KR101405477B1 - A method of producing a cell for a metal-supported solid oxide fuel cell and cell for a metal-supported solid oxide fuel cell - Google Patents

Abstract

In one embodiment of the present invention, there is provided a method of manufacturing a cell for a solid oxide fuel cell having a metal support, a microporous metal layer, a fuel electrode layer, a solid electrolyte layer and a cathode layer, (WIP) process using a green sheet prepared by tape-casting a raw material powder constituting at least one of a metal layer, the anode layer and the solid electrolyte layer, and then laminating the green sheet in this order by using a warm isostatic press Wherein the metal-supported solid oxide fuel cell is manufactured by a method of manufacturing a solid oxide fuel cell.
The present invention can further form a diffusion preventing layer selectively on the micropore metal layer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing a metal support type solid oxide fuel cell, and a metal support type solid oxide fuel cell,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cell for a solid oxide fuel cell and a method of manufacturing the same, and more particularly, to a metal pellet type solid oxide fuel cell and a method of manufacturing the same.

A solid oxide fuel cell (SOFC) has a structure in which a plurality of electricity generating units each comprising a unit cell and a separator plate are stacked. The unit cell includes a solid electrolyte layer, a fuel electrode (cathode) located on one side of the solid electrolyte layer, and an air electrode (anode) located on the other side of the solid electrolyte layer (membrane).

When oxygen is supplied to the air electrode and hydrogen is supplied to the fuel electrode, oxygen ions generated by the reduction reaction of oxygen in the air electrode move to the fuel electrode through the solid electrolyte layer, and then water reacts with hydrogen supplied to the fuel electrode. At this time, the electrons generated in the anode are transferred to the cathode and consumed, and electrons flow to the external circuit, and the unit cell generates electric energy using the electron flow. Therefore, the solid electrolyte layer is formed of a dense ion conductive layer which can not directly pass through the gas, and the air electrode and the fuel electrode should exhibit a porous structure that facilitates gas permeation and mixed conduction (electron and ion conductivity).

As the solid oxide fuel cell, there are an electrolyte support-type cell (ESC) type and an air electrode support type cell type or an anode support type cell type. Among them, the electrolyte support type cell type (ESC) Electrolyte layer, and a thin anode layer and a cathode layer. When a solid electrolyte having a thickness of 100 to 500 μm is used as a mechanical support for an electrolyte-supported cell, the ohmic resistance of the solid electrolyte is large. To achieve single-cell performance, the fuel cell must be operated at a high temperature of 850 to 1000 ° C. In this case, since expensive expensive heat-resistant and oxidation-resistant materials must be used for the stack and peripheral equipment (BOP) .

The anode support type cell can reduce the temperature of the SOFC operation temperature to a middle temperature of less than 800 ° C. by reducing the Ohmic of the electrolyte by forming a thin solid electrolyte layer of 5 to 30 μm thickness on the anode layer of 300 to 1,000 μm thickness Although economical efficiency is improved, reliability of the SOFC stack can be secured only if the brittle fracture problem unique to ceramics is overcome.

On the other hand, since the metal support cell (MSC) uses a metal as a support, it is not only inexpensive to manufacture a cell, but also has excellent strength and flexibility.

Such a metal-supported solid oxide fuel cell has a cell structure in which a metal support / an anode / a solid electrolyte are stacked in this order.

In such a laminated structure, it is preferable that the metal support layer and the anode layer have a porous structure that permits easy permeation of gas, and the solid electrolyte layer has a dense structure that does not permeate gas.

Further, since the solid electrolyte layer has a resistance higher than that of the metal support and the anode layer, it is preferable that the thickness of the solid electrolyte layer is as small as possible within a range where gas permeation does not occur.

As a method of manufacturing a metal-supported solid oxide fuel cell, there is a method of forming an anode layer, a solid electrolyte layer and a cathode layer on a porous metal sintered body by a plasma spraying process. Since the solid electrolyte layer formed by the Plasma spraying process is low in density, the solid electrolyte should be thickened to about 50 to 70 μm. Therefore, the cell for the metal support type solid oxide fuel cell manufactured by the plasma spraying method must have a high operating temperature, so that the deterioration of the cell performance is fast.

As a method of manufacturing a metal-supported solid oxide fuel cell, a green sheet prepared by tape-casting a metal support, an anode layer, and a powder forming a solid electrolyte layer is laminated, followed by co- firing.

However, in the above method, the composition of the metal, the particle size, the surface roughness and the surface roughness are controlled so that the solid electrolyte layer, the thermal expansion coefficient of each of the anode layer and the metal support layer, and the sintering shrinkage ratio are precisely controlled and the metal support has a sufficient porosity even after high- And the firing atmosphere must be precisely controlled. Also, this manufacturing method is disadvantageous in that, when the cell is large-sized, the probability of occurrence of pin-holes or warping is increased due to the difference in the sintering shrinkage ratio and the thermal expansion coefficient between the respective layers.

In addition, in the above method, the reducing atmosphere sintering is performed in order to prevent the oxidation of the metal support in the co-firing process. At this time, NiO, which is a fuel electrode material, is reduced to Ni and abrupt particle growth phenomenon occurs, Is lowered.

There is provided a method of manufacturing a cell for a metal-supported solid oxide fuel cell using a thin metal plate having a plurality of holes required for gas permeation as a support in manufacturing a cell for a metal support type solid oxide fuel cell.

First, the plurality of holes and upper layer portions thereof are covered with a metal layer having micropores to facilitate formation of a diffusion preventing layer, a fuel electrode layer, and a solid electrolyte layer necessary for forming a cell for a solid oxide fuel cell on a plurality of holes formed on the metal thin plate Thereby providing a metal foil support having a dual structure.

As a method of forming the diffusion preventing layer, the anode layer and the solid electrolyte layer on the metal thin plate support, a green sheet prepared by tape-casting each constituent layer powder is laminated on the metal support with a warm isostatic press The present invention provides a method for manufacturing a metal support solid oxide fuel cell having excellent interlayer adhesion and mass productivity in conventional methods such as slurry coating and electrophoresis.

Then, the binder of the metal thin plate supporter / diffusion preventing layer / fuel electrode layer / solid electrolyte laminate is removed and cold isostatic pressed, and the layers are sintered at the same time, so that the temperature is lower than the general sintering temperature of the solid electrolyte layer , A metal support solid oxide fuel having excellent adhesion and a solid solid electrolyte layer between each constituent layer and minimizing the number of times of sintering and reducing the number of times of sintering while minimizing the oxidation of the metal support and the grain growth of the Ni component of the anode layer, A method for manufacturing a battery cell is provided.

In one embodiment of the present invention, there is provided a method of manufacturing a cell for a solid oxide fuel cell having a metal support, a microporous metal layer, a fuel electrode layer, a solid electrolyte layer and a cathode layer, A hole for forming a hole in the metal support, filling the hole with a metal powder paste, laminating a green sheet constituting a micropore metal layer on the metal support, and sintering bonding in an inert atmosphere. A method of manufacturing a cell is provided.

The green sheet constituting the metal powder paste or the microporous metal layer may be made of the same material as the metal support, and the metal powder paste may be made of an Fe-Cr alloy or a ferritic stainless steel alloy.

