KR101796502B1 - Method of manufacturing interconnect coating layer and ceramic interconnects including the interconnect coating layer - Google Patents

Abstract

One embodiment of the present invention is a method for manufacturing an electrode support type connecting member or a separator by simultaneous sintering, comprising: forming a support; Mixing the conductive ceramic powder with a binder and a solvent to prepare a slurry or a tape-cast green sheet, and coating the support on the support to form a first coating layer; Preparing a slurry or tape-cast green sheet of the conductive ceramic powder by drying or heat-treating the first coating layer, and coating the first slurry on the first coating layer to form a second coating layer; Co-sintering the support on which the first coating layer and the second coating layer are formed; To a process for producing a support type coupling material coating film.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a support-type connection material coating film, a method of manufacturing a support-type connection material coating film,

The present invention relates to a ceramic connecting material applied to an electrochemical cell including an electrolytic cell or a fuel cell, and a method of manufacturing the same.

Solid Oxide Electrolysis Cells (SOEC) and Solid Oxide Fuel Cells (SOFCs) are composed of ceramics, which are excellent in heat resistance, as electrolytes and electrodes, which are basic components of the cell. Similarly, solid oxide fuel cells are known as fuel cells that operate over a relatively wide temperature range compared to other fuel cells and are being developed as generators for large scale distributed generation as well as for residential and small residential complexes and transportation.

In addition, the dual solid oxide electrolytic cell can be used as a high temperature electrolytic apparatus for producing hydrogen from steam by a reverse reaction process of a fuel cell. In the United States, a high temperature electrolytic cell We are developing the production technology and have developed hydrogen production system of stacked scale high temperature electrolytic hydrogen production system in Korea.

In recent years, the use of solid oxide electrolytic cells to produce syngas by electrolyzing greenhouse gases and carbon dioxide, which are the main causes of global warming, together with steam, and to convert them into various liquid fuels such as methanol and gasoline. .

Therefore, researches on hydrogen production and carbon dioxide conversion associated with renewable energy have been actively conducted using high temperature electrolysis technology composed of solid oxide electrolytic cells, and fuel cells and technology can be shared in many parts such as devices and operation methods Fuel cell technology can be used for hydrogen production and carbon dioxide conversion as it can be expected to develop in conjunction with fuel cell technology.

The solid oxide electrolytic cell and the fuel cell can be classified into three types of tubular type, flat tubular type, and flat type, depending on the cell shape. The solid oxide electrolytic cell and the fuel cell can be classified into three types, that is, a fuel electrode and an air electrode, Depending on the constituent elements, it is divided into the anode support type, the electrolyte support type, and the metal support type.

A planar solid oxide electrolytic cell and a fuel cell having a double anode-supported structure have a very thin (10 to 30 μm) electrolyte membrane coated on an anode support and have a lower temperature (700 to 800 ° C.) than a conventional electrolyte- Not only is it operable, but it also has the advantage of being able to use cheap metal connectors (separator plates).

The solid oxide electrolytic cell and the fuel cell are stacked and stacked so as to obtain a desired electric output and electrolytic capacity. When a planar solid oxide electrolytic cell and a fuel cell are stacked to form a stack, a separator is required, which is an interconnect that connects the anode of one cell and the cathode of neighboring cells to provide electrical contact.

In addition to the function of providing electrical contact, the separator also distributes the respective gases supplied to the fuel electrode and the air electrode to the cell surface uniformly so that the gases of the fuel electrode and the air electrode are not mixed with each other, And to provide a sealing portion for preventing the leakage of the gas. Metal and ceramic materials are used as the separator, and the metal separator having high temperature durability is superior to the ceramic separator. However, the surface of the metal separator (or the connecting material) that is in contact with the air (oxygen) rapidly increases resistance loss due to an oxide film as an oxidative corrosion reaction proceeds rapidly at a high temperature at which the electrolytic cell or the fuel cell stack operates, The degradation occurs very quickly.

Therefore, development of a separator (or a connection material) using conductive ceramics is desperately required. However, in the case of such a ceramic connection material, when the total electrical conductivity is 1 mm or more in thickness, a voltage drop occurs relatively and the loss in the connection material or the separator becomes very large, which means that the electric efficiency becomes small. Therefore, in order to improve the efficiency and increase the flow rate, development of a high-conductivity supporter thin film type conductor is a very important technology. However, in the case of a thin film ceramic connection material using simultaneous (co) sintering, it is difficult to form a thin film, so that it has been mainly used as a bulk sintered body. In case of the bulk type connecting material, the powder of the connecting material is press-molded or extruded and then sintered. In this case, the thickness of the separating plate must be more than about 0.5 mm. In this case, the area specific resistance corresponding to the entire connecting material is increased, It has been difficult to commercialize it because the resistance is increased and the performance is lowered due to the voltage drop.

Accordingly, by thinning the connecting material, such a membrane can be utilized as a ceramics connecting material or a separating plate as a supporting thin film type.

On the other hand, a thin film manufacturing method is involved in the manufacture of thin films having such functions. As a method for producing a dense coating film (several to several tens of 탆) directly on the surface of a support using a support, there are a vapor phase method and a liquid phase method. Various methods such as CVD (Chemical Vapor Deposition), sputtering, ion beam, EB (Electron Beam) and the like are available as the vapor deposition method, including electrochemical vapor deposition (EVD) , At least one of the disadvantages of expensive manufacturing equipment and limitations of starting materials, difficulty in producing thick specimens due to slow growth rate of thin films, insufficient adhesion to substrate, peeling due to residual stress, and limitation of sample size I have. Therefore, the relatively easy liquid method does not require a specially designed device or expensive equipment, and is proposed as a method that can be used in practice. Particularly, the liquid phase method includes a method such as a sol-gel method, a slip casting method, a tape casting or doctor blade method, a slurry coating method, a spin coating method, Dipping method, electrochemical method, electrophoretic method, hydrothermal decomposition method and the like are used. Among them, as a method of using a sol or a slurry, a slurry coating method including a dipping method, a spin coating method, a spray coating method, a sol-gel method and the like may cause drying or gelation at an early stage due to low green density of the coating layer. As the process progresses, large shrinkage occurs. Such a large shrinkage is particularly a composite type, and when two or more powders are mixed and coated, stress is generated between the support and the coating layer, and the tendency further proceeds in a subsequent sintering process, so that cracks or scales And the like.

Until heretofore, it has been known that the conventional method of using a semiconductor process such as CVD and EVD in manufacturing a dense film is not suitable for manufacturing a large-area support-type film because the manufacturing equipment is expensive, have.

Therefore, in the present invention, the anode support or the general ceramics support fabricated in advance in the plasticized form is used as the substrate, and even if the conductor ceramics are laminated in a single layer or multilayer and heat treatment is performed at the same time, uniformity without undulation or delamination This is related to the technique of making a microstructure thin-film connector (the same meaning as a separator). Particularly, a ceramics connecting material (or a separator) is to be manufactured by drying a green sheet of these components prepared by separately screen printing or tape casting ceramics powder, and drying the resultant by sintering the same to form a dense film.

In particular, in the case of the co-sintered material, if there is a difference in shrinkage between sintering between the support and the coating layer, uniform coating can not be achieved, and the performance of the joint material can not be realized as a thin film coating layer. In addition, when the co-sintered separator is manufactured, the single cell (cell) and the connecting material (separator) can be integrally manufactured. Therefore, the use of metal in the middle can be completely eliminated and the cell and the entire stack are composed of ceramics, A single cell or a stacked module having a high degree of sealing that prevents fuel such as carbon monoxide and methane from leaking can be manufactured.

Therefore, this technology has commercial significance because it can develop a solid oxide fuel cell (SOFC) and a solid oxide electrolytic cell (SOEC) by improving the manufacturing cost, performance (efficiency) and durability of a unit cell and a stack module.

It is an object of the present invention to provide a method for manufacturing interconnects using a multifunctional membrane including a membrane structure such as an electrochemical device, an electrolytic cell, or a fuel cell, A method of manufacturing a support type coupling material coating film having a multilayer structure including a dense film structure, and a method of manufacturing a supporting type coupling material.

One embodiment of the present invention is a method for manufacturing an electrode support type connecting member or a separator by simultaneous sintering, comprising: forming a support; Mixing the conductive ceramic powder with a binder and a solvent to prepare a slurry or a tape-cast green sheet, and coating the support on the support to form a first coating layer; Preparing a slurry or tape-cast green sheet of the conductive ceramic powder by drying or heat-treating the first coating layer, and coating the first slurry on the first coating layer to form a second coating layer; Co-sintering the support on which the first coating layer and the second coating layer are formed; To a process for producing a support type coupling material coating film.

The step of forming the support may include forming a support composition comprising an organic binder and then heat-treating the support composition to produce a plasticizer.

The step of forming the support may comprise: a step of forming a support comprising nickel metal or its oxide (NiO); And a yttria-stabilized zirconia-based oxide (SZ) are mixed, a support composition containing an organic binder, a solvent and a pore-forming agent is added, and the support composition is heat-treated to form a calcined support.

The support powder NiO and CoO, CuO, Fe ₂ O ₃ And Cr ₂ O ₃ A fuel electrode material containing at least one of powders; Zirconia, ceria, bismuth oxide, barium / strontium citrate compound and lanthanum strontium gallium magnesia oxide; And a pore-forming agent are mixed and then ball-milled, dried and formed, and then heat-treated at 600 ° C to 1,500 ° C to form a porous porous anode support.

