KR20180061126A - A method of producing a cell for a metal-supported solid oxide fuel cell - Google Patents

Abstract

The present invention provides a method for manufacturing a metal support-type solid oxide fuel cell by a room-temperature coating process without a high-temperature sintering process. A method for manufacturing a cell for a meta support-type solid oxide fuel cell according to the present invention comprises the steps of: i) preparing a metal support; ii) forming an anode layer on one side surface of the metal support; iii) forming a solid electrolyte layer on the surface of the anode layer; iv) selectively forming a cathode interface reaction prevention layer on the surface of the solid electrolyte layer; and v) forming the cathode layer on the surface of the solid electrolyte layer or the cathode interface reaction prevention layer. Here, a step of forming the anode layer, the solid electrolyte layer, and the cathode interface reaction prevention layer is performed by an aerosol spraying scheme.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a metal-supported solid oxide fuel cell,

The present invention relates to a solid oxide fuel cell, and more particularly, to a method for manufacturing a cell for a metal support type solid oxide fuel cell at room temperature.

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 travel through the solid electrolyte layer to the fuel electrode, 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) is a thick electrolyte Layer, and a thin anode layer and a cathode layer. In the case of an electrolyte support-type cell, when a solid electrolyte having a thickness of 100 to 500 μm required for a mechanical support is used, the Ohmic resistance of the solid electrolyte is large. In order to obtain the battery 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 (balance-of-plant, BOP) .

The anode-supported cell can form a thin solid electrolyte layer with a thickness of 5 to 20 μm on the anode layer of 0.3 to 1000 μm thickness to reduce the ohmic of the electrolyte, thereby lowering the temperature of the SOFC operation temperature to a middle temperature of less than 800 ^° C. However, 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.

A method of manufacturing a metal-supported solid oxide fuel cell includes co-firing a metal support, an anode layer, and a powder forming the solid electrolyte layer, respectively, in a reducing atmosphere after tape casting and lamination.

However, such a manufacturing method by co-firing can be carried out in such a manner that the solid electrolyte layer, the fuel electrode layer, and the metal support layer each have precise control of the thermal expansion coefficient, sintering shrinkage rate, and the like, and that the metal support has sufficient porosity even after high- The particle size, the surface roughness and the calcination 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, the co-firing process is a reducing atmosphere sintering process in order to prevent the oxidation of the metal support during the co-firing process. In this case, the physical properties of the fuel electrode material change due to the phase change or the thermal change of the metal support itself .

In addition, the co-firing method is a reducing atmosphere sintering in order to prevent the oxidation of the metal support during the co-firing process. In this case, the metal support may undergo phase change due to the interfacial reaction between the anode material and the metal support material, There is a problem that the cell performance is deteriorated due to a decrease in chemical activity.

The present invention also provides a method of manufacturing a metal-supported solid oxide fuel cell by a room temperature coating process without sintering at a high temperature.

A metal-supported solid oxide fuel cell manufactured by a normal-temperature coating process without a high-temperature sintering process.

According to an embodiment of the present invention, there is provided a method of manufacturing a cell for a metal-supported solid oxide fuel cell including a metal support, a fuel electrode layer, a solid electrolyte layer, and a cathode layer, wherein each of the layers has a metal support A method of manufacturing a cell for a body-type solid oxide fuel cell is provided.

The method for manufacturing a cell for a metal-supported solid oxide fuel cell includes the steps of: i) preparing the metal support; Ii) forming the anode layer on one side of the metal support; Iii) forming the solid electrolyte layer on the surface of the anode layer; Iv) selectively forming the air electrode interface reaction preventing layer on the surface of the solid electrolyte layer; And (v) forming the air electrode layer on the surface of the solid electrolyte layer or the air electrode interface reaction preventing layer. .

At this time, it is preferable that the step of forming the anode layer, the solid electrolyte layer and the air electrode interface reaction prevention layer is formed by the aerosol spraying method.

The forming of the cathode layer may be performed by a screen printing method or a spray painting method.

The metal support is preferably a porous metal having a pore structure, a porosity of 25% to 60%, a pore of 50um or less, and a thickness of the metal support of 0.2 to 2 mm.