And the green sheet constituting the microporous metal layer may be one of Crofer22APU, Crofer22H or ZMG232L, or the Fe-Cr-based stainless steel alloy may be Fe-26Cr- (Mo, Ti, Y ₂ O ₃ ) alloy or an Fe-Cr-Mx alloy (Mx = Ni, Ti, Ce, Mn, Mo, Co, La, Y and Al).

The thickness of the microporous metal layer after sintering is preferably 50 to 70 mu m.

According to another embodiment of the present invention, a diffusion preventing layer may be further formed between the micropore metal layer and the anode layer.

The diffusion barrier layer is _{CeO 2, Ce 1 - x Ln} x O 2 -δ, (Ln = Gd, Sm, Y, x = 0.1 ~ 0.3, δ = 0 ~ 0.2) (La 1 - x A x) Cr 1 - _{y B y O 3 ± δ (} A = Sr, Ca, or mixtures thereof x = 0.1 ~ 0.4; B = Mn, Co, Cu, Ni, V, Fe, Ti, Ce, Ru or mixtures thereof, y = 0 ~ 0.5, δ = 0 ~ 0.3) , (1-x A x La) s Ti 1-y B y O 3 ± δ (A = Sr, Ca, or mixtures thereof x = 0.1 ~ 0.6; B = Mn, Co, Ti, Ce, Ru or a mixture thereof, y = 0 to 0.5, s = 0.9 to 1.0, and? = 0 to 0.3), (Sr _{1 - x} A _x ) _s Ti _{1 - y} Nb _y O _{3 ± δ} (A = Y, La, Gd, Sm or a mixture thereof, x = 0.05 to 0.2; y = 0 to 0.5; s = 0.9 to 1.0 and δ = 0 to 0.3) Complex.

The diffusion preventive layer preferably has a composition of Ce _{0 .9} Gd _{0 .1} O _{1 .95} or a composition containing 0.2 to 0.8 wt% of Co ₃ O ₄ in the composition. The diffusion preventive layer has an average thickness after sintering of 1 To 10 [mu] m.

In addition, the fuel electrode layer is NiO and _{(ZrO 2) 1-x (} Y 2 O 3) composite of _{x (x = 0.08 ~ 0.1)} , NiO and _{(ZrO 2) 0.90 (Sc 2} O 3) 0.1-x (Yb 2 O ₃ ) _x (x = 0 to 0.06) of Complex, and NiO Ce _{1 -} to _{x Ln x O 2 -δ, (} Ln = Gd, Sm, Y, x = 0.1 ~ 0.3, δ = 0 ~ 0.2) of any one of the complex or mixture of complexes is preferable.

The anode layer is preferably a composite of NiO and Ce _{0 .9} Gd _{0 .1} O _{2 -δ} (δ = 0 to 0.2) solid electrolyte powder, wherein the content of NiO is 50 to 75 wt% .

The anode layer preferably has an average thickness after sintering of 10 mu m to 50 mu m.

In addition, the solid electrolyte layer is Ce _{1 -} preferably _{x Ln x O 2 -δ (Ln} = Gd, Sm, Y, x = 0.1 ~ 0.3, δ = 0 ~ 0.2) of oxide.

The solid electrolyte layer is a mixture in which at least any one or more of transition metal oxides of Co ₃ O ₄ , CoO, CuO, MnO and MnO ₂ is added to the solid oxide electrolyte in an amount of 0.2 to 2 wt% desirable.

The solid electrolyte layer has a composition of Ce _{0 .9} Gd _{0 .1} O _{1 .95} or a composition containing 0.2-0.8 wt% of Co ₃ O ₄ in the composition. The solid electrolyte layer has an average thickness after sintering of 5 μm To 30 [micro] m.

Also, the air electrode layer _{(A 1- x B x) s} Fe 1 - y Co y O 3 -δ (A = La, Gd, Y, Sm, Ln or mixtures thereof, B = Ba, Sr, Ca, and mixtures thereof , Ln = lanthanides) and _{(La 1 - x Sr x)} s MnO 3 -δ preferably made of the same electrically conductive oxide, or a powder of a solid electrolyte composition on the electrically conductive oxide as the complex was added to a 0 ~ 50 vol% range Do.

This layer is the air electrode _{(La 0 .6, Sr 0 .4} ) (Co 0 .2, Fe 0 .8) O 3 is preferably in a mixture of Ce _0.9 Gd _0.1 O _1.95 of 40 ~ 60 wt%.

The average thickness of the cathode layer after sintering is preferably in the range of 10 [mu] m to 50 [mu] m.

A method of manufacturing a cell for a solid oxide fuel cell according to another embodiment of the present invention includes:

I) a first step of preparing the metal support;

Ii) filling a plurality of holes formed in the metal support with metal powder paste;

Iii) a third step of laminating a green sheet constituting the micropore metal layer on one surface of the metal support using the warm isostatic pressing (WIP) process;

Iv) a fourth step of sintering and bonding the micropore metal layer;

V) laminating the green sheet of the anode layer on the micropore metal layer;

Vi) a sixth step of laminating the green sheet of the solid electrolyte layer on the anode layer;

(7) a seventh step of sintering the solid electrolyte layer green sheet; And

(E) screen printing the cathode layer on the sintered solid electrolyte layer; The present invention also provides a method of manufacturing a cell for a metal-supported solid oxide fuel cell.

The method may further include a fourth step of laminating a diffusion preventing green sheet on the micropore metal layer between the fourth step and the fifth step.

In each of the third, fourth, fifth, and sixth steps, each green sheet may be formed by tape casting.

It is preferable to arrange the green sheets in the 4-1st, 5th, and 6th steps in order and laminate the green sheets constituting each layer using a warm isostatic press (WIP) process.

Each of the formed green sheets was vacuum packed, and the vacuum packed laminate was placed in a warm isostatic pressing apparatus in which the water temperature inside the cylinder was maintained at 60 to 80 DEG C, To 300 kgf / cm < ² > for 10 to 40 minutes.

The method may further include removing the binder and the plasticizer from the laminate after the warm isostatic pressing (WIP) process.

Here, the step of removing the binder and the plasticizer is preferably carried out at 200 ° C, 350 ° C, and 500 ° C for 2 to 5 hours or more, respectively, while the temperature is raised at a rate of 1 ° C to 3 ° C per minute in air.

The method may further include a step of compressing the diffusion preventing layer, the anode layer and the solid electrolyte layer by a cold isostatic press (CIP) process on the laminate from which the binder and the plasticizer have been removed.

At this time, in the cold isostatic press (CIP) process, the laminate is packed in a vacuum and then is put in a cold isostatic press, and isotropic pressure of 1,000 to 5,000 kgf / cm ² is applied for 5 to 30 minutes in a cold isostatic press .

Further, the shaped body may be further subjected to a heat treatment in a sintering furnace in an argon atmosphere at a temperature in the range of 1000 to 1070 ° C for 1 to 5 hours by the cold isostatic press (CIP) process.

In another embodiment of the present invention, in the fourth step, the sintering may be performed in a sintering furnace in a hydrogen atmosphere for 1 to 5 hours at 1,100 to 1,200 ° C.

The ninth step further preferably includes a step of sintering the cathode layer. The ninth step is preferably performed at a temperature of 750 to 850 ° C, which is a bonding temperature of the sealing material during stacking or cell evaluation, without performing any heat treatment in the cell manufacturing process.