Wherein the support is at least one of La, Sr, Ca, and Ba at site A and ABO _{3 (at} least one site of B, Mn, Co, Fe, A cathode material comprising a perovskite structure compound or a non-organosilicate high conductivity ceramics material; Zirconia, ceria, bismuth oxide, barium / strontium citrate compound and lanthanum strontium gallium magnesia oxide; And pore-forming agents; , Followed by ball milling, drying and molding, and then heat treatment at 600 ° C to 1,500 ° C to form a porous porous cathode support.

The support may be prepared by preparing a support composition comprising a ceramic powder, an organic binder, a solvent and a pore-forming agent, forming the support composition into a flat plate, a tube or a mixture thereof, And a fuel electrode support.

The step of forming the first coating layer or the step of forming the second coating layer may include coating the conductive ceramics or the composite slurry with at least one of slurry coating, dipping, spray coating, spin coating, and screen printing, can do.

The conductive ceramic powder may include lanthanum-based perovskite.

The conductive ceramic powder may be at least one selected from the group consisting of lanthanum perovskite or SrCo _0.8 Fe _0.2 O ₃ -δ, Sm _{0 . 6} Sr _{0 . 4 CoO 3 -δ, Y 0. 1} Ba 0. ₉ CoO _{3 -δ,} BaBi _{0. 4} Co _{0 . 2} Fe _{0 . 4} O _{3 - ?,} (Sr _0.85 Y _0.1 ) (Ti _0.95 Co _0.05 ) O ₃ , and the conductive ceramic powder; At least one electrolyte material selected from zirconia, ceria, bismuth oxide, barium / strontium citrate compound and lanthanum strontium gallium magnesia oxide; Organic binders; And a solvent are coated with at least one of slurry coating, dipping, spray coating, spin coating, and screen printing, and heat treatment is performed.

Wherein the conductive ceramic powder comprises non-lanthanum-based conductive ceramics, the conductive ceramic powder; At least one electrolyte material selected from zirconia, ceria, bismuth oxide, barium / strontium citrate compound and lanthanum strontium gallium magnesia oxide; Organic binders; And a solvent are coated with at least one of slurry coating, dipping, spray coating, spin coating, and screen printing, and heat treatment is performed.

The step of forming the first coating layer or the forming of the second coating layer may be performed by using TiO ₂ , MnO ₂ , Sr ₂ CO ₃ , SiO ₂ , Cr ₂ O ₃ , Bi ₂ O ₃ And Y ₂ O ₃ , to prepare a coating film using a slurry or a paste.

The support type coupling material coating film is a multi-layer film including a reducing atmosphere stable conductive ceramic film and an oxidative atmosphere stable conductive ceramics film, wherein the first and second coating layers are overlaid and coated with a heat treatment.

The step of forming the first coating layer or the step of forming the second coating layer may be performed by preparing a slurry from the conductive ceramic powder, forming the slurry into a sheet using tape casting, attaching the slurry on the support, To form a ceramic layer, and then heat-treating the ceramic layer to produce a coating film.

Wherein the final thickness of the support type coupling material coating film is 0.1 to 900 탆.

The sintered density of the support type coupling material coating layer may be 30% or more.

The thickness of the support linking material coating layer may be controlled by the number of times that the formation of the first coating layer or the second coating layer is repetitively performed or by the number of times the adhesion of the green sheet is repeatedly performed.

Another embodiment of the present invention relates to a support-type ceramic connector made by the above-described method for producing a supportive connector coating film.

The support is a fuel electrode support which is a mixture of NiO and YSZ, and the first coating layer is a lanthanum perovskite which is a high conductivity ceramics in a reducing atmosphere with a conductive ceramics or a composite thereof, as an LST compound ((La _x Sr _{1 - x)} TiO ₃ (Where 0? _{X? 1} ) or an LSF compound ((La _x Sr _{1 -x} ) FeO ₃ (Where 0? _X? 1)), and the second coating film is a high-conductivity ceramics LCCC ((La _x Ca _{1 -x} ) (Co _y Cr _{1 -y} ) O ₃ x < = 1, 0 < = y < = 1)), and the first coating layer or the second coating layer is composed of at least one compound selected from zirconia, ceria, bismuth oxide, barium / strontium citrate compound, and lanthanum strontium gallium- ; An organic binder and a solvent, and applying the slurry or paste to a tape by casting or by coating one or more of slurry coating, dipping, spray coating, spin coating and screen printing, and then heat-treating the slurry or paste. .

The support is an air electrode support which is a mixture of lanthanum-based perovskite, and the first coating film is a conductive ceramic or a composite thereof, which is LCCC (La _x Ca _{1 -x} ) (Co _y Cr _{1 -y} ) O ₃ (where 0? x? 1, 0? y? 1)) and the second coating film is a lanthanum-based perovskite which is a highly conductive ceramic in a reducing atmosphere, _x Sr _{1 -x} ) TiO ₃ (Where 0? _{X? 1} ) or an LSF compound ((La _x Sr _{1 -x} ) FeO ₃ (Where 0? X? 1)), and the first coating film or the second coating film is at least one compound selected from the group consisting of zirconia, ceria, bismuth oxide, barium / strontium citrate compound and lanthanum strontium gallium magnesia oxide; An organic binder and a solvent, and applying the slurry or paste to a tape by casting or by coating one or more of slurry coating, dipping, spray coating, spin coating and screen printing, and then heat-treating the slurry or paste. .

And a structure for promoting the densification of the first connecting material coating layer by inserting a functional layer between the supporting conductive ceramic film and the supporting body.

Another embodiment of the present invention relates to a single cell using the above-described support-type ceramic connecting material as a connecting material or separator.

The unit cell may be a combination of a support-type connecting material coating film with a unit cell of an electrolytic cell or a fuel cell formed on a fuel electrode or an air electrode.

Another embodiment of the present invention relates to a stacking apparatus using the aforementioned supportive ceramic connecting material as a connecting material or a separating plate.

The stack device may be a combination of a supporting type connecting material coating film with a unit cell of an electrolytic cell or a fuel cell formed on a fuel electrode or an air electrode.

The present invention relates to a multi-layered structure having a dense film structure for use as a separator for manufacturing interconnects using an electrochemical device, a multi-functional film including a membrane structure such as an electrolytic cell or a fuel cell, Of the ceramic separator or the connecting material.

1 is a schematic view showing a manufacturing process of a fuel electrode support ceramic connecting member (separator plate) according to the present invention.
FIG. 2 is a flow chart of a manufacturing process of a fuel electrode-supported ceramic connecting member (separator plate) according to the present invention.
FIG. 3 is a schematic view illustrating a manufacturing process of an air electrode support ceramic connecting member (separator) according to the present invention.
FIG. 4 is a flow chart showing a manufacturing process of an air electrode-supported ceramic connector (separator) according to the present invention.
Fig. 5 is a cross-sectional microscopic microphotograph (low magnification) of the anode-supported ceramic connecting material produced according to the present invention.
6 is a cross-sectional microscopic micrograph (high magnification) of an anode-supported ceramic connecting material including an LST / Ni-YSZ thin film coated with a thin film on a Ni-YSZ support by a conventional method.
7 is a cross-sectional microscopic micrograph (high magnification) of an anode-supported ceramic connecting material including an LSF / Ni-YSZ thin film coated with a thin film on a Ni-YSZ support by a conventional method.
8 is a cross-sectional photograph of a multi-layered structure of LCCC / LST / Ni-YSZ prepared according to the present invention and coated with a thin film on a Ni-YSZ anode support.
9 is a graph showing the results of measurement of OCV during operation for about 1,200 hours of a multi-layer structure of LCCC / LST / Ni-YSZ coated with a thin film on a Ni-YSZ anode support prepared according to the present invention Fig.
10 is a graph showing the measurement results of the impedance resistance change during operation for about 1,200 hours of a multi-layered structure of LCCC / LST / Ni-YSZ coated with a thin film on a Ni-YSZ anode support prepared according to the present invention .

In the present invention, a dense film is produced by forming a ceramic layer by screen printing or tape casting in double or multiple layers to form a uniform and dense thin film type connecting material layer, and sintering (simultaneous sintering) the same. In this case, it is proposed that a thin film type connection material having a dense form is prepared by adding an additive to improve the sinterability, and an electronic conductive ceramic material is coated again on the outside thereof, thereby reducing the contact resistance with the cell. On the other hand, such a multilayered ceramic connection material can not only make a dense layer but also use a high electrical conductivity and an electronic conductivity as a ceramic separator or a connecting material. Therefore, in the present invention, it is composed of a ceramic separator or a connecting material in the form of a thin film made of such a dense thin film.

In order to accomplish the above object, the present invention provides a method of manufacturing a separator using a composite connector, comprising: forming a porous support; Forming a manufactured functional layer; Preparing a dense ceramic connecting material coating film as a connecting material; Forming and manufacturing a multi-layered coating film for improving sintering shrinkage and conductivity; A method for manufacturing a multi-layered connector and a separator including the steps of manufacturing a porous connecting material is provided.

The present invention relates to a multi-layer structure having a dense film structure for use as a separator to fabricate a multi-functional film including a membrane structure such as a general electrochemical device, an electrolytic cell or a fuel cell, To a method of manufacturing a ceramic separator or connector of the structure.