The metal support may be formed by molding a metal powder, a metal powder, a pore-forming material, or ceramic particles in a sheet form by powder metallurgy, tape casting or extrusion molding, , Vacuum, or an inert atmosphere at a temperature in the range of 1000 to 1400 ° C.

The aerosol spraying method used in one embodiment of the present invention comprises preparing a ceramic powder constituting each layer, injecting a conveying gas while applying mechanical vibration to the ceramic powder to generate an aerosol, And the coating layer is formed by kinetic energy of the ceramic powder.

In this case, the ceramic powder preferably has an average particle diameter of 0.2 to 5 μm, more preferably 0.3 to 3 μm.

The thickness of the anode layer coated in the step of forming the anode layer is preferably 5 to 30 μm.

The thickness of the solid electrolyte layer coated in the step of forming the solid electrolyte layer is preferably 5 to 30 μm.

Meanwhile, the thickness of the air electrode interface reaction prevention layer coated in the step of forming the air electrode interface reaction preventing layer is preferably 1 um to 30 um.

At this time, it is more preferable that the thickness of the air electrode interface reaction prevention layer coated in the step of forming the air electrode interface reaction preventing layer is 2 um to 6 um.

Here, the cathode layer formed in the cathode layer formation step sinters the fuel cell stack while maintaining the temperature of the fuel cell stack at 600 ^° C to 850 ^° C for 2 hours or more during the initial operation raising of the fuel cell system.

The metal support used in one embodiment of the present invention is preferably a ferritic stainless steel or an Fe-Cr alloy.

And the metal support is Crofer22APU and Crofer22H and use ZMG232L, or the Fe-Cr alloy is Fe _{x 1 -x} -Cr (x = 16 ~ 30) and Fe-26Cr- (Mo, Ti, Y 2 O 3), Fe-Cr-M x alloy _{(M x = Ni, Ti,} Ce, Mn, Mo, Co, La, Y, Al) of which use one or the Fe-Cr-based, if the alloy the Fe-Cr alloy in 0 ~ 50 vol% of metal oxide _{(doped-Al 2 TiO 5,} doped-Zirconia, doped-Ceria, MgO, to _{CaO, SrO, CoO x, ZnO} , VO x, Cr 2 O 3, FeO, MoO x, WO x, Ga 2 O 3, Al 2 O 3, the mixture is a mixture of TiO _2, and mixtures thereof) are preferred.

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 ~ 0.06) of the composite, and NiO and _{Ce 1 - x Ln x O 2} -δ, (Ln = Gd, Sm, Y, x = 0.1 ~ 0.3, lt; RTI ID = 0.0 ># = 0 ~ 0.2). < / RTI >

The NiO content of the composite is preferably 50 to 75 wt%.

The solid electrolyte layer used in one embodiment of the present invention may be one or more of (ZrO ₂ ) _{1- x} (Y ₂ O ₃ ) _x (x = 0.03-0.1), (ZrO ₂ ) _0.89 (Sc ₂ O ₃ ) _{0.1 2} ) _0.01 , (ZrO ₂ ) _0.90 (Sc ₂ O ₃ ) _0.1 -x (Yb ₂ O ₃ ) _x (x = 0 to 0.06), Ce _1-x Ln _x O _{2 -δ} , (Ln = Gd, Sm, Y, x = 0.1 to 0.3, (x = 0.1 to 0.3, y = 0.1 to 0.3, z = 0.01 to 0.15, and? = 0 to 0.2) and La _{1 - x} Sr _x Ga _{1 - y} Mg _{y - z} Co _z O ₃ . 0.2), or a mixture thereof.

In addition, the air electrode interface reaction preventing layer used in the embodiment of the present invention has Ce _{1 -x} Ln _x O _{2 -δ} (Ln = Gd, Sm, Y, x = 0.1 to 0.3, δ = 0 to 0.2) based oxide.

It is preferable to use a composite in which the powder of the solid electrolyte composition is added to the cathode electroconductive oxide or the electroconductive oxide in the range of 0 to 50 vol%.