A cell for a metal-supported solid oxide fuel cell according to another embodiment of the present invention includes a metal support having a plurality of holes, a micropore metal layer formed on the metal support, an anode layer formed on the micropore metal layer, A solid electrolyte layer formed on the anode layer, and a cathode layer formed on the solid electrolyte layer, wherein the hole is filled with a sintered metal powder paste.

The metal powder paste may be made of the same material as the metal support and / or the micropore metal layer.

The cell for a metal-supported solid oxide fuel cell may further include a diffusion barrier layer on the micropore metal layer.

The metal powder paste is preferably made of an Fe-Cr-based stainless steel alloy or a waste-light-based stainless steel alloy.

And the green sheet composing the metal support, the metal powder paste and the microporous metal layer may be any one of Crofer22APU, Crofer22H and ZMG232L, or the Fe-Cr alloy may be Fe-26Cr- (Mo, Ti, Y ₂ O ₃ ) alloy or an Fe-Cr-Mx alloy (Mx = Ni, Ti, Ce, Mn, Mo, Co, La, Y and Al).

Also, a cell for a metal support type solid oxide fuel cell may be formed with a plurality of pores in the micropore metal layer and the metal powder paste layer.

The method of manufacturing a metal-supported solid oxide fuel cell according to an embodiment of the present invention is different from the conventional method of manufacturing a metal support as a whole porous structure for gas permeation, A plurality of holes for transmission can be formed.

Therefore, since the metal foil is left on the edge of the cell, the mechanical durability of the stack can be improved because it can serve as a conventional glass-based cell seal by welding or brazing the metal separator with the metal separator.

In the method of manufacturing a metal-supported solid oxide fuel cell according to an embodiment of the present invention, a metal powder paste is filled in a hole formed by chemical etching on a metal thin plate support, and a micropore metal layer is sintered and bonded. Pores having a very small size can be formed, thereby ensuring a gas permeation path and forming a continuous and dense solid electrolyte layer.

Therefore, the same effect can be realized at a low cost as compared with a case where a very small hole is formed on a metal foil plate by laser machining.

Further, in the case of manufacturing a cell for a solid oxide fuel cell by a manufacturing method according to an embodiment of the present invention, a method of laminating a green tape of each constituent layer with a warm isostatic press is used. Therefore, The constituent layers can be laminated in a convenient and economical manner.

Further, when the fuel cell is manufactured by the manufacturing method according to the embodiment of the present invention, the number of stacking and sintering processes can be reduced, thereby reducing the overall manufacturing cost.

Then, the binder of the metal thin plate supporter / diffusion preventing layer / fuel electrode layer / solid electrolyte multilayer body is removed, and the resultant is sintered at a temperature lower than the general sintering temperature of the solid electrolyte layer by cold isostatic pressing, And a dense solid electrolyte layer can be obtained, and there is a technical effect that particle growth of the Ni component of the anode layer can be suppressed and oxidation of the metal support can be minimized.

Further, when the fuel cell is manufactured by the manufacturing method according to the embodiment of the present invention, the number of stacking and sintering processes can be reduced, thereby reducing the overall manufacturing cost.

In addition, since a metal support is used in manufacturing a fuel cell according to an embodiment of the present invention, the manufacturing cost is lower than that of a ceramic support type solid oxide fuel cell, and a technical effect .

Accordingly, the fuel cell stack and the fuel cell power generation system using the metal-supported solid oxide fuel cell fabricated according to an embodiment of the present invention can be applied to thermal and mechanical shock and vibration There is a technical effect that strong and rapid thermal cycling is possible.

In addition, the use of the manufactured fuel cell can improve the thermal and mechanical reliability, which is a weak point of the conventional ceramic support type SOFC stack in the field of power sources such as transportation equipment, mobile equipment, and portable equipment, and commercialization of the solid oxide fuel cell can be expected have.

1 is a cross-sectional view illustrating a cell for a solid oxide fuel cell according to an embodiment of the present invention.
2A to 2F are views for explaining a method of manufacturing a solid oxide fuel cell according to an embodiment of the present invention.
3 is a flowchart illustrating a method of manufacturing a solid oxide fuel cell according to an embodiment of the present invention.
4 is a photograph showing a surface of a cell for a solid oxide fuel cell according to an embodiment of the present invention.
5 is a photograph showing a cross section of a cell for a solid oxide fuel cell according to an embodiment of the present invention.
6 is a FIB and SEM image of a laminate of a dual structure metal support / diffusion-preventing layer / fuel electrode layer / solid electrolyte layer prepared according to Example 2 of the present invention.
7 is a graph showing an open circuit voltage and a voltage-output curve of an SOFC cell manufactured according to the third embodiment of the present invention.
FIG. 8 is a comparative diagram of a conventional cell for explaining usefulness of a cell for a solid oxide fuel cell according to another embodiment of the present invention.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. The singular forms as used herein include plural forms as long as the phrases do not expressly express the opposite meaning thereto. Means that a particular feature, region, integer, step, operation, element and / or component is specified, and that other specific features, regions, integers, steps, operations, elements, components, and / And the like.

Unless otherwise defined, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Commonly used predefined terms are further interpreted as having a meaning consistent with the relevant technical literature and the present disclosure, and are not to be construed as ideal or very formal meanings unless defined otherwise.

Hereinafter, embodiments of the present invention will be described in detail. These embodiments are only for illustrating the present invention, and the present invention is not limited thereto.

A cell for a metal support type solid oxide fuel cell according to an embodiment of the present invention includes a metal support 11 and a micropore metal layer 14 formed on the metal support 11, a fuel electrode layer 14 formed on the micropore metal layer 14 16, a solid electrolyte layer 17 formed on the anode layer 16, and a cathode layer 18 formed on the solid electrolyte layer 17.

Alternatively, a diffusion prevention layer 15 may be optionally formed between the micropore metal layer 14 and the anode layer.

A plurality of holes 11a are formed in the metal support 11 in the thickness direction and the metal powder paste 12 can be filled in the holes 11a. At this time, the plurality of holes 11a formed in the metal support may use a metal support already formed with a plurality of holes, or may directly form a plurality of holes in the metal support.

Fine pores may be formed in the sintered metal powder paste and the micropore metal layer.

A method of manufacturing a metal-supported solid oxide fuel cell according to an embodiment of the present invention includes:

I) a first step (Sl) of preparing a metal support (11);

Ii) a second step (S2) of filling the metal powder paste (12) into the plurality of holes (11a) formed in the metal support (11);

(Iii) a third step of laminating a green sheet of metal powder produced by tape casting on one side of the metal support 11 using a warm isostatic press (WIP) process to form a micropore metal layer 14 S3);

Iv) a fourth step (S4) of sintering the metal support (11) and the micropore metal layer (14);

V) a fifth step (S5) of laminating a green sheet of the anode layer (16) on the micropore metal layer (14) having fine pores after sintering;

Vi) sixth step (S6) of laminating the green sheet of the solid electrolyte layer (17) on the anode layer (16);

(7) seventh step (S7) of sintering the solid electrolyte layer 17 and the anode layer 16;

(E) an eighth step (S8) of screen printing the cathode layer 18 on the sintered solid electrolyte layer 17; And

(E) sintering the cathode layer 18 in the ninth step (S9).