In order to actually produce a dense electronic conductive or linking material coating film, the support is heat treated in a plastic state so as not to have a difference in shrinkage ratio between the sparsely fired coating film and the support so as to obtain a breathable porous sintered body, ), And then heat-treating the assembly or the ceramic component of the desired component to form a sintered body. Lastly, the connector or cathode (or anode) is attached to the compacted membrane of the composite type and heat treated to form a relatively thin A support type coating connecting material having a coating layer or a separating film or the like is prepared.

The method of producing a composite membrane in accordance with the present invention comprises the steps of: preparing a solid oxide electrolyte cell (Solid Oxide Electrolysis Cell), a solid oxide fuel cell (SOFC), a direct carbon fuel cell , Direct Carbon Fuel Cell) can be used as separators for electronic conductive ceramic interconnects.

In the step of forming the negative electrode (or positive electrode) support according to the present invention, it is preferable to form the support for the support of the negative electrode (or the positive electrode) containing the binder and heat treatment to form the plated support.

In the step of forming the functional layer of the cathode (or the anode) according to the present invention, a thick film is prepared by printing a ceramic slurry of a cathode (or an anode) containing a binder and a solvent, followed by heat treatment to plasticize. According to the present invention, there is provided a method for producing a slurry, comprising the steps of preparing a slurry by adding an additive as a conductive ceramic and a sintering aid, mixing the binder and a solvent, 2 coating layer was prepared, and finally a sintered body having a support and a dense layer was prepared as a final defective defect.

According to the present invention, a thin film type connection member (separator) having a multi-structure conductive ceramic film composed of a high-conductivity first coating layer and a second coating film layer, which is a dense layer, is manufactured.

In the present invention, the final mixed conductive coating film preferably has a final thickness of 0.1 to 900 탆, and the coating film has a sintered density of 50% or more.

In the present invention, the thickness and composition (porosity) of the coating film can be controlled by repeating the number of times and adjusting the concentration by screen printing, slurry coating, or adhesion of a tape gelling sheet.

In the present invention, the support may be an anode or a cathode and an insulator, and the support may be a flat plate, a tube, or a mixture thereof.

According to the present invention, the coating film is composed of a first coating film and a second coating film which are suitable as the connecting material for the respective atmosphere.

The present invention also provides a support-type ceramic connecting material and a separator plate coating film by simultaneous sintering which are produced according to the above-described method.

The present invention also provides a connecting member and a separator including the support-type coating film.

In order to develop a thin film ceramic connection material, in the present invention, a slurry is prepared by screen printing or tape casting under the conditions of a slurry from a conductive ceramic powder and then screen-printed or screened to produce a sheet, dried, A method of directly coating a sheet on a support is proposed.

For this purpose, the porous sintered body is manufactured by heat treating the support body in a plastic state so that there is no difference in shrinkage ratio between the support body and the support body during the simultaneous sintering, and then attaching a functional layer or a protective (catalyst) layer for controlling the heat treatment shrinkage ratio A step of coating or adhering a ceramics dense film of a desired component as a connecting material or a conductive film or a step of heat-treating the same (first connecting material coating layer) as a connecting material or a conductive film, and finally regulating a heat shrinkage ratio on a connecting material or a conductive film (2) a step of adhering a functional layer or a protective (catalyst) layer for heat treatment or a heat treatment to the entire surface of the substrate, (Thin film) of a support type.

On the other hand, in electrochemical devices such as a fuel cell or an electrolytic cell, since characteristic gases (fuel gas and oxidizing gas) that are different from each other flow at both ends of a connecting material (meaning a separator) By coating the structural connecting material, excellent performance can be obtained. Therefore, in order to manufacture a support-type ceramic connecting member (separator plate), a multi-layered thin-plate-shaped connecting member should be applied by selecting a material suitable for both the fuel electrode and the air electrode according to the present invention.

Typically, (La _x Ca _{1 -x} ) (Co _y Cr _{1 -y} ) _{O 3} (hereinafter referred to as LCCC, where 0? X? 1, 0? Y? y). < / RTI > (La _x Sr _1-x ) TiO ₃ (hereinafter referred to as LST, where 0? _X? 1) or (La _x Sr _1-x ) FeO ₃ ≤ x ≤ 1) are the most likely candidates for phase stability and electron conductivity in oxygen atmosphere or hydrogen separation. However, LST is stable in the reducing atmosphere (H ₂ rich) but is rather unstable in the oxidizing atmosphere (O ₂ rich), and the electric conductivity tends to decrease. On the other hand, LCCC is stable in the oxidizing atmosphere, but is rather unstable in the reducing atmosphere and the electric conductivity tends to decrease.

Accordingly, the present invention proposes a method of manufacturing a fuel electrode support ceramic connection member (separator plate) by manufacturing a thin film bilayer conductive film of a porous support (fuel electrode) / reducing dense conductive film / oxidative conductive film using a wet process. In addition, a thin film bilayer conductive membrane of a porous support (air electrode) / oxidative dense conductive membrane / reducing conductive membrane is manufactured as a corresponding structure to propose a method of manufacturing an air electrode support ceramic connecting member (separator plate).

For example, when the support thin film type connector is applied to an electrolytic cell or a fuel cell for an electrochemical device as in the present invention, a support (NiO-YSZ) A slurry is prepared by adding an organic binder or the like to a powder material of a material to be coated, such as an electrolyte, and then screen printing or another green sheet sheet is formed through another tape casting process Next, the sheet is directly attached to the surface of the plasticized anode (or air electrode) support and closely bonded, and then the composite of the anode (or air electrode) support having the electrolyte green sheet is simultaneously sintered (Or air electrode) support having a membrane is formed on the surface of the conductive dense membrane, and finally, ) By printing a paste of the material, it dried and heat-treated can be manufactured according to a fuel electrode or an air electrode support consolidated or membrane.

As described above, a precursor of a dense film is prepared from a slurry containing an organic binder and a powder of a material (oxide or non-oxide) using a screen printing or a tape casting apparatus, attached to a porous support and dried or aged By finally co-firing, it is possible to form a coating layer film having a uniform thickness without defects between the support and the coating layer film.

Such support type composite electrolyte electrolyte membranes can be used for high performance high performance fuel cells such as multi-functional solid oxide electrolytic cells, carbon dioxide electrolytic cells and fuel cells, such as high performance solid oxide fuel cells (SOFC) and direct methanol fuel cells (DCFC) have. In addition, ceramics or the like made of alumina or mullite can be used as a support to uniformly coat the conductive ceramic connecting material on a part thereof.

 As shown in FIG. 7, a method of manufacturing a support-type thin film type connector according to a preferred embodiment of the present invention includes the steps of: 1) forming a pre-sintered support by forming and heating a support (anode or cathode) 2) forming a ceramic conductive slurry containing an organic binder and screen-printing or tape-casting the ceramic green sheet so that the ceramic green sheet is first coated with a ceramics binder and then heat-treating or drying the ceramic slurry; 3) A step of heat-treating or drying the conductive slurry to prepare a conductive ceramic slurry containing the complex type and screen-printing or tape casting to secondarily coat the connecting green sheet to adjust the sintering shrinkage during the heat treatment to improve electrical conductivity, Supported connection by sintering heat treatment To prepare a (bipolar plate) it is composed of a sintered body to form a coating. 4) Ceramic green sheets may be coated by screen printing or tape casting to improve the contactability of the final product or to produce a ceramic conductive slurry again as an oxidation-reduction catalyst layer, and then classified into final heat treatment.

Therefore, in this invention, a porous support / dense thin film bilayer membrane using a wet process has been successfully manufactured to produce a dense membrane of a connecting material. 5 and 6 show the case of LCCC and LST.

In the present invention, a composite membrane of a composite type composite conductor is prepared to produce a dense membrane which can be operated at a low temperature. When the electronic conductivity is high, the membrane can be used as a thin film type connector.

 In order to accomplish the above object, the present invention provides a method of manufacturing a separator using a multi-membrane structure connecting material, comprising: forming a porous support; Forming a manufactured functional layer; Producing a dense first linking coating film as a connecting material suitable for an inner atmosphere (reducing or oxidizing); The present invention also provides a method of manufacturing a multifunctional thin film connector and a separator comprising the steps of producing a dense or porous connecting material second connecting material coating film suitable for an outer atmosphere (oxidizing or reducing).

In the step of forming the negative electrode (or positive electrode) support according to the present invention, it is preferable to form the support for the support of the negative electrode (or the positive electrode) containing the binder and heat treatment to form the plated support. On the other hand, a ceramics support in which the components of the support are nonconductive may be used at the time of manufacturing the oxygen permeation and hydrogen permeation separation membranes.

In the step of forming the functional layer of the cathode (or the anode) according to the present invention, a thick film is prepared by printing a ceramic slurry of a cathode (or an anode) containing a binder and a solvent, followed by heat treatment to plasticize.

According to the present invention, an additive is added to an electronic conductive ceramics as a sintering auxiliary agent to prepare a slurry by mixing a binder and a solvent, followed by coating and attaching the slurry, and finally a sintered body having a support and a dense layer.

According to the present invention, in the final step, a multilayer structure of a conductive coating film as a dense layer is formed, and a thick film is manufactured by printing a ceramic slurry of a cathode (or a cathode) containing a binder and a solvent, To form a plate (connection member).