At this time, the electrically conductive oxide _{(Ln 1 - x B x)} s MO 3 ± δ (Ln = lanthanide , or mixtures thereof, B = Ba, Sr, Ca , or mixtures thereof, M = Co, Fe, Mn , Ni, Cu or mixtures thereof, x = 0.05 ~ 0.4, s = 0.9 ~ 1.0, δ = 0 ~ 0.3) and _{(A 1- x B x) s} Fe 1 - y Co y O 3 ± δ (A = La, Gd, Sm X, y = 0 to 1.0, s = 0.9 to 1.0,? = 0 to 0.3) and (La1 _- xSr _x ) _s MnO _{3 ± δ} (x = 0.05 to 0.4, s = 0.9 to 1.0, ? = 0 to 0.3) or a mixture thereof can be used.

The present invention can be applied to a fuel cell stack (Fuel Cell Stack) and a fuel cell power generation system (Fuel Cell Power Generation System) manufactured using the fuel cell manufactured by any one of the above- .

Since the method for manufacturing a metal-supported solid oxide fuel cell according to an embodiment of the present invention includes the steps of: coating a fuel electrode layer, a solid electrolyte layer, an air electrode interface reaction prevention layer, and a cathode layer on a metal support, The sintering shrinkage does not occur, so that there is a technical effect that a cell having excellent dimensional stability can be provided.

Also, when manufacturing a fuel cell according to an embodiment of the present invention, the manufacturing yield is high and there is a technical effect of minimizing warping of the cell due to the difference in thermal expansion coefficient between the respective components.

The manufacturing method of the fuel cell according to one embodiment of the present invention has the technical effect of suppressing the deterioration of performance due to the high-temperature particle growth of the fuel electrode and the interface reaction between the metal support and the fuel electrode.

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 conceptual view showing an aerosol spraying apparatus used in manufacturing a fuel cell according to an 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 method of manufacturing a metal-supported solid oxide fuel cell according to an embodiment of the present invention includes forming a fuel electrode layer, a solid electrolyte layer, and an air electrode interface reaction prevention layer on a metal support using an aerosol of an oxide powder constituting each layer, Coating is carried out sequentially at room temperature by spraying method. The air electrode layer is coated on the air electrode interface reaction preventive layer thus coated at room temperature by a screen printing method or a spray painting method.

When manufacturing a cell constituting a metal-supported solid oxide fuel cell according to an embodiment of the present invention, the fuel cell cell can be manufactured at room temperature by completing all steps of cell fabrication without going through a sintering process.

In order to manufacture a metal-supported solid oxide fuel cell according to an embodiment of the present invention, a metal support is first prepared.

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 / ^oC . The reason why the thermal expansion coefficient of the metal support is limited is to reduce the difference in thermal expansion coefficient between the metal support and each of the ceramic functional layers stacked thereon to prevent the separation of the functional layer and the warping of the cell due to the difference in thermal expansion coefficient between the respective components to be.

Ferrite-based stainless steel, Crofer22APU and Crofer22H from Tyssenkrupp, Germany, and ZMG232L from Hitachi Metal, Japan, are examples of materials for the metal support having such characteristics.

Further, as the Fe-Cr alloy having such characteristics, Fe _{1- x} -Cr _x (x = 16 ~ 30) and Fe-26Cr- (Mo, Ti, Y 2 O 3), Fe-Cr-M x alloy _{(M x = Ni, Ti,} Ce, Mn, Mo, Co, La, Y, Al). In case of such an Fe-Cr alloy, 0 to 50 vol% of a metal oxide (doped-Al ₂ TiO ₅ , 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.

The metal support may be prepared by mixing the metal powder of the above composition alone or in combination with a metal powder, a pore-forming body or ceramic particles, and molding the mixture into a sheet by powder metallurgy, tape casting or extrusion molding Later, it is prepared by sintering in the range of 1000 ^° C to 1400 ^° C in a reducing, vacuum, or inert atmosphere.

At this time, the metal support has a connection pore structure to facilitate permeation of gas, and preferably has a porosity ranging from 25% to 60%. In addition, if the maximum pore size of the metal support is not less than a certain size, a pin-hole is formed in the anode layer formed on the pore, so that the metal support preferably has a maximum pore size of 50um or less.