Hereinafter, each detailed process of a method of manufacturing a metal-supported solid oxide fuel cell according to an embodiment of the present invention will be described in sequence.

First, referring to FIG. 2A, a first step S1 of preparing the metal support 11 will be described.

It is preferable that the metal support 11 be a sintered body of metal powder or a metal thin plate which is not shrunk in the subsequent heat treatment step as a substrate. The metal support 11 is provided with a plurality of holes 11a for forming gas flow paths, and the holes 11a may be formed by chemical etching. Here, the metal support 11 may be formed to have a thickness of 0.2 mm, and the plurality of holes 11a forming the gas flow path may be formed to have a diameter of 250um or less.

The metal support 11 preferably has a three-dimensional continuous pore structure or a structure in which a plurality of through holes are formed, more preferably, a structure in which the two structures are fused, in order to pass the fuel gas.

The material for the metal support is preferably a material having a small decrease in electrical conductivity due to high-temperature oxidation, a redox stability, and a thermal expansion coefficient of about 10 to 13 x 10 ^-6 / ^{° C.} The reason for limiting the coefficient of thermal expansion of the metal support 11 is that the difference in thermal expansion coefficient between the metal support and each of the ceramic functional layers stacked thereon is reduced so that the functional layer is peeled off due to the difference in thermal expansion coefficient between the components, .

Ferrite-based stainless steel, Crofer 22 APU and Crofer 22H from Tyssenkrupp, Germany, and ZMG232L from Hitachi Metal, Japan, are examples of materials for the metal support having such characteristics.

In addition, Fe - Cr - (Mo, Ti, Y ₂ O ₃ ) and Fe - Cr - M _x alloy (M _x = Ni, Ti, Ce, Mn, Mo, Co, La, Y, Al). In the case of such an Fe-Cr alloy, 0 to 50 vol% of a metal oxide (doped-zirconia, doped-ceria, MgO, CaO, SrO, CoO _x , ZnO, VO _x , Cr ₂ O ₃ , FeO, MoO _x , WO _x , Ga ₂ O ₃ , Al ₂ O ₃ , TiO ₂ and mixtures thereof) may be used.

Next, referring to FIG. 2B, a second step S2 of filling the metal powder paste 12 into the plurality of holes 11a formed in the metal support 11 will be described.

In the second step, the metal powder paste 12 is filled with Fe-Cr ferritic stainless steel or the same metal as the material for the metal support Alloy powder. The metal powder paste 12 is placed on the surface of the metal support 11 and the metal powder paste is inserted into the hole formed on the metal support 11 using a scraper.

Next, referring to FIG. 2C, iii) a green sheet of metal powder produced by tape casting is laminated on either side of the metal support 11 using a warm isostatic press (WIP) process to form a micro pore metal layer 14 The third step (S3) of forming the film is described below.

In the third step, the micropore metal layer 14 is formed by tape casting and disposed between the metal support 11 and the anode layer 16. The fine pore metal layer 14 may be made of ferrite stainless steel, which is an Fe-Cr alloy, or a powder of the same metal or alloy as the material for the metal support. The fine pore metal layer 14 is composed of a metal powder paste and a metal support 11 ). ≪ / RTI > The micropore metal layer 14 may be formed to have a thickness of 50 to 70 um.

In the third step, the micro pore metal layer 14 is laminated by a warm isostatic pressing (WIP) process. In this case, the average thickness of the green sheet of the micropore metal layer 14 formed by tape casting is 50 to 70 um. In the warm isostatic pressing (WIP) process, the green sheet of metal powder is coated on one side of the prepared metal support 11 and then, put into a warm, such as bangap press apparatus in which the water temperature in the cylinder kept at 60 ~ 80 ℃ 100 ~ 300kgf / cm 2 pressure of 10 to 40 minutes of the fine pore metal layer 14 is disposed, and a vacuum packing consisting of , More preferably 250 to 300 kgf / cm ² for 15 to 30 minutes, more preferably 280 kgf / cm ² for 30 minutes to laminate the green sheet.

Such a warm isostatic pressing (WIP) method is a process useful for laminating and joining not only the same or different types of green sheets but also various components constituting a cell for fuel cells on a sintered porous metal support or a metal foil plate on which gas channels are formed.

Next, referring to FIG. 2C, the following will describe iv) a fourth step (S4) of sintering the micropore metal layer 14. FIG.

The sintering process is preferably performed in a hydrogen atmosphere sintering furnace at a temperature in the range of 1,100 to 1,180 ° C for 1 to 5 hours, more preferably at 1,160 ° C for 3 hours.

In the fourth step, a micropore metal layer 14 composed of a green sheet layer of a metal powder paste 12 and a metal powder and a metal layer having micropores on the surface of the metal support are formed by sintering.

FIG. 4 is a photograph showing a surface of a cell for a solid oxide fuel cell according to an embodiment of the present invention, and FIG. 5 is a cross-sectional view of a cell for a solid oxide fuel cell according to an embodiment of the present invention.

As shown in FIGS. 4 and 5, it is confirmed that the metal powder paste 12 and the micropore metal layer 14 are formed on the surface of the metal support. The metal layer 11 having the fine pores is formed on the surface of the metal support by filling the holes with the metal powder paste 12 and laminating and sintering the green sheet of the metal powder on the surface thereof. The size of the fuel electrode layer 16 or the diffusion preventing layer 15 can be increased by the following process without causing defects such as cracks or depressions that are generated while forming the anode layer 16 and the solid electrolyte layer 17 And the like.

Next, referring to FIG. 2D, v) step 5 (S5) of stacking the green sheet of the anode layer 16 on the micropore metal layer 14 will be described.

In the fifth step, the anode layer 16 is made of a green sheet prepared by tape casting and laminated on the metal support 11. [ The average thickness of the green sheet constituting the anode layer 16 is 60 to 70 mu.

A fuel electrode layer 16 is a ceramic powder NiO and _{(ZrO 2) 1-x (} Y 2 O 3) x (x = 0.08 ~ 0.1) of the composite, NiO and _{(ZrO 2) 0.90 (Sc 2} O 3) 0.1- _{x (Yb 2 O 3) x} (x = 0 ~ 0.06) of Complex, and NiO A complex of any one of Ce _{1 -x} Ln _x O _{2 -δ} (Ln = Gd, Sm, Y, x = 0.1 to 0.3, and δ = 0 to 0.2) or a mixture thereof is preferable.

More preferably, the ceramic powder constituting the anode layer 16 is a composite of NiO and (ZrO ₂ ) _0.92 (Y ₂ O ₃ ) _0.08 solid electrolyte powder or NiO and Ce _{0 .9} Gd _{0 .1} O _{2 -δ} = 0 ~ 0.2) solid electrolyte powder. Here, the content of NiO in such a composite is preferably in the range of 50 to 75 wt%, and more desirably in the range of 60 wt%. The anode layer preferably has an average thickness after sintering of 10 탆 to 50 탆, more preferably 30 to 40 탆.

Next, the sixth step (S6) of laminating the green sheet of the solid electrolyte layer 17 on the anode layer 16 will be described with reference to FIG. 2 (e).