In the present invention, the final mixed conductive coating film preferably has a final thickness of 0.1 to 900 탆, and the coating film has a sintered density of 50% or more.

In the present invention, the thickness and composition (porosity) of the coating film can be controlled by repeating the number of times and adjusting the concentration by screen printing, slurry coating, or adhesion of a tape gelling sheet.

In the present invention, the support may be an anode or a cathode and an insulator, and the support may be a flat plate, a tube, or a mixture thereof.

According to the present invention, the coating film may be a connecting material or a separating film.

The present invention also provides a multi-layered or multi-layered support-type coating film prepared according to the above-described method.

The present invention also provides a unit cell module unit having a connecting member including the support-type coating film and a separator plate.

When the module unit is manufactured, it is convenient to use a green sheet-like current collector in the case of a flat plate type and a paste-like current collector in the case of a tube type.

One embodiment of the present invention is a method for manufacturing an electrode support type connecting member or a separator by simultaneous sintering, comprising: forming a support; Mixing the conductive ceramic powder with a binder and a solvent to prepare a slurry or a tape-cast green sheet, and coating the support on the support to form a first coating layer; Preparing a slurry or tape-cast green sheet of the conductive ceramic powder by drying or heat-treating the first coating layer, and coating the first slurry on the first coating layer to form a second coating layer; Co-sintering the support on which the first coating layer and the second coating layer are formed; To a process for producing a support type coupling material coating film.

The step of forming the support may include forming a support composition comprising an organic binder and then heat-treating the support composition to produce a plasticizer.

The step of forming the support may comprise: a step of forming a support comprising nickel metal or its oxide (NiO); And a yttria-stabilized zirconia-based oxide (SZ) are mixed, a support composition containing an organic binder, a solvent and a pore-forming agent is added, and the support composition is heat-treated to form a calcined support.

The support powder NiO and CoO, CuO, Fe ₂ O ₃ And Cr ₂ O ₃ A fuel electrode material containing at least one of powders; Zirconia, ceria, bismuth oxide, barium / strontium citrate compound and lanthanum strontium gallium magnesia oxide; And a pore-forming agent are mixed and then ball-milled, dried and formed, and then heat-treated at 600 ° C to 1,500 ° C to form a porous porous anode support.

Wherein the support is at least one of La, Sr, Ca, and Ba at site A and ABO _{3 (at} least one site of B, Mn, Co, Fe, A cathode material comprising a perovskite structure compound or a non-organosilicate high conductivity ceramics material; Zirconia, ceria, bismuth oxide, barium / strontium citrate compound and lanthanum strontium gallium magnesia oxide; And pore-forming agents; , Followed by ball milling, drying and molding, and then heat treatment at 600 ° C to 1,500 ° C to form a porous porous cathode support.

The support may be prepared by preparing a support composition comprising a ceramic powder, an organic binder, a solvent and a pore-forming agent, forming the support composition into a flat plate, a tube or a mixture thereof, And a fuel electrode support.

The step of forming the first coating layer or the step of forming the second coating layer may include coating the conductive ceramics or the composite slurry with at least one of slurry coating, dipping, spray coating, spin coating, and screen printing, can do.

The conductive ceramic powder may include lanthanum-based perovskite.

The conductive ceramic powder may be at least one selected from the group consisting of lanthanum perovskite or SrCo _0.8 Fe _0.2 O ₃ -δ, Sm _{0 . 6} Sr _{0 . 4 CoO 3 -δ, Y 0. 1} Ba 0. ₉ CoO _{3 -δ,} BaBi _{0. 4} Co _{0 . 2} Fe _{0 . 4} O _{3 - ?,} (Sr _0.85 Y _0.1 ) (Ti _0.95 Co _0.05 ) O ₃ , and the conductive ceramic powder; At least one electrolyte material selected from zirconia, ceria, bismuth oxide, barium / strontium citrate compound and lanthanum strontium gallium magnesia oxide; Organic binders; And a solvent are coated with at least one of slurry coating, dipping, spray coating, spin coating, and screen printing, and heat treatment is performed.

Wherein the conductive ceramic powder comprises non-lanthanum-based conductive ceramics, the conductive ceramic powder; At least one electrolyte material selected from zirconia, ceria, bismuth oxide, barium / strontium citrate compound and lanthanum strontium gallium magnesia oxide; Organic binders; And a solvent are coated with at least one of slurry coating, dipping, spray coating, spin coating, and screen printing, and heat treatment is performed.

The step of forming the first coating layer or the forming of the second coating layer may be performed by using TiO ₂ , MnO ₂ , Sr ₂ CO ₃ , SiO ₂ , Cr ₂ O ₃ , Bi ₂ O ₃ And Y ₂ O ₃ , to prepare a coating film using a slurry or a paste.

The support type coupling material coating film is a multi-layer film including a reducing atmosphere stable conductive ceramic film and an oxidative atmosphere stable conductive ceramics film, wherein the first and second coating layers are overlaid and coated with a heat treatment.

The step of forming the first coating layer or the step of forming the second coating layer may be performed by preparing a slurry from the conductive ceramic powder, forming the slurry into a sheet using tape casting, attaching the slurry on the support, To form a ceramic layer, and then heat-treating the ceramic layer to produce a coating film.

Wherein the final thickness of the support type coupling material coating film is 0.1 to 900 탆.

The sintered density of the support type coupling material coating layer may be 30% or more.

The thickness of the support linking material coating layer may be controlled by the number of times that the formation of the first coating layer or the second coating layer is repetitively performed or by the number of times the adhesion of the green sheet is repeatedly performed.

Another embodiment of the present invention relates to a support-type ceramic connector made by the above-described method for producing a supportive connector coating film.

The support is a fuel electrode support which is a mixture of NiO and YSZ, and the first coating layer is a lanthanum perovskite which is a high conductivity ceramics in a reducing atmosphere with a conductive ceramics or a composite thereof, as an LST compound ((La _x Sr _{1 - x)} TiO ₃ (Where 0? _{X? 1} ) or an LSF compound ((La _x Sr _{1 -x} ) FeO ₃ (Where 0? _X? 1)), and the second coating film is a high-conductivity ceramics LCCC ((La _x Ca _{1 -x} ) (Co _y Cr _{1 -y} ) O ₃ x < = 1, 0 < = y < = 1)), and the first coating layer or the second coating layer is composed of at least one compound selected from zirconia, ceria, bismuth oxide, barium / strontium citrate compound, and lanthanum strontium gallium- ; An organic binder and a solvent, and applying the slurry or paste to a tape by casting or by coating one or more of slurry coating, dipping, spray coating, spin coating and screen printing, and then heat-treating the slurry or paste. .

The support is an air electrode support which is a mixture of lanthanum-based perovskite, and the first coating film is a conductive ceramic or a composite thereof, which is LCCC (La _x Ca _{1 -x} ) (Co _y Cr _{1 -y} ) O ₃ (where 0? x? 1, 0? y? 1)) and the second coating film is a lanthanum-based perovskite which is a highly conductive ceramic in a reducing atmosphere, _x Sr _{1 -x} ) TiO ₃ (Where 0? _{X? 1} ) or an LSF compound ((La _x Sr _{1 -x} ) FeO ₃ (Where 0? X? 1)), and the first coating film or the second coating film is at least one compound selected from the group consisting of zirconia, ceria, bismuth oxide, barium / strontium citrate compound and lanthanum strontium gallium magnesia oxide; An organic binder and a solvent, and applying the slurry or paste to a tape by casting or by coating one or more of slurry coating, dipping, spray coating, spin coating and screen printing, and then heat-treating the slurry or paste. .

And a structure for promoting the densification of the first connecting material coating layer by inserting a functional layer between the supporting conductive ceramic film and the supporting body.

Another embodiment of the present invention relates to a single cell using the above-described support-type ceramic connecting material as a connecting material or separator.

The unit cell may be a combination of a support-type connecting material coating film with a unit cell of an electrolytic cell or a fuel cell formed on a fuel electrode or an air electrode.

Another embodiment of the present invention relates to a stacking apparatus using the aforementioned supportive ceramic connecting material as a connecting material or a separating plate.

The stack device may be a combination of a supporting type connecting material coating film with a unit cell of an electrolytic cell or a fuel cell formed on a fuel electrode or an air electrode.

Example

Hereinafter, examples and comparative examples of the present invention will be described. It should be understood, however, that these examples are provided for illustration only and are not intended to limit the scope of the present invention.

Example 1 Preparation of Anode Support Component (Separate Plate): A method for producing a second linking coating film of LST (or LSF) first linking coating film and LCCC using tape casting method

A fuel electrode support system was used for manufacturing a connection material (separator) for use in an electrolytic cell or a fuel cell, and a support was first prepared for this purpose. NiO powder (Alfa Co., 99.9%) and 8 mol% YSZ (Tosho Co., or 1 mol% to 20 mol% yttria-stabilized zirconium oxide) were used to prepare the anode support. First, the NiO powder was ball milled in a planetary mill for 2 hours and then dried in an oven. The 8YSZ powder was pre-calcined at 1,400 ° C and then crushed into a mortar. The NiO and YSZ were mixed at a weight ratio of 5: 5, and wet ball milling was performed for 24 hours. At this time, graphite, an organic binder and ethyl alcohol for pore formation were added to the mixture, Lt; / RTI > In the case of graphite added for pore formation, the particle size and mixing ratio should be appropriately controlled. In order to manufacture a unit cell, a flat plate-shaped support was formed by uniaxial molding with a square mold having a desired size. In order to manufacture a tubular support, an extruder was used to form a plate- A tubular or planar support having a length of about 1 m was formed. After drying at room temperature, they were heat treated at about 1,200 ~ 1,450 ℃ to obtain a pre - sintered body of fuel electrode component. In some cases, the fuel electrode functional layer was coated on the anode support and reheated at about 1,250 ° C.