The thickness of such a metal support is preferably 0.2 to 2 mm. If the thickness of the metal support is less than 0.2 mm, the strength to the support is weak and it may be bent during use. If the thickness of the metal support is 2 mm or more, the gas permeability is decreased and it is difficult to use the support as a support.

Next, an anode layer, a solid electrolyte layer, and an air electrode interface reaction preventing layer are sequentially formed on the prepared metal support by an aerosol spraying method.

When the fuel electrode layer, the solid electrolyte layer and the air electrode interface reaction preventing layer are sequentially formed on the metal support by the aerosol spraying method, the ceramic powder constituting each layer is sprayed on the metal support or another layer .

When the ceramic powder is sprayed on the metal support or another layer already deposited at high speed in an aerosol state, a high-density ceramic coating layer having a crystal structure such as a raw powder can be produced at room temperature.

Hereinafter, a deposition method for coating each layer using an aerosol spraying method will be described with reference to FIG.

As shown in FIG. 1, when the carrier gas is first delivered from the carrier gas storage chamber 10, the carrier gas is injected into the aerosol chamber 13 along the transfer pipe 11. As the carrier gas to be used at this time, an inert gas of any one of nitrogen, helium and argon may be used, or a mixed gas in which these gases are mixed with each other, or a mixed gas in which these gases are mixed with compressed air may be used.

The carrier gas injected into the aerosol chamber 13 is transferred into the vacuum deposition chamber 15 together with the ceramic powder in the chamber 13. At this time, the aerosol chamber 13 is vibrated vertically or horizontally by the vibration device 16. In this state, the carrier gas injected into the aerosol chamber 13 is mixed with the ceramic powder to generate an aerosol.

On the other hand, the vacuum deposition chamber 15 is maintained in a vacuum state by a vacuum device 17. The vacuum device 17 is constituted by a booster pump and a rotary vacuum pump and the vacuum device 17 also functions to exhaust the transfer gas in the aerosol sucked into the vacuum deposition chamber 15. At this time, the degree of vacuum of the vacuum deposition chamber 15 is preferably maintained at 1 to 10 Torr. A pressure difference is generated between the aerosol chamber 13 and the vacuum deposition chamber 15 so that the aerosol formed in the aerosol chamber 13 is sucked into the vacuum deposition chamber 15 through the nozzle 19 toward the substrate 20 .

At this time, the distance between the nozzle 19 and the substrate 20 is preferably adjusted in the range of 1 to 20 mm. The slit through which the aerosol formed at the end of the nozzle 19 is discharged preferably has a width of 0.3 to 0.5 mm and a length of 10 to 40 mm.

However, the width and the length of the slit of the nozzle 19 can be selected as optimum conditions depending on the composition of the ceramic powder forming the aerosol and the state of the deposited layer to be deposited.

The aerosol sprayed from the nozzle 19 onto the substrate 20 collides with the substrate 20 to deposit a dense ceramic film. As described above, the area of the ceramic film deposited on the substrate 20 can be controlled to a desired size while moving the nozzle to the left and right, and the thickness thereof can be controlled in proportion to the spraying time of the aerosol.

When the ceramic powder in an aerosol state is injected at high speed toward the substrate 20 through the nozzle 19, the kinetic energy held by the ceramic powder is transferred to the substrate 20. At this time, the particles of the ceramic powder are finely pulverized due to the impact thereof, and at the same time, deformation occurs to form a high-density coating layer. The coating layer formed in this way maintains the crystallinity of the ceramic powder without forming additional heat treatment, and forms a high-density film having excellent bonding strength with the substrate.

When the ceramic vapor deposition film is formed on the substrate by the aerosol spraying method, the particle size of the ceramic powder used has a great influence on the film formation. Therefore, in the embodiment of the present invention, the average particle size of the ceramic powder to be deposited is limited to 0.2 to 5 μm. More preferably, the average particle size of the ceramic powder is from 0.3 mu m to 3 mu m.