In the sixth step, the solid electrolyte layer 17 is made of a green sheet prepared by tape casting and laminated on the anode layer 16. The average thickness of the green sheet constituting the solid electrolyte layer 17 is in the range of 25 to 35 μm. The final thickness of the solid electrolyte layer 17 can be adjusted by changing the thickness of the green sheet and changing the number of layers.

In the sixth step, a laminate composed of a metal support (substrate) / micropore metal layer (sintered body) / anode layer (green sheet) / solid electrolyte layer (green sheet) is produced through a lamination process.

The solid electrolyte layer 17 to be laminated in the step 6 is Ce _{1 -} may be _{x Ln x O 2 -δ Ln =} Gd, Sm, Y, x = 0.1 ~ 0.3, δ = 0 ~ 0.2) based oxide. Here, in order to further improve the sinterability of the solid electrolyte, Co ₃ O ₄ , CoO, CuO, MnO and MnO ₂ Is added in an amount of 0.2 to 2 wt%, more preferably 0.8 to 1.2 wt%, and still more preferably 1 wt% of Co ₃ O _{4 based} on the solid electrolyte powder .

Transition metal oxides added as a sintering aid act as a temporary liquid phase near the sintering temperature to aid densification by helping densification and grain boundary movement through mass transfer. When the addition amount is too small, the effect of promoting sintering is small. , It is necessary to add the optimum amount since the open circuit voltage can be reduced due to the electronic conductivity due to the residual transition metal after sintering.

The average thickness of the solid electrolyte layer 17 thus formed is in the range of 5 to 30 [mu] m, more preferably 10 to 20 [mu] m after sintering. The performance of the SOFC cell increases as the thickness of the solid electrolyte layer 17 decreases as the ionic conduction resistance decreases. When the thickness of the SOFC cell is too thin, the performance of the SOFC cell is degraded by the fuel gas and air A cross-over phenomenon occurs, which causes a decrease in electromotive force. In addition, a hot spot is generated around the portion, causing deterioration of the cell performance. Therefore, a cross-over phenomenon It is required to have a proper thickness at a level that does not occur.

Next, the seventh step (S7) of sintering the solid electrolyte layer 17 will be described with reference to FIG. 2E.

In the seventh step S7, the solid electrolyte layer 17 is sintered in an inert atmosphere, preferably in an argon atmosphere in a sintering furnace at 1,000 to 1,070 DEG C for 1 to 5 hours, more preferably at 1,050 DEG C 3 hours. ≪ / RTI >

This heat treatment temperature range is insufficient for the denseness and adhesiveness of the solid electrolyte layer 17 at a temperature of 1,000 DEG C or lower, and the oxidation of the metal support 11 is severely generated at 1,070 DEG C or higher. When sintering is performed in this manner, the oxidation of the metal support 11 can be prevented, and the adhesion between layers and the densification of the solid electrolyte can be simultaneously achieved.

For example, as a ceramic material of the solid electrolyte layer 17, a ceria-based solid electrolyte such as Ce _{0 .9} Gd _{0 .1} O _{1 .95} is usually sintered at a sintering temperature of 1,350 ~ A mixture obtained by adding Co ₃ O ₄ to the solid electrolyte powder in the range of 0.2 to 2 wt%, more preferably 0.8 to 1.2 wt%, further preferably 1 wt% The pores of the solid electrolyte layer 17 are sufficiently removed only by relatively low-temperature sintering at about 1,000 to 1,070 DEG C to cause the fuel gas and air to directly contact with each other through the residual pores to cause a combustion reaction It can be sintered sufficiently densely.

In addition, in the conventional methods known heretofore, the ceramic layer formed on the substrate such as the metal thin plate or the sintering metal support, which can not be accompanied by the sintering shrinkage during the subsequent heat treatment step, hinders the shrinkage behavior of the laminated ceramic layer However, when the solid electrolyte layer is formed by the seventh step as described above, the adhesion force with respect to the metal support and the molding density are maximized, and the amount of shrinkage required for densification is increased to a large extent So that the solid electrolyte layer is sufficiently dense that the fuel gas in the fuel electrode layer and the air in the air electrode layer meet directly in the range of 1,000 to 1,070 ° C and can not cause the combustion reaction.

Although the process of forming the micropore metal layer 14 by the fourth step process and sequentially stacking the fuel electrode layer (fifth step) and the solid electrolyte layer (sixth step) has been described above, the present invention is not limited thereto A fourth step of forming a micropore metal layer (fourth step) and then forming a diffusion barrier layer before forming the anode layer (fifth step) may be selectively added.

Step 4-1 is a step of laminating the diffusion preventive layer 15. The diffusion preventive layer 15 prevents diffusion of the Fe and Cr components of the metal support and Ni of the Ni-based anode while allowing gas and electricity to pass therethrough. Function.

To this end, use as diffusion barrier layer 15. The material is available _{CeO 2, Ce 1 - x Ln} x O 2 -δ, (Ln = Gd, Sm, Y, x = 0.1 ~ 0.3, δ = 0 ~ 0.2) (La 1 _{- x} A _x ) Cr _{1 - y} B _y O _{3 ± δ} (A = Sr, Ca or a mixture thereof x = 0.1 to 0.4; B = Mn, Co, Cu, Ni, V, Fe, (A = Sr, Ca, or a mixture thereof, x = 0.1 to 0.3), (La _1-x A _x ) _s Ti _1-y B _y O _{3 +} 0 to 0.5; s = 0.9 to 1.0;? = 0 to 0.3), (Sr _{1 - x} A _{x) s Ti 1 - y Nb} y O 3 ± δ (A = y, La, Gd, Sm or mixtures thereof, x = 0.05 ~ 0.2; y = 0 ~ 0.5; s = 0.9 ~ 1.0, δ = 0 ~ 0.3 ) Are preferably used alone or in combination.

The material used as the diffusion preventing layer 15 is more preferably a Ce _{0 .9} Gd _{0 .1} O _{1 .95} composition or a composition containing 0.2 to 0.8 wt% of Co ₃ O ₄ , more preferably 0.3 to 0.6 wt% %, More preferably 0.5 wt%. The addition of Co ₃ O ₄ promotes the sintering of Ce _{0 .9} Gd _{0 .1} O _1.95 to improve adhesion between the substrate and the anode layer. However, as the amount of addition increases, the density of the diffusion barrier increases, Thereby reducing cell performance. The average thickness after sintering is preferably in the range of 1 to 10 μm, more preferably in the range of 3 to 6 μm, and still more preferably in the range of 3 to 4 μm.

The diffusion preventing layer preferably has an average thickness after sintering of 1 to 10 μm, more preferably 2 to 6 μm, and still more preferably 3 to 4 μm.

If the thickness of the diffusion preventing layer is too small, there is a possibility that a diffusion reaction partially occurs due to a part where the fuel electrode and the metal support come in direct contact with each other due to the influence of the surface roughness of the metal support.

In step 4-1, the diffusion preventing layer 15 is made of a green sheet prepared by tape casting and laminated on the micropore metal layer 14. After the green sheets of the diffusion preventing layer 15 are stacked in the step 4-1, the green sheets of the anode layer 16 and the solid electrolyte layer 17 described above are sequentially laminated.