As shown in Figs. 1 and 2, in order to prepare a reducing atmosphere high-conductivity ceramics membrane for such a support, a compound of LST or LSF as a lanthanum-based perovskite, which is a highly conductive ceramics in a reducing atmosphere with conductive ceramics or a composite thereof That is, (La _x Sr _{1 -x} ) TiO ₃ (Where 0? _X? 1) or (La _x Sr _{1 -x} ) FeO ₃ (Where 0? X? 1)) was used to form a first coating film (dense film). (La _x Ca _{1 -x} ) (Co _y Cr _{1 -y} ) O ₃ (where 0? _{X? 1} ), which is high-conductivity ceramics in an oxidizing atmosphere in the opposite atmosphere as in FIGS. 1 and 2, 1, 0? Y? 1)) was used to form a second coating film. In particular, each layer is mixed with 0 to 100% of at least one compound selected from zirconia, ceria, bismuth oxide, barium-strontium titanate and lanthanum strontium gallium magnesia-based oxide to form an organic binder and a solvent Slurry or paste with tape casting or by slurry coating, dipping, spray coating, spin coating, or screen printing.

In particular, the first connector coating layer has a dense membrane structure, and the second connector coating layer is less dense and has no problem in use. Therefore, the connector layer is made of a dense membrane or a porous membrane. (La _x Sr _1-x ) TiO ₃ (where 0? _X? 1) or (La _x Sr _{1 -x} ) FeO ₃ A (where, 0≤x≤1)) were conducted to use a representative composition of _{(La 0. 7 Sr 0.} 3) TiO 3 or _{(La 0. 7 Sr 0.} 3) FeO 3. The first binder (coating) film may be prepared using only pure LST or LSF coupling material, or may be made in the form of a composite. In order to use it as a composite, zirconium oxide (ZrO ₂ ) doped with yttrium (Y) (0 to 20%) was mixed at a weight ratio of 5: 5 and ball milled with ethyl alcohol for about 24 hours. Milling and mixing were carried out. In order to improve densification and sintering densities, the additives were added as a sintering additive in order to improve the final sintering property of the first binder coating layer, which is a linking material for the LST or LSF of a single material or a composite material of the composite. TiO ₂ , Bi ₂ O ₃ , Cr ₂ O ₃ , CoO, and Y ₂ O ₃ in an amount of 0 to 30%. After drying, a tape casting green sheet was produced, and then a green sheet film having a thickness of about 60 μm was formed. At this time, the used mylar film was attached to the surface of the preliminarily sintered anode support at the same time, and the mylar film was removed. The dried tape casting green sheet was reattached to the final composite composite conductor The thickness of the film was adjusted, and the coating was usually applied two times, followed by heat treatment at 600 to 1500 占 폚 for aging treatment (Aging: homogenization in an oven at about 70 占 폚 for about 1 hour).

The second connecting material coating film according to the present invention was prepared as a coating film on the fuel electrode support type connecting material (separating plate) manufactured by the above method. (La _x Ca _{1 -x} ) (Co _y Cr _{1 -y} ) O ₃ (where 0? _{X? 1} , 0? _{Y? 1} ), which is high-conductivity ceramics in a circulating atmosphere It was carried out a representative composition of _{(La 0. 1 Ca 0 .9} ) (Co 0. 2 Cr 0. 8) O 3. The second connecting material (Coatane) film may be manufactured using only pure LCCC connecting material, or may be manufactured in the form of a composite. In order to use it as a composite, zirconium oxide (ZrO ₂ ) doped with yttrium (Y) (0 to 20%) was mixed at a weight ratio of 5: 5 and ball milled with ethyl alcohol for about 24 hours. Milling and mixing were carried out. In order to improve densification and sintering densities, the additives were added as a sintering additive in order to improve the final sintering property of the second binder coating layer, which is a connecting material of the single-piece LCCC binder or composite, and TiO ₂ , Bi ₂ O ₃ , Cr ₂ O ₃ , CoO, and Y ₂ O ₃ in an amount of 0 to 30%. After drying, a tape casting green sheet was produced, and then a green sheet film having a thickness of about 60 μm was formed. In general, it was coated with two times of coating, followed by heat treatment at 600 to 1500 占 폚 for aging treatment (aging (homogenization treatment in an oven at about 70 占 폚 for about one hour), followed by plasticizing treatment. Finally, the supports were subjected to final co-firing at 1400 ~ 1650 ℃ in a heat treatment process to develop an anode-support type high conductivity multilayered interconnector (separator). Finally, the thickness of the high-conductivity dense conductive film was set to 5 to 50 μm.

Hereinafter, a method of manufacturing a green sheet of a ceramic conductive film will be described. Green sheet material for tape casting A mixture of LST and LSF or LCCC together with ceramics powder including YSZ and the like was mixed with ethyl alcohol and toluene at a ratio of 1: 0 to 5: 1 as a solvent. To prepare a slurry for casting, first, a solvent in which a fish oil is dissolved is put into a ball mill jar, and a fuel electrode or an air electrode current collector powder (specific surface area 2 to 200 m ³ / g) (PVB, polyvinyl butyral) and a plasticizer (DBP, dibutyl phthalate) were further added to the resultant, followed by secondary milling. The viscosity of the prepared slurry was controlled to be between 10 ² and 10 ⁵ cps, and then a tape casting process was performed. The casting film is formed by using a Mylar (electrically insulating material, U.S. Du Pont) film (40 to 400 탆) coated with silicon on one side, and is fed at a feeding rate of 1 to 50 cm / min. A tape casting green sheet having a desired thickness in the range of 20 to 2,000 mu m in height was prepared. Table 1 shows the content of additives added per 100 grams of conductive ceramic powder in the production of slurry for tape casting.

Types of additives Addition amount (g) Remarks The solvent 10 to 200 Ethyl alcohol and toluene were added
1: mixed at a ratio of 0 to 5 Dispersant (fish oil) 0.1 to 10 The organic binder (PVB) 1 to 10 Plasticizer (DBP) 1 to 10

The coating film for the production of the anode support type coupling material is prepared by mixing (mixing) with pure YSZ (yttria stabilized zirconium oxide) powder having a particle size of 0.01 to 10 mu m in pure LST or LSF powder having a particle size of 0.01 to 10 mu m 0 to 50%). Similarly, (La _x Ca _1-x ) (Co _y Cr _1-y ) O ₃ (0 _{? X} ? 1, 0? (0 to 50%) powders and YSZ (yttria stabilized zirconium oxide) powders having a particle size of 0.01 to 10 μm were mixed with an organic binder (polyvinyl butyral, PVB) and a plasticizer dibutyl phthalate (DBP), and then tape cast to a thickness of 10 to 600 μm to prepare a green sheet. In each step, the support type connecting material and the separating plate of the sintered body are firstly prepared by heat treatment at a temperature of 600 ° C or more, and finally heat-treated (sintered) at a temperature of 800 to 1650 ° C to form a concurrent sintered conductive ceramic film structural connector .

When a slurry in which particles of a coating component are dispersed is cast by tape casting and dried to obtain a composite mixed conductor film of the present invention, it is possible to obtain a film composed of a green sheet and a release film, which is adhered onto the air electrode or anode support, To form a coating film, and finally to a sintering heat treatment to produce a support-type connecting material or separator.

In the present invention, the release film includes a PET-based film (polyethylene-based or Myllock film) coated with silica or the like. The slurry is tape-cast on the MylLock film to form a green sheet of the mixed conductor film having a desired thickness. The desired coating film laminate may be attached to the surface of the air electrode or the overlying fuel electrode support, the green sheet of the laminate may be attached to the fuel electrode or air electrode, and the mylar film may be separated and removed. At this time, if a small amount of oil or solvent (for example, terpineol) is lightly applied and attached in order to increase the uniformity of contact, a ceramic conductive film can be produced by easily and uniformly contacting and attaching.

6 is a cross-sectional microscopic micrograph (high magnification) of a cross-sectional view of an anode-supported ceramic connection material (separator plate) prepared by a conventional method and coated with a thin film on a Ni-YSZ support. The sintered film shows undulation defects.

7 is a cross-sectional microscopic microphotograph (high magnification) of a cross-sectional view of a thin-film coated LSF / Ni-YSZ thin-film joint of a fuel electrode support ceramic plate prepared by a conventional method and having a thin film coated on a Ni- Membrane shows pore formation or peeling defect due to reaction during sintering.