The reason for limiting the average particle size of the ceramic powder to be used is that if the average particle size of the ceramic powder is 0.2 μm or less, a dense film is not formed and a compressed powdery film is formed. If the average particle size is 5 μm or more, The substrate or coating layer is shaved by the coarse particles existing in the coating layer and the coating layer is not formed well. The particle size of the ceramic powder is controlled by calcining and milling the object powder, and this method is the same as the method for controlling the general ceramic particle diameter, and thus a detailed description thereof will be omitted.

Next, a method of forming an anode layer, a solid electrolyte layer and an air electrode interface reaction prevention layer on a metal support using the above-described aerosol spraying apparatus will be described in order

First, a method of forming an anode layer on a metal support will be described.

A ceramic powder to be used as an anode layer is prepared to form the anode layer. The composition of the ceramic powder forming the anode layer is a composite of NiO and (ZrO ₂ ) _{1 -x} (Y ₂ O ₃ ) _x (x = 0.08 to 0.1), 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 Ce _{1 - x} Ln _x O ₂ is one of the complex or mixture of complexes of _{-δ (Ln = Gd, Sm,} Y, x = 0.1 ~ 0.3, δ = 0 ~ 0.2).

More preferably, the fuel electrode layer ceramic powder 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} (δ = 0 to 0.2) solid electrolyte powder. Here, the content of NiO in such a composite is preferably in the range of 50 to 75 wt%. This is because NiO is reduced to Ni when the fuel cell is operated, and thus about 15 to 30% of pores are generated. Thus, the high-density anode layer produced by aerosol vacuum injection can form a porous structure.

The fuel electrode layer ceramic powder prepared as described above is charged into the aerosol chamber 13, and mechanical vibration is applied to the aerosol chamber 13, and a transport gas is injected to generate an aerosol of the ceramic powder. The aerosol is sprayed on the metal support mounted on the substrate 20 at a high speed under vacuum to form a fuel electrode coating layer.

The anode layer thus coated on the metal support is preferably coated to a thickness of 5 to 30 μm.

The following describes the process of depositing the solid electrolyte powder on the coated anode layer.

The ceramic powder to be used as the solid electrolyte layer is (ZrO ₂ ) _{1 - x} (Y ₂ O ₃ ) _x (x = 0.03 ~ 0.1), (ZrO 2) 0.89 (Sc 2 O 3) 0.1 (CeO 2) 0.01, (ZrO 2) 0.90 (Sc 2 O 3) 0.1- x (Yb 2 O 3) x (x = _{0 ~ 0.06), Ce 1 -} x Ln x O 2 - δ Ln = Gd, Sm, y, x = 0.1 ~ 0.3, δ = 0 ~ 0.2) , and _{La 1 - x Sr x Ga 1} - y Mg y - z CozO _{3 - ?} X = 0.1 to 0.3, y = 0.1 to 0.3, z = 0.01 to 0.15,? = 0 to 0.2) or a mixture thereof is preferable.

The method of forming the solid electrolyte layer formed on the anode layer is the same as the method of forming the anode layer, and thus a detailed description thereof will be omitted.

The coating thickness of the solid electrolyte layer formed on the anode layer is preferably 5 to 30 μm.

The following describes the process of depositing the air electrode interface reaction preventive layer on the coated solid electrolyte layer.

The air electrode interface reaction preventing layer may be selectively deposited on the upper portion of the solid electrolyte layer.

That is, when the solid electrolyte layer is a zirconia-based material, the material forming the air electrode, which will be described later, and the interfacial layer are caused to form SrZrO ₃ , La ₂ Zr ₂ O ₇ And such An interface reaction layer having a high electrical resistance can be produced. Therefore, in order to prevent such an interfacial reaction, the air electrode interface reaction preventing layer is coated on the upper part of the solid electrolyte layer.

Zirconia based solid electrolytes _{(ZrO 2) 1- x (Y} 2 O 3) x (x = 0.03 ~ 0.1), (ZrO 2) 0.89 (Sc 2 O 3) 0.1 (CeO 2) 0.01 and _{(ZrO 2) 0.90 (Sc 2} O 3) 0.1- x (Yb 2 O 3) x (x = 0 to 0.06) It is one of them. The interfacial reaction preventive layer coated on the zirconia-based solid electrolyte includes Ce _1-x Ln _x O _{2 -δ} Ln = Gd, Sm, Y, x = 0.1 to 0.3, and δ = 0 to 0.2.