Thus, a laminate composed of a metal support (substrate), a micropore metal layer (sintered body), a diffusion preventing layer (green sheet), an anode layer (green sheet), and a solid electrolyte layer .

Here, when a diffusion preventing layer (green sheet), a fuel electrode layer (green sheet) and a solid electrolyte (green sheet) are stacked on an upper portion where a micropore metal layer (sintered body) is formed on a metal support (substrate), a warm isostatic press ). ≪ / RTI >

When the three green sheets are laminated using a warm isostatic press (WIP) as described above, the warm isostatic press (WIP) process is a method in which the above-described micropore metal layer 14 is formed by a warm isostatic pressing (WIP) And therefore the detailed description of the warm isostatic press (WIP) process will be omitted.

After the diffusion barrier layer (green sheet), the anode layer (green sheet) and the solid electrolyte (green sheet) are laminated by the warm isostatic pressing (WIP) process, the binder and the plasticizer are removed do.

Then, the diffusion preventing layer, the anode layer and the solid electrolyte layer can be compression-molded by a cold isostatic pressing (CIP) process.

In this case, the method of removing the binder and the plasticizer from the three green sheet laminate is preferably carried out at 200 ° C, 350 ° C, and 500 ° C for 2 to 5 hours or more while raising the temperature at a rate of 1 ° C to 3 ° C per minute in air.

And a step for cold-like bangap press (CIP) with respect to the laminated body to remove the binder is packing the laminate in a vacuum, and then cold pressing machine, such as an isotropic state of bangap 1,000 ~ 5,000kgf / cm ² in a press machine such as a cold in bangap In the It is preferable that the pressure is applied for 5 to 30 minutes.

After the laminate is subjected to cold isostatic pressing as described above, it is sintered after being charged into a sintering furnace preferably in an argon atmosphere rather than an inert atmosphere.

Here, the sintering method is the same as the sintering process of the solid electrolyte layer 17 in the seventh step S7, and thus a detailed description thereof will be omitted.

2F) in which the diffusion preventing layer 15 is formed and the laminate (FIG. 2F) in which the diffusion preventing layer 15 is not formed, Can be applied to all of them.

Next, the eighth step of screen printing the cathode layer 18 on the solid electrolyte layer 17 will be described with reference to FIG. 2F.

In the eighth step, the cathode layer 18 is formed on the solid electrolyte layer 17 by a screen printing process. The composition of the air electrode layer 18, formed from the eighth stage _{(A 1- x B x) s} Fe 1 - y Co y O 3 -δ (A = La, Gd, Y, Sm, Ln or mixtures thereof, B = Ba, Sr, Ca and mixtures thereof, Ln = lanthanides) and _{(La 1 - x Sr x)} s MnO 3 as _-δ An electrically conductive oxide, or a composite in which a powder of a solid electrolyte composition is added to the electrically conductive oxide in a range of 0 to 50 vol%. Such an air electrode layer _{(La 0 .6, Sr 0 .4} ) (Co 0 .2, Fe 0 .8) of 40 ~ 60wt% to the O _3, and more preferably 50wt% Ce _{0 .9} Gd _{0 .1} O _{1 . 95} may be used.

The average thickness of the air electrode layer is preferably in the range of 10um to 50um.

Finally, the ninth step (S9) of sintering the cathode layer 18 will be described.

In the ninth step S9, the cathode layer 18 is sintered at a temperature of 750 to 850 deg. C, more preferably 800 deg. C, which is a temperature at which the sealing material is bonded in the stack or cell evaluation process without a separate heat treatment in the cell manufacturing process, Thereby completing a support-type solid oxide fuel cell.

Hereinafter, a specific embodiment of the present invention will be described.

(Example 1) Preparation of a double structure metal support

A 14 mm diameter concentric circle area was chemically etched in the center of a thin metal plate with a thickness of 0.2 mm and a diameter of 27 mm to form a hole having a diameter of 0.25 mm and a center distance of 0.5 mm arranged in a lattice form To prepare a metal substrate.

When a diffusion barrier layer, an anode layer, and a solid electrolyte layer are formed on such a metal substrate, there is a high possibility that cracks will occur in the ceramic layer formed on the hole. Therefore, Crofer 22APU alloy powder having the same composition as the substrate is mixed with ethyl cellulose binder and Buthyl Carbitol Acetate The mixed metal powder paste was prepared, the paste was press-fitted into a hole formed in a metal substrate, and then dried at 100 ° C to fabricate a hole formed by chemical etching.

In the next step, a Crofer 22APU alloy powder having the same composition as the substrate is cast by tape casting to prevent cracks in the ceramic layer formed thereon due to the height difference between the substrate surface and the portion of the hole-processed portion, place and this then vacuum plastic wrap, 70 ℃, 200kgf / cm ^2, such as in hot 20 minutes bangap pressing (WIP) by laminating a green sheet metal powder on said metal substrate, the green sheet on the produced sheet, and the plugging substrate Respectively.

The binder and the plasticizer of the laminate were kept in air at 200 ° C, 350 ° C, and 500 ° C for 2 hours to be removed, and heat treated in a hydrogen atmosphere at 1,180 ° C for 3 hours to form a metal substrate, The green sheet of the powder was bonded.

The green sheets of the Crofer 22APU alloy powder pasted with WIP and the Crofer 22APU alloy powder after the heat treatment are "microporous metal layers" after the heat treatment, and serve as a diffusion barrier for the fuel gas and a conduction path for electrons as well as for diffusion prevention layer, fuel electrode layer, Layer serves as a cover layer (see FIG. 4) that can be stably implemented on a perforated metal substrate without defect.

The use of a metal support having a double structure as shown in FIG. 5 enables high-temperature gas sealing by airtight welding of the metal support-type cells and the metal separator using the outer portion of the substrate on which the holes are not formed, It is possible to increase the capacity of the stack by welding several small cells.

(Example 2) Metal support / Diffusion reaction prevention layer / Anode  layer/ Solid electrolyte The laminate  Produce

The green sheet for the diffusion barrier layer was prepared by adding 0.5 wt% of Co ₃ O ₄ to Ce _{0 .9} Gd _{0 .1} O _{1 .95} (Anan Kasei) powder and tape casting it to prepare a green sheet having a thickness of 6 μm.

As the green sheet for the anode layer, 60 wt% of Ce _{0 .9} Gd _{0 .1} O _{1 .95} was mixed with NiO and tape cast to prepare a green sheet having a thickness of 60 탆. The green sheet for the solid electrolyte layer was prepared by adding 0.5 wt% of Co ₃ O ₄ to Ce _{0 .9} Gd _{0 .1} O _{1 .95} (Anan Kasei) powder and tape casting it to prepare a green sheet having a thickness of 30 μm.

The diffusion preventing layer, the fuel electrode layer, a solid place the green sheet of the electrolyte layer, and then, after the vacuum plastic wrap, 70 ℃, 20 bungan hot isostatic pressure from 200kgf / cm ² on the double structure metal support prepared in Example 1 with the following step The green sheets of the diffusion preventing layer, the anode layer, and the solid electrolyte layer were laminated in order by pressing (WIP).