On the other hand, as shown in Fig. 6 and Fig. 7, in the case of pure LST and LSF, the area specific resistivity was less than 1 Ωcm ² , indicating electrical characteristics as a connecting material. On the other hand, as shown in FIG. 6, in the case of LST, the shrinkage ratio during sintering is relatively small, which is smaller than NiO-YSZ (Y ₂ O ₃ doped (1 to 15 mol%) ZrO ₂ ) 7 shows that the LST layer and the Ni-YSZ layer are separated from each other and peeled off. In FIG. 7 and FIG. 7, the case of LSF reacts with NiO-YSZ, which is a base material during sintering, The area specific resistivity is large. Therefore, when Ni-YSZ base material (support) is used as a single thin-film type connection material, LST and LSF can not have a uniform microstructure due to difference in reaction or shrinkage ratio with the co-sintered base material (support) It can be seen that it is unsuitable as a connecting material in a cell.

 8 is a cross-sectional view of a cross-section of a multi-layered structure of LCCC / LST / Ni-YSZ prepared according to the present invention and coated with a thin film on a Ni-YSZ (anode) Microscopic cross-sectional micrographs (high magnification) show dense structure due to dense-conduction extracellular multiplication (reductive, oxidative).

9 and 10 illustrate the electrical characteristics of a connection material (separator plate) made of a multilayer structure of LCCC / LST / Ni-YSZ prepared according to the present invention and coated with a thin film on a Ni-YSZ (OCV) and impedance resistance change measurement results during the test.

On the other hand, in the case of LST, the sintering aid was further placed on the surface to form a bilayer thin film type connecting film (film). As a result, as shown in FIG. 8, the connecting thin film was coated with Ni (O) It can be seen that it is usable as a ceramic connecting material because it shows dense and uniform cross-sectional microstructure. In particular, LCCC has a high electronic conductivity like LST and LSF, and therefore, it is difficult to completely densify the void due to the difference in shrinkage ratio between NiO-YSZ support and itself. However, LSF and LST are stabilized in the reducing atmosphere, while they are stable in the oxidizing atmosphere rather than in the reducing atmosphere and maintain the higher electrical conductivity in the oxidizing atmosphere.

Accordingly, as shown in FIG. 9, the impedance characteristics and the I-V characteristics together with the long-term operation test showed very good ceramic connecting material characteristics, and it was confirmed from the I-V curve for 1,200 hours as shown in FIG. 9 (a).

In particular, as shown in FIG. 9 (b), it was possible to develop a ceramic connecting material having an area resistivity of 0.4 Ωcm ² or less even during 1,200 hours of operation time from the impedance spectrum over time.

In particular, the first and second connector coating layers may be formed by a common method such as a screen printing method in addition to the tape casting method. In some cases, the film may be appropriately combined and used for manufacturing. Particularly, the production conditions of the paste or slurry for screen printing are the same as those of the second embodiment.

Example 2 Preparation of fuel electrode support type connecting plate (separator plate): A method of producing LST (or LSF) first linking coating film and LCCC second linking coating film by screen printing

Likewise, a fuel electrode support system was used for manufacturing a connection material (separator plate) for use in an electrolytic cell or a fuel cell. NiO powder (Alfa Co., 99.9%) and 8 mol% YSZ (Tosho company, or 2 mol% ~ 20 mol% yttria-stabilized zirconium oxide) were used to prepare the anode support. First, the NiO powder was ball milled in a planetary mill for 2 hours and then dried in an oven. The 8YSZ powder was pre-calcined at 1,400 ° C and then crushed into a mortar. The NiO and YSZ were mixed at a weight ratio of 5: 5, and wet ball milling was performed for 24 hours. At this time, graphite, an organic binder and ethyl alcohol for pore formation were added to the mixture, Lt; / RTI > In the case of graphite added for pore formation, the particle size and mixing ratio should be appropriately controlled. In order to manufacture a unit cell, a flat plate-shaped support was formed by uniaxial molding with a square mold having a desired size. In order to manufacture a tubular support, an extruder was used to form a plate- A tubular support having a length of about 1 m was formed. After drying at room temperature, they were heat treated at about 1,200 ~ 1,450 ℃ to obtain a pre - sintered body of fuel electrode component. In some cases, the fuel electrode functional layer was coated on the anode support and reheated at about 1,250 ° C.

As shown in FIGS. 1 and 2, in order to prepare a highly-reducing ceramics membrane having a reduced atmosphere, a conductive ceramic or a composite thereof is used as a lanthanum-based perovskite, which is a highly conductive ceramic in a reducing atmosphere, That is, (La _x Sr _{1 -x} ) TiO ₃ (Where 0? _X? 1) or (La _x Sr _{1 -x} ) FeO ₃ (Where 0 ≤ x ≤ 1)) was used to form a first linker coating film (dense film). Similarly, exemplary representative composition is _{(La 0. 7 Sr 0.} 3) TiO 3 or _{(La 0.7 Sr 0.3) FeO 3} . The first binder (coating) film may be prepared using only pure LST or LSF coupling material, or may be made in the form of a composite. For use in the form of a complex, it is the same as in Example 1 below.

(La _x Ca _{1 -x} ) (Co _y Cr _{1 -y} ) O ₃ (where 0? _{X? 1} ), which is high-conductivity ceramics in an oxidizing atmosphere in the opposite atmosphere as in FIGS. 1 and 2, 1, 0? Y? 1)) was used to form a second connector coating film. Representative exemplary composition of a _{(La 0. 1 Ca 0 .9} ) (Co 0. 2 Cr 0. 8) O 3. The second connecting material (Coatane) film may be manufactured using only pure LCCC connecting material, or may be manufactured in the form of a composite. For use in the form of a composite, it is the same as in Example 1. When the sintering aid is included, it is mixed in a proportion of 0 to 100% with zirconia, ceria, bismuth oxide, barium-strontium titanate and lanthanum strontium gallium magnesia-based oxide in each layer, A slurry or a paste containing a binder and a solvent, and the slurry or paste is applied by tape casting or by slurry coating, dipping, spray coating, spin coating or screen printing.

In particular, the first connector coating layer has a dense membrane structure, and the second connector coating layer is less dense and has no problem in use. Therefore, the connector layer is made of a dense membrane or a porous membrane. (La _x Sr _1-x ) TiO ₃ (where 0? _X? 1) or (La _x Sr _{1 -x} ) FeO ₃ Zirconium oxide (ZrO ₂ ) doped with yttrium (Y) (0 to 20%) in order to use pure compounds or to form a composite in the case of preparing a compound of the formula ( ₁ ) 5, and the mixture was ball milled with ethyl alcohol for about 24 hours to perform mechanical pulverization and mixing. The sintering additive was added as a sintering additive in order to improve densification and sintering density by improving the final sintering property of the composite. One or more of TiO ₂ , Bi ₂ O ₃ , Cr ₂ O ₃ , CoO and Y ₂ O ₃ Was added to 0 to 30%.

 The slurry or paste was prepared by screen printing or slurry coating on the surface of the preliminarily sintered anode support, and the thickness of the final composite mixed conductor film was controlled by controlling the number of times of application. The average thickness of the final composite conductive film was adjusted to about 5 ~ Lt; / RTI > After that, it is subjected to final simultaneous sintering heat treatment at 1400 ~ 1650 ° C in a heat treatment process after aging (homogenization treatment in an oven at about 70 ° C for about 1 hour), and a connecting material having a fuel electrode support composite composite conductive film . Finally, the thickness of the complex mixed conducting membrane was about 5 ~ 40 μm.

A coating layer of a composite mixed conductor according to the present invention is prepared by screen printing or slurry coating method on an anode support material type connection plate (separator plate) manufactured by the above method, and then dried and formed on a support and heat treated to form a final connection material ).

Hereinafter, a method for producing a paste or slurry of a composite mixed conducting membrane will be described. In the preparation of the paste (slurry) for screen printing, isopropyl alcohol and toluene were mixed at a ratio of 1: 0 to 5: 1 as a solvent. To prepare a slurry, firstly, a solvent in which a fish oil is dissolved is put into a ball mill jar, and a fuel electrode or an air electrode collector powder (specific surface area 2 to 200 m ³ / g) is first milled (PVB, polyvinyl butyral) and a plasticizer (DBP, dibutyl phthalate) were further added thereto, followed by secondary milling. Screen printing was performed after the viscosity of the prepared slurry was adjusted to be between 10 ¹ and 10 ⁵ cps. Screen printing was performed using a 200 mesh stainless steel net. In addition to the desired pattern, the desired thickness was covered with an epoxy resin, and the paste was coated in a patterned shape. Table 2 shows the contents of additives added per 100 grams of the conductive ceramics powder in the production of the paste for screen printing (slurry).

Types of additives Addition amount (g) Remarks The solvent 5 to 500 Isopropyl alcohol and toluene were added
1: mixed at a ratio of 0 to 5 Dispersant (fish oil) 0.1 to 10 The organic binder (PVB) 1 to 10 Plasticizer (DBP) 1 to 10

The coating film for the production of the anode support type coupling material is prepared by mixing (mixing) with pure YSZ (yttria stabilized zirconium oxide) powder having a particle size of 0.01 to 10 mu m in pure LST or LSF powder having a particle size of 0.01 to 10 mu m 0 to 50%) was prepared similarly to the second consolidated coating film produced is _{(La x Ca 1-x)} (Co y Cr 1-y having a particle size of 0.01 to _{10 μm) O 3 (0≤x≤1,} 0 (0 to 50%) with a YSZ (yttria stabilized zirconium oxide) powder having a particle size of 0.01 to 10 mu m. An organic binder (polyvinyl butyral, PVB) and a plasticizer dibutyl phthalate (DBP), and then tape cast to a thickness of 10 to 600 μm to produce a green sheet. In each step, the support type connecting material and the separating plate of the sintered body are firstly prepared by heat treatment at a temperature of 600 ° C or more, and finally heat-treated (sintered) at a temperature of 800 to 1650 ° C to form a concurrent sintered conductive ceramic film structural connector . The conditions for producing the paste or slurry for screen printing at this time are as described above.