The method of forming the air electrode interface reaction prevention layer on the solid electrolyte layer is the same as the method of forming the anode layer described above, and thus a detailed description thereof will be omitted.

The thickness of the air electrode interface reaction preventive layer formed on the solid electrolyte layer is 1 um to 30 um, more preferably 2 to 6 um.

As described above, the fuel electrode layer, the solid electrolyte layer, and optionally the air electrode interface reaction prevention layer are coated on the metal support, and then the air electrode layer is formed on the air electrode interface reaction prevention layer.

The cathode layer must be permeable to gas during operation of the fuel cell, so that its structure must be porous.

In the case of the anode layer, NiO is decomposed into Ni in the constituent powder during the operation of the fuel cell, resulting in pores ranging from 15 to 30%. Therefore, the anode layer functions even when it is coated by the aerosol spraying method. However, in the case of the cathode layer, it is difficult to form pores by self-decomposition of the material forming the cathode layer. Therefore, it is not preferable to coat the air electrode layer with the aerosol spray method.

Therefore, it is preferable that the cathode layer is formed by a paste or slurry of ceramic powder on the surface of the air electrode interface reaction prevention layer by a screen printing method or a spray coating method.

Thus, the cathode layer formed at room temperature is not heat-treated and the cell fabrication is completed. When the fuel cell system is operated directly after the cathode layer is formed without heat treatment, the temperature of the fuel cell stack is maintained in the range of 600 ^° C to 850 ^° C for 2 hours in the initial temperature raising process, thereby replacing the heat treatment .

The ceramic powder constituting the cathode layer is preferably a composite obtained by adding an electroconductive oxide or a powder of a solid electrolyte composition to the electroconductive oxide in a range of 0 to 50 vol%. The electrically conductive oxide, the _{(Ln 1 - x B x)} s MO 3 ± δ (Ln = lanthanide , or mixtures thereof, B = Ba, Sr, Ca , or mixtures thereof, M = Co, Fe, Mn , Ni, Cu , or This mixture, x = 0.05 ~ 0.4, s = 0.9 ~ 1.0, δ = 0 ~ 0.3) and _{(A 1- x B x) s} Fe 1 - y Co y O 3 ± δ (A = La, Gd, Sm, Pr, or a mixture thereof, B = Ba, Sr, Ca , or mixtures thereof, x = 0.05 ~ 0.4, y = 0 ~ 1.0, s = 0.9 ~ 1.0, δ = 0 ~ 0.3) , and (La _{1 - x} Sr _x ) _s MnO _{3 ± δ} (x = 0.05 to 0.4, s = 0.9 to 1.0, ? = 0 to 0.3)), or a mixture thereof.

As described above, the thickness of the air electrode layer formed on the air electrode interface reaction prevention layer is preferably from 10 μm to 50 μm.

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.

Claims (19)