The binder and the plasticizer component of the laminate were maintained at 200 ° C, 350 ° C, and 500 ° C in the air for 2 hours to remove them. After vacuum vinyl packaging, they were subjected to cold isostatic pressing (CIP) treatment at 2,000kgf / cm ² for 10 minutes , And then heat-treated at 1,070 ° C for 3 hours in an argon (Ar) gas atmosphere to complete a laminate of a dual structure metal support / diffusion preventing layer / anode layer / solid electrolyte layer.

6 (a) to 6 (d), the microstructure of the laminate of the dual structure metal support / diffusion preventing layer / fuel electrode layer / solid electrolyte layer was observed through FIB and SEM. As a result, It was confirmed that a dense solid electrolyte membrane was formed even though the porous diffusion preventing layer and the anode layer were formed on the formed dual structure metal support and the limited sintering was performed thereon at a low temperature.

As shown in FIG. 6 (c), a Cr ₂ O ₃ -based oxide phase of 0.5 μm level was formed at the interface between the diffusion barrier layer and the dual structure metal support. 6 (b) is an enlarged circle of the dotted line in FIG. 6 (a), and FIG. 6 (c) is an enlarged circle of the dotted line in FIG. 6 (b).

( Example  3) Metal support / diffusion prevention layer / Anode  Floor / Solid electrolyte  Floor / To the air pole  Configured metal support body SOFC  Cell development and performance evaluation.

(La _{0 .6} , Sr _{0 .4} ) (Co _{0 .2} , Fe _{0 .8} ) O ₂ (Fe _{0 .8} ) were used to prepare the cathode layer on the dual structure metal support / diffusion barrier layer / anode layer / solid electrolyte layer prepared in Example 2 ₃ to 50 wt% Ce _{0 .9} Gd _{0 .1} O _{1 . 95} was mixed with a paste of the cathode powder to form a cathode layer through screen printing.

The cathode layer was heat treated in a process of maintaining the cell at 800 ° C for 2 hours at the temperature of bonding the sealant in the cell performance evaluation process without any heat treatment.

After the air cathode screen printing, the cells which had been dried were mounted on the button cell measuring jig and the performance was measured.

Performance at the time of measurement, the anode-to Air (500sccm) to the air electrode 4 vol% H sloppy the ₂ O H ₂ (250sccm) and N ₂ (250sccm) containing at the same time, the voltage and the open circuit voltage-measured output curve 500 Excellent cell performance as shown in Table 1 and FIG. 7 below was obtained in the middle and low temperature range of ~ 550 ° C.

Measuring temperature Open circuit voltage P _max (W / cm ² ) P (W / cm ² ) @ 0.7 V 500 ℃ 0.941V 0.32 (0.64A, 0.5V) 0.24 (0.34 A) 550 ℃ 0.911V 0.50 (1.00 A, 0.5 V) 0.39 (0.56A)

FIG. 8 illustrates an example of a metal-supported solid oxide fuel cell when applied to an SOFC stack to be implemented by forming a solid oxide fuel cell on a thin metal plate having holes.

Since the conventional metal-supported solid oxide fuel cell having a porous metal support as a whole is porous, it is difficult to provide a strong airtight joint such as direct welding or brazing with the metal separator because the metal support is porous. Therefore, Seal between them using glass.

However, as a preferred embodiment of the present invention, the metal supporting body cell starting from the metal thin plate to be sought starts to selectively perforate only a portion necessary for the electrode reaction of the metal thin plate, and the metal supporting body at the edge of the cell maintains the state of the metal plate. Since the airtight connection with the metal separator is possible by a robust and reliable method such as welding or intermetallic brazing as in the image, it is necessary to improve the stability of the entire stack including the robustness of the gas- It is possible to improve the robustness of the apparatus.

While the invention has been shown and described with reference to certain exemplary embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the scope of the following claims. Those who do it will easily understand.

11: metal support 11a: hole
12: metal powder paste 14: fine pore metal layer
15: diffusion-permitting layer 16: fuel electrode layer
17: solid electrolyte layer 18: cathode layer

Claims (38)