Example 3 Fabrication of SOFC and SOEC Single Cells and Module Using Fuel-electrode Supported Connector (Additional Items)

A single cell unit is fabricated by combining a support thin film type SOFC single cell and a connecting material (separator plate). A single cell unit module comprising a single cell (including ion conductor slabs) manufactured by the same manufacturing method and a connection material separator plate (high conductivity multi-film type connection material) .

First, a plate or tubular support is first made of a fuel electrode material (NiO-YSZ), and a ceramic film serving as an electrolyte or a conductive film is formed and attached by a tape casting method. And may be produced by a screen printing method.

Here is a more detailed explanation.

In the present invention, an anode support was prepared, and a NiO-YSZ mixed powder was used for preparing the support. (Organic or aqueous) and pore-forming agent, which are advantageous in terms of cost, and at least one of compounds such as zirconia-based oxide, alumina-based oxide, mullite-based oxide, silica-based oxide or carbide and nitride, Shaped, tubular or mixed type, and then heat-treated at a high temperature of 1,000 ° C. or higher to prepare a preliminarily sintered (calcined) support. In the case of graphite added for pore formation, the particle size and mixing ratio should be appropriately controlled. In order to manufacture a unit cell, a plate-shaped support was formed by uniaxial molding with a square mold having a desired size. In order to manufacture a tubular support, a tubular support having a length of about 1 m was formed by using an extruder. After drying at room temperature, they were heat treated at about 1,200 ~ 1,450 ℃ to obtain a pre - sintered body of fuel electrode component. In some cases, a porous catalyst layer is first coated on the oxide support as a functional layer with the same components as the anode, and then heat treated at about 900 to 1,500 ° C.

The upper surface of this support is coated with an ion conductor film containing YSZ as a main component, and a single cell plate is fabricated. Likewise, on the lower surface (tubular type) of the support or the plate surface, a ceramic conductive film . Particularly, such a multi-layered ceramic conductive film uses a tape casting method, a screen printing method or the like as in the case of Embodiment 1 or Embodiment 2. [ The flat plate type is manufactured by attaching the electrolyte plate and the connection plate formed by forming the flow path in each of them. The mixed powder of NiO-YSZ is faced and applied to the contact area, and is heat treated at the pre- And the lower plate are attached first. Then, the unit cell module unit can be manufactured by simultaneously sintering the electrolyte-coated upper plate at 1000 to 1650 ° C and the lower plate coated with the high-conductivity ceramic membrane. On the other hand, the air electrode of the single cell module unit manufactured by final sintering using the anode support is formed in the final stage, and the paste of the CeO ₂ powder (GDC or SDC) doped with the electrolyte layer Gd ₂ O ₃ or Sm ₂ O ₃ is electrolyzed And then heat-treated at 1000 to 1500 ° C. Then, GDC or SDC is mixed with LSCF ((La _x Sr _{1 -x} ) (Co _y Fe _{1 -y} ) O ₃ (where 0 x 1, 0 ≤ y ≤ 1)) was prepared, screen-printed on a buffer layer, dried, and finally heat-treated at 600 to 1300 ° C to complete air electrode formation.

The following are mentioned in the first and second embodiments.

Example 4 Production of air electrode supporter type connecting material (separation plate): Tape casting method or screen printing method

A fuel electrode support system was used for manufacturing a connection material (separator) for use in an electrolytic cell or a fuel cell, and a support was first prepared for this purpose. To prepare the anode support, LSM (La _x Sr _1-x ) MnO ₃ (Where 0? X? 1) and 8 mol% YSZ (Tosho Co., or 1 mol% to 20 mol% yttria-stabilized zirconium oxide) were used. First, the LSM powder was ball milled in a planetary mill for 2 hours and then dried in an oven. The 8YSZ powder was pre-calcined at 1,400 ° C and then crushed into a mortar. The LSM and YSZ were mixed at a weight ratio of 5: 5, and wet ball milling was performed for 24 hours. At this time, graphite, an organic binder and ethyl alcohol for pore formation were added to the mixture, Lt; / RTI > In the case of graphite added for pore formation, the particle size and mixing ratio should be appropriately controlled. In order to manufacture a unit cell, a flat plate-shaped support was formed by uniaxial molding with a square mold having a desired size. In order to manufacture a tubular support, an extruder was used to form a plate- A tubular support having a length of about 1 m was formed. After drying at room temperature, they were heat treated at about 1,200 ~ 1,450 ℃ to obtain a pre - sintered body of fuel electrode component. In some cases, the air electrode functional layer is coated on the air electrode support and reheated at about 1,250 ° C.

As shown in FIG. 3 and FIG. 4, in order to manufacture an oxidizing atmosphere high-conductivity ceramics membrane for such an air electrode support, conductive ceramics or a composite thereof is used as a lanthanum-based perovskite which is highly conductive ceramics in an oxidizing atmosphere, LCCC (Denoted _by (La _x Ca _{1 -x} ) (Co _y Cr _{1 -y} ) O ₃ (where 0 x 1, 0 y 1)) was used to form a first coating film .

Representative exemplary composition of a _{(La 0. 1 Ca 0 .9} ) (Co 0. 2 Cr 0. 8) O 3. The first connecting material (corundum) film may be manufactured using only pure LCCC connecting material, or may be manufactured in the form of a composite. For use in the form of a composite, it is the same as in Example 1

Similarly, as shown in FIG. 3 and FIG. 4, the LST or LSF compound in a reducing atmosphere (i.e., (La _x Sr _{1 -x} ) TiO ₃ (Where 0? _X? 1) or (La _x Sr _{1 -x} ) FeO ₃ (Where 0 ≤ x ≤ 1)) was used to form the second connector coating film. In particular, each layer is mixed with 0 to 100% of at least one compound selected from zirconia, ceria, bismuth oxide, barium-strontium titanate and lanthanum strontium gallium magnesia-based oxide to form an organic binder and a solvent Slurry or paste with tape casting or by slurry coating, dipping, spray coating, spin coating, or screen printing.

In particular, the first coating layer essentially has a dense film structure, and the second coating layer is less dense but has no problem in use, so it is made of a dense film or a porous film. (La _x Ca _{1 -x} ) (Co _y Cr _1-y ) O ₃ (where 0? _{X? 1} , 0 _{? Y? 1} ), which is an oxidizing atmosphere high-conductivity ceramics, is used as the first coating film , And a compound of LST or LSF (i.e., (La _x Sr _{1 -x} ) TiO ₃ (Where 0? _X? 1) or (La _x Sr _{1 -x} ) FeO ₃ Zirconium oxide (ZrO ₂ ) doped with yttrium (Y) (0 to 20%) in order to use pure compounds or to form a composite in the case of preparing a compound of the formula ( ₁ ) 5, and the mixture was ball milled with ethyl alcohol for about 24 hours to perform mechanical pulverization and mixing. In order to improve the densification and sintering density of the composite, the additive was added as a sintering additive. TiO ₂ , Bi ₂ O ₃ , Cr ₂ O ₃ , CoO, Y ₂ O ₃ Were added in an amount of 0 to 30%. After drying, a tape casting green sheet was produced, and then a green sheet film having a thickness of about 60 μm was formed. At this time, the used mylar film was attached to the surface of the preliminarily sintered anode support at the same time, and the mylar film was removed. The dried tape casting green sheet was reattached to the final composite composite conductor The thickness of the film was adjusted, and the coating was usually applied two times, followed by heat treatment at 600 to 1500 占 폚 for aging treatment (Aging: homogenization in an oven at about 70 占 폚 for about 1 hour).

The second coating layer according to the present invention was prepared as a coating layer on the air electrode support type connection member (separator plate) manufactured by the above method. (La _x Ca _{1 -x} ) (Co _y Cr _{1 -y} ) O ₃ (where 0? _{X? 1} , 0? _{Y? 1} ), which is high-conductivity ceramics in a polycrystalline atmosphere (0-20%) zirconium oxide (ZrO ₂ ) doped with yttrium (Y) in a weight ratio of 5: 5 to make pure compounds or to form complexes, and this is mixed with ethyl alcohol for about 24 hours And then subjected to mechanical milling and mixing. In order to improve the densification and sintering density of the composite, the additive was added as a sintering additive. TiO ₂ , Bi ₂ O ₃ , Cr ₂ O ₃ , CoO, Y ₂ O ₃ Were added in an amount of 0 to 30%. After drying, a tape casting green sheet was produced, and then a green sheet film having a thickness of about 60 μm was formed. In general, it was coated with two times of coating, followed by heat treatment at 600 to 1500 占 폚 for aging treatment (aging (homogenization treatment in an oven at about 70 占 폚 for about one hour), followed by plasticizing treatment. Finally, the supports were subjected to final co-firing at 1400 ~ 1650 ℃ in a heat treatment process to develop an anode-support type high conductivity multilayered interconnector (separator). Finally, the thickness of the high-conductivity dense conductive film was set to 5 to 50 μm.