A method of manufacturing a cell for a metal-supported solid oxide fuel cell including a metal support, an anode layer, a solid electrolyte layer, and a cathode layer,
Each of the layers is formed at room temperature without being subjected to a sintering process,
A method of manufacturing a cell for a metal-supported solid oxide fuel cell includes:
Preparing the metal support;
Forming the anode layer on one side of the metal support;
Forming the solid electrolyte layer on the surface of the anode layer;
Forming an air electrode interface reaction preventing layer on a surface of the solid electrolyte layer; And
And forming the air electrode layer on the surface of the air electrode interface reaction preventing layer,
Wherein the step of forming the anode layer, the solid electrolyte layer and the air electrode interface reaction preventing layer is performed by an aerosol spraying method,
Wherein the cathode layer is formed by a screen printing method or a spray painting method. The method according to claim 1,
Wherein the metal support is a porous metal having a pore structure and a porosity of 25% to 60%. 3. The method of claim 2,
Wherein the pores of the metal support are 50um or less and the thickness of the metal support is 0.2 to 2mm. 3. The method of claim 2,
The metal support may be formed by forming a metal powder in a form of sheet by powder metallurgy, tape casting or extrusion, or by mixing the metal powder with a metal powder, a pore-forming body or ceramic particles, In a vacuum or in an inert atmosphere at a temperature in the range of 1000 to 1400 ° C. The method according to claim 1,
In the aerosol spraying method, a ceramic powder constituting each layer is prepared, an aerosol is generated by injecting a conveying gas while applying mechanical vibration to the ceramic powder, and the aerosol is sprayed at high speed onto a substrate in a vacuum state, Wherein the coating layer is formed by the kinetic energy of the solid oxide fuel cell. 6. The method of claim 5,
Wherein the ceramic powder has an average particle diameter of 0.2 to 5 占 퐉. 6. The method of claim 5,
Wherein the ceramic powder has an average particle diameter of 0.3 mu m to 3 mu m. The method according to claim 6,
Wherein the anode layer coated in the step of forming the anode layer has a thickness of 5 um to 30 um. The method according to claim 6,
Wherein the solid electrolyte layer coated in the step of forming the solid electrolyte layer has a thickness of 5 to 30 μm. The method according to claim 6,
Wherein the air electrode interface reaction preventing layer coated in the step of forming the air electrode interface reaction preventing layer has a thickness of 1 um to 30 um. The method according to claim 6,
Wherein the air electrode interface reaction preventing layer coated in the forming step of the air electrode interface reaction preventing layer has a thickness of 2 μm to 6 μm. The method according to claim 1,
The cathode layer formed in the cathode layer formation step is formed by maintaining the temperature of the fuel cell stack at 600 ° C. to 850 ° C. for 2 hours or more during sintering of the fuel cell system during the initial operation of the fuel cell system, Way. 13. The method according to any one of claims 1 to 12,
Wherein the anode layer comprises a composite of NiO and (ZrO2) 1-x (Y2O3) x (x = 0.08 to 0.1), NiO and (ZrO2) 0.90 (Sc2O3) 0.1-x (Yb2O3) x And a composite of any one of NiO and Ce1-xLnxO2-delta, (Ln = Gd, Sm, Y, x = 0.1 to 0.3, A method of manufacturing a cell for a solid oxide fuel cell. 14. The method of claim 13,
Wherein the NiO content of the composite is 50 to 75 wt%. 13. The method according to any one of claims 1 to 12,
(ZrO2) 1-x (Y2O3) x (x = 0.03-0.1), (ZrO2) 0.89 (Sc2O3) 0.1 (CeO2) 0.01, (ZrO2) 0.90 (x = 0.1 to 0.3,? = 0 to 0.2) and La1-xSrxGa1-yMgy-zCozO3? (x = 0 to 0.06), Ce1-xLnxO2-delta (Ln = Gd, Sm, Y, 0.3, y = 0.1 to 0.3, z = 0.01 to 0.15, and? = 0 to 0.2) or a mixture thereof. 13. The method according to any one of claims 1 to 12,
Wherein the air electrode interface reaction preventing layer is a system oxide of Ce1-xLnxO2-delta (Ln = Gd, Sm, Y, x = 0.1 to 0.3, and delta = 0 to 0.2). The method according to claim 1,
Wherein the electrically conductive oxide is selected from the group consisting of (Ln1-xBx) sMO3 占 隆 (Ln = lanthanide or a mixture thereof, B = Ba, Sr, Ca or a mixture thereof, M = Co, Fe, Mn, Ni, Cu, Ba, Sr, Ca, Ca, Sr, Ca, Sr, Ca, Ca, X = 0.05 to 0.4, s = 0.9 to 1.0, s = 0.9 to 1.0,? = 0 to 0.3) and (La1-xSrx) sMnO3? δ = 0 to 0.3), or a mixture thereof. The method of manufacturing a cell for a metal-supported solid oxide fuel cell according to claim 1, A fuel cell stack fabricated using the fuel cell according to any one of claims 1 to 12. A fuel cell power generation system manufactured by using the fuel cell of any one of claims 1 to 12.

Images