A method of manufacturing a cell for a solid oxide fuel cell comprising a metal support, a microporous metal layer, an anode layer, a solid electrolyte layer and a cathode layer,
A plurality of holes are formed in the metal support, a green powder paste is filled in the holes of the metal support, a green sheet constituting a micropore metal layer is laminated on the metal support, and sintering is performed in an inert atmosphere A method of manufacturing a cell for a metal-supported solid oxide fuel cell. The method according to claim 1,
Wherein the metal powder paste or the green sheet constituting the micropore metal layer is made of the same material as the metal support. 3. The method of claim 2,
Wherein the green sheet constituting the metal powder paste or the micropore metal layer comprises an Fe-Cr-based stainless steel alloy or a waste-light-based stainless steel alloy. The method of claim 3,
Wherein at least one of Crofer22APU, Crofer22H, and ZMG232L is selected from the group consisting of Fe-26Cr- (Mo, Ti, Ti) and the green sheet constituting the metal support, the metal powder paste and the micro- , Y ₂ O ₃ ) alloy or Fe-Cr-Mx alloy (Mx = Ni, Ti, Ce, Mn, Mo, Co, La, Y, Al). 5. The method of claim 4,
Wherein the thickness of the microporous metal layer after sintering is 50 to 70 um. 6. The method according to any one of claims 1 to 5,
And a diffusion barrier layer is further formed between the micropore metal layer and the anode layer. The method according to claim 6,
The diffusion barrier layer is _{CeO 2, Ce 1 - x Ln} x O 2 -δ, (Ln = Gd, Sm, Y, x = 0.1 ~ 0.3, δ = 0 ~ 0.2) (La 1 - x A x) Cr 1 - _{y B y O 3 ± δ (} A = Sr, Ca, or mixtures thereof x = 0.1 ~ 0.4; B = Mn, Co, Cu, Ni, V, Fe, Ti, Ce, Ru or mixtures thereof, y = 0 ~ 0.5, δ = 0 ~ 0.3) , (1-x A x La) s Ti 1-y B y O 3 ± δ (A = Sr, Ca, or mixtures thereof x = 0.1 ~ 0.6; B = Mn, Co, (Sr _{1 - x} A _x ) _s Ti _{1 - y} Nb (where n is an integer from 0 to 3) _y O _{3 ± δ} (A = Y, La, Gd, Sm or a mixture thereof, x = 0.05 to 0.2; y = 0 to 0.5; s = 0.9 to 1.0 and δ = 0 to 0.3) Wherein said solid support is a composite metal supported solid oxide fuel cell. 8. The method of claim 7,
Wherein the diffusion preventive layer has a composition of Ce _{0 .9} Gd _{0 .1} O _{1 .95} or a composition comprising 0.2 to 0.8 wt% of Co ₃ O ₄ in the composition. 9. The method of claim 8,
Wherein the diffusion preventing layer has an average thickness after sintering of 1 to 10 μm. 8. The method of claim 7,
The fuel electrode layer is NiO and _{(ZrO 2) 1-x (} Y 2 O 3) x (x = 0.08 ~ 0.1) of the composite, NiO and _{(ZrO 2) 0.90 (Sc 2} O 3) 0.1-x (Yb 2 O ₃ ) _x (x = 0 to 0.06) of Complex, and NiO A composite of any one of Ce _{1 - x} Ln _x O _{2 - δ} , (Ln = Gd, Sm, Y, x = 0.1 to 0.3 and δ = 0 to 0.2) or a mixture thereof. ≪ / RTI > 11. The method of claim 10,
Wherein the anode layer is a composite of NiO and Ce _{0 .9} Gd _{0 .1} O _{2 -δ} (δ = 0 to 0.2) solid electrolyte powder. 12. The method of claim 11,
Wherein the NiO content in the composite is in the range of 50 to 75 wt%. 13. The method of manufacturing a solid oxide fuel cell according to claim 12, wherein the anode layer has an average thickness of 10 [mu] m to 50 [mu] m after sintering. 11. The method of claim 10,
_Wherein the solid electrolyte layer is a system oxide of Ce _{1 - x} Ln _x O _{2 -?} (Ln = Gd, Sm, Y, x = 0.1 to 0.3,? = 0 to 0.2) . 15. The method of claim 14,
The solid electrolyte layer may be formed of a metal support which is a mixture obtained by adding at least one of Co ₃ O ₄ , CoO, CuO, MnO, and MnO ₂ transition metal oxide to the solid oxide electrolyte in the range of 0.2 to 2 wt% A method of manufacturing a cell for a solid oxide fuel cell. 16. The method of claim 15,
Wherein the solid electrolyte layer has a composition of Ce _{0 .9} Gd _{0 .1} O _{1 .95} or a composition containing 0.2 to 0.8 wt% of Co ₃ O ₄ in the composition. 17. The method of claim 16,
Wherein the solid electrolyte layer has an average thickness after sintering of 5 占 퐉 to 30 占 퐉. 16. The method of claim 15,
Wherein the air electrode layer comprises a material selected from the group consisting of (A _1-x B _x ) _s Fe _{1 -y} Co _y O _{3 -δ} (A = La, Gd, Y, Sm, Ln or a mixture thereof, B = Ba, Sr, Ca, Ln = lanthanides) and _{(1-x Sr x La)} s MnO 3-δ electroconductive oxide comprising, or metal support consisting of a powder of a solid electrolyte composition on the electrically conductive oxide as the complex was added to a 0 ~ 50 vol% range A method of manufacturing a cell for a solid oxide fuel cell. 19. The method of claim 18,
The air electrode layer _{(La 0 .6, Sr 0 .4} ) (Co 0 .2, Fe 0 .8) O 3 in the _{40 ~ 60 wt% Ce 0 .9} Gd 0 .1 O 1. _{95. A} method of manufacturing a cell for a metal-supported solid oxide fuel cell, 20. The method of claim 19,
Wherein the cathode layer has an average thickness after sintering of 10 [mu] m to 50 [mu] m. The method according to claim 1,
The method for manufacturing the solid oxide fuel cell
A first step of preparing the metal support;
A second step of filling a metal powder paste in a plurality of holes formed in the metal support;
A third step of laminating a green sheet constituting the micropore metal layer on one surface of the metal support using a warm isostatic pressing (WIP) process;
A fourth step of sintering and bonding the micropore metal layer;
A fifth step of laminating the green sheet of the anode layer on the micropore metal layer;
A sixth step of laminating the green sheet of the solid electrolyte layer on the anode layer;
A seventh step of sintering the solid electrolyte layer green sheet; And
An eighth step of screen-printing the cathode layer on the sintered solid electrolyte layer;
Wherein the solid oxide fuel cell comprises a metal-supported solid oxide fuel cell. 22. The method of claim 21,
Further comprising a fourth step of laminating a green sheet of a diffusion preventing layer on the micropore metal layer between the fourth step and the fifth step. 23. The method of claim 22,
Wherein each of the green sheets is formed by tape casting in the third, fourth, fifth, and sixth steps. 24. The method of claim 23,
Wherein the green sheets in the 4-1st, 5th, and 6th steps are arranged in order and the green sheets constituting the respective layers are laminated using a warm isostatic press (WIP) process, A method of manufacturing a fuel cell cell. 25. The method of claim 24,
In the warm isostatic pressing (WIP) process, each formed green sheet is vacuum packed, and the vacuum packed laminate is placed in a warm isostatic pressing apparatus in which the water temperature inside the cylinder is maintained at 60 to 80 DEG C, cm < ² > for 10 to 40 minutes. The method of manufacturing a cell for a metal-supported solid oxide fuel cell according to claim 1, 26. The method of claim 25,
Further comprising the step of removing the binder and the plasticizer from the laminate after the warm isostatic pressing (WIP) process. 27. The method of claim 26,
Wherein the step of removing the binder and the plasticizer is carried out at 200 ° C, 350 ° C, and 500 ° C for 2 to 5 hours or more at a temperature rising rate of 1 to 3 ° C per minute in air, Gt; 28. The method of claim 27,
Further comprising the step of compression-molding the diffusion preventing layer, the fuel electrode layer and the solid electrolyte layer by a cold isostatic press (CIP) process on the laminate from which the binder and the plasticizer have been removed, to manufacture a metal support solid oxide fuel cell Way. 29. The method of claim 28,
In the cold isostatic press (CIP) process, the laminate is packed in a vacuum, and then is put in a cold isostatic press, and isotropic pressure of 1,000 to 5,000 kgf / cm ² is applied for 5 to 30 minutes in a cold isostatic press Wherein the metal-supported solid oxide fuel cell is a metal-supported solid oxide fuel cell. 30. The method of claim 29,
(CIP) process and then sintering in a sintering furnace in an argon atmosphere for 1 to 5 hours at a temperature in the range of 1,000 to 1,070 ° C to manufacture a metal support solid oxide fuel cell Way. 26. The method of claim 25,
In the fourth step, the sintering is performed in a sintering furnace in a hydrogen atmosphere at a temperature of 1,100 to 1,180 ° C for 1 to 5 hours, thereby producing a cell for a solid oxide fuel cell. 31. The method according to any one of claims 21 to 31,
The method for producing a cell for a solid oxide fuel cell further comprises a ninth step of sintering the cathode layer,
Wherein the ninth step is sintered at 750-850 ° C, which is a bonding temperature of the sealing material at the time of stack or cell evaluation, without performing any heat treatment in the cell manufacturing process. A metal support having a plurality of holes;
A micropore metal layer formed on the metal support;
A fuel electrode layer formed on the micropore metal layer;
A solid electrolyte layer formed on the anode layer; And
A cathode layer formed on the solid electrolyte layer;
/ RTI >
And a metal powder paste is sintered and filled in the hole. 34. The method of claim 33,
Wherein the metal powder paste is made of the same material as the metal support and / or the micropore metal layer. 35. The method of claim 34,
And a diffusion barrier layer further formed on the micropore metal layer. 37. The method according to any one of claims 33 to 35,
Wherein the metal powder paste comprises an Fe-Cr-based stainless steel alloy or a waste-light-based stainless steel alloy. 37. The method of claim 36,
Wherein at least one of Crofer22APU, Crofer22H, and ZMG232L is selected from the group consisting of Fe-26Cr- (Mo, Ti, Ti) and the green sheet constituting the metal support, the metal powder paste and the micro- , Y ₂ O ₃ ) alloy or Fe-Cr-Mx alloy (Mx = Ni, Ti, Ce, Mn, Mo, Co, La, Y, Al). 39. The method of claim 37,
Wherein the microporous metal layer and the sintered metal powder paste have a plurality of pores formed therein.

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