paste containing a mixture of LaMnO ₃ oxide, a binder, and a solvent having a perovskite structure substituted with at least one element selected from Pd, Mo, W, and Si.
The method of claim 10,
The n-type conductor layer is a part of Sr is substituted with one or more elements selected from La, Y, Ce, Pr, Nd, Sm, Gd and Pm, or part of Ti Co, Mn, Fe, Cr, Cu, V, Ni, It is formed by coating a paste of a mixture of SrTiO ₃ oxide, a binder and a solvent having a perovskite structure substituted with at least one element selected from Zn, Ag, Au, Pt, Pd, Mo, W and Si. Method of manufacturing a solid oxide fuel cell.
delete The method according to claim 10 or 11,
The binder is a manufacturing method of a solid oxide fuel cell, characterized in that mixed in 3 to 20 parts by weight based on 100 parts by weight of oxide.
The method according to claim 10 or 11,
The solvent is a method for producing a solid oxide fuel cell, characterized in that the mixture of 40 to 120 parts by weight based on 100 parts by weight of oxide.
The method according to claim 10 or 11,
And said binder is selected from the group consisting of ethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, polyvinyl alcohol and polyvinyl butyral.
The method according to claim 10 or 11,
Preparation of the solid oxide fuel cell, characterized in that the solvent is selected from the group consisting of α-terpinol, ethyl alcohol, toluene, amyl alcohol, butyl alcohol, ethyl lactate, isopropyl alcohol, ethanol, acetone and ethylel glycol Way.

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