Hereinafter, a method of manufacturing a green sheet of a ceramic conductive film and using the method are same as in the first embodiment.

Also, a paste similar to that of Example 2 was prepared, and an LCCC layer, which is a first coating layer stable in an oxidizing atmosphere, was used as a second coating layer, and a high- A ceramic paste or slurry was prepared as in Example 2, and a film was prepared using the ceramic paste or slurry.

Example 5 Production of SOFC and SOEC Single Cells and Module Using Airgel Supporting Material

A single cell unit is fabricated by combining a support thin film type SOFC single cell and a connecting material (separator plate). A single cell unit module comprising a single cell (including ion conductor slabs) manufactured by the same manufacturing method and a connection material separator plate (high conductivity multi-film type connection material) .

A green sheet is prepared by tape casting and is attached and coated by preparing a plate or tubular support made of a cathode material (LSM) first and a ceramic film serving as an electrolyte or a conductive film thereon. Alternatively, it can be produced by a screen printing method.

Here is a more detailed explanation.

In the present invention, a fuel electrode support was prepared, and pure LSM or LSM-YSZ mixed powder was used for preparing the support. (Organic or aqueous) and pore-forming agent, which are advantageous in terms of cost, and at least one of compounds such as zirconia-based oxide, alumina-based oxide, mullite-based oxide, silica-based oxide or carbide and nitride, Shaped, tubular or mixed type, and then heat-treated at a high temperature of 1,000 ° C. or higher to prepare a preliminarily sintered (calcined) support. In the case of graphite added for pore formation, the particle size and mixing ratio should be appropriately controlled. In order to manufacture a unit cell, a plate-shaped support was formed by uniaxial molding with a square mold having a desired size. In order to manufacture a tubular support, a tubular support having a length of about 1 m was formed by using an extruder. After drying at room temperature, they were heat treated at about 1,200 ~ 1,450 ℃ to obtain a pre - sintered body of fuel electrode component. In some cases, a porous catalyst layer is first coated on the oxide support as a functional layer with the same components as the anode, and then heat treated at about 900 to 1,500 ° C.

The upper surface of this support is coated with an ion conductor film containing YSZ as a main component, and a single cell plate is fabricated. Likewise, on the lower surface (tubular type) of the support or the plate surface, a ceramic conductive film . In particular, the multi-layered ceramic conductive film uses a tape casting method, a screen printing method or the like as in the fourth embodiment. The flat plate type is manufactured by attaching the electrolyte plate and the connection plate made by forming the flow path in each of them. The mixed powder of LSM-YSZ is paced and applied to the contact part, dried and heat- And the lower plate are attached first. Then, the unit cell module unit can be manufactured by simultaneously sintering the electrolyte-coated upper plate at 1000 to 1650 ° C and the lower plate coated with the high-conductivity ceramic membrane. On the other hand, the air electrode of the single cell module unit manufactured by final sintering using the air electrode support is formed in the final step, and the paste of the CeO ₂ powder (GDC or SDC) doped with the electrolyte layer Gd ₂ O ₃ or Sm ₂ O ₃ is electrolyzed And then heat-treated at a temperature of 1000 to 1500 ° C. Then, GDC or SDC is mixed with LSCF ((La _x Sr _1-x ) (Co _y Fe _1-y ) O ₃ 1, 0 ≤ y ≤ 1)) was prepared, screen-printed on a buffer layer, dried, and finally heat-treated at 600 to 1300 ° C to complete air electrode formation.

The following is the same as mentioned in Example 4.

While the present invention has been described in connection with what is presently considered to be fictitious by those skilled in the art, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. It will be understood that various modifications and changes may be made in the present invention. Accordingly, the technical scope of the present invention should not be limited to the contents described in the detailed description of the specification, but should be defined by the claims.

10: anode electrode support
20: functional layer
30: reducing atmosphere stabilizing first coating layer
40: oxidative atmosphere stabilization Second coating film
60: air electrode support
70: functional layer
80: Stable oxidative atmosphere First coating layer
90: reducing atmosphere stabilizing second coating film

Claims (24)

As a method for producing a support type linking material coating of an electrode support type linking member or a separating plate by simultaneous sintering
Forming a support;
Preparing a conductive ceramic powder as a slurry or a tape cast green sheet, and coating the conductive ceramic powder on the support to form a first coating film;
Preparing a slurry or tape-cast green sheet of the conductive ceramic powder by drying or heat-treating the first coating layer, and coating the first slurry on the first coating layer to form a second coating layer;
Co-sintering the support on which the first coating layer and the second coating layer are formed; Lt; / RTI >
Wherein the support is an anode support or an air support,
The conductive ceramics of the first coating layer of the anode support are LST compound ((La _x Sr _1-x ) TiO ₃ (where 0 _{? X? 1} ) as the lanthanum perovskite, which is a high conductivity ceramics in a reducing atmosphere, ) Or an LSF compound ((La _x Sr _1-x ) FeO ₃ (where 0 _{? X} ? 1)) and the conductive ceramics of the second coating film of the anode support are LCCC (La _x Ca _1-x ) (Co _y Cr _{1 -y} ) O ₃ (where 0 _{? X} ? ₁ , 0 _{? Y} ? 1)
The conductive ceramics of the first coating layer of the air electrode supporter are made of a high conductivity ceramics LCCC ((La _x Ca _1-x ) (Co _y Cr _1-y ) O ₃ (where 0≤x≤1, 0≤y 1)), and the conductive ceramics of the second coating layer of the air electrode support is a lanthanum perovskite, which is a high conductivity ceramic in a reducing atmosphere, as an LST compound ((La _x Sr _1-x ) TiO ₃ 0? _{X? 1} ) or an LSF compound ((La _x Sr _1-x ) FeO ₃ (where 0 _{? X} ? 1)).
The method according to claim 1,
Wherein the forming of the support comprises forming a support composition comprising an organic binder and then subjecting the support composition to a heat treatment to produce a plasticizer.
The method according to claim 1,
The step of forming the support may comprise: a step of forming a support comprising nickel metal or its oxide (NiO); And yttria-stabilized zirconia-based oxide (YSZ) are mixed, and a support composition comprising an organic binder, a solvent and a pore-forming agent is added, and the mixture is heat-treated to form a plasticized support. .
The method according to claim 1,
The support powder NiO and CoO, CuO, Fe ₂ O ₃ And Cr ₂ O ₃ A fuel electrode material containing at least one of powders; Zirconia, ceria, bismuth oxide, barium / strontium citrate compound and lanthanum strontium gallium magnesia oxide; And a pore-forming agent,
And drying the resultant mixture at a temperature of 600 ° C to 1,500 ° C to form a calcined porous fuel electrode support.
The method according to claim 1,
Wherein the support is at least one of La, Sr, Ca, and Ba at site A and ABO _{3 (at} least one site of B, Mn, Co, Fe, A cathode material comprising a perovskite structure compound or a non-organosilicate high conductivity ceramics material; Zirconia, ceria, bismuth oxide, barium / strontium citrate compound and lanthanum strontium gallium magnesia oxide; And pore-forming agents; After mixing,
And drying the resultant mixture at a temperature of 600 ° C to 1,500 ° C to form a calcined porous cathode support.
The method according to claim 1,
The support may be prepared by preparing a support composition containing a mixture of conductive ceramics, an organic binder, a solvent and a pore-forming agent, molding the support composition into a flat plate, a tube or a mixture thereof, Wherein the anode support member is formed of an anode support member.
The method according to claim 1,
The step of forming the first coating layer or the step of forming the second coating layer may include coating the conductive ceramics or the composite slurry with at least one of slurry coating, dipping, spray coating, spin coating, and screen printing, Wherein the coating layer is formed on the support substrate.
delete The method according to claim 1,
The conductive ceramic powder may be at least one selected from the group consisting of lanthanum perovskite or SrCo _0.8 Fe _0.2 O ₃ -δ, Sm _{0 . 6} Sr _{0 . 4 CoO 3 -δ, Y 0. 1} Ba 0. ₉ CoO _{3 -δ,} BaBi _{0. 4} Co _{0 . 2} Fe _{0 . 4} O _{3 - ?,} (Sr _0.85 Y _0.1 ) (Ti _0.95 Co _0.05 ) O ₃ ,
The conductive ceramic powder; At least one electrolyte material selected from zirconia, ceria, bismuth oxide, barium / strontium citrate compound and lanthanum strontium gallium magnesia oxide; Organic binders; Wherein the slurry or paste is coated with at least one of slurry coating, dipping, spray coating, spin coating, and screen printing to heat treat the slurry or paste.
The method according to claim 1,
Wherein the conductive ceramic powder comprises non-lanthanum-based conductive ceramics,
The conductive ceramic powder; At least one electrolyte material selected from zirconia, ceria, bismuth oxide, barium / strontium citrate compound and lanthanum strontium gallium magnesia oxide; Organic binders; Wherein the slurry or paste is coated with at least one of slurry coating, dipping, spray coating, spin coating, and screen printing to heat treat the slurry or paste.
The method according to claim 1,
The step of forming the first coating layer or the step of forming the second coating layer may be performed by using TiO ₂ , MnO ₂ , Sr ₂ CO ₃ , SiO ₂ , Cr ₂ O ₃ , Bi ₂ O ₃ , Y ₂ O _{3, and the like} , to form a coating film using the slurry or paste.
The method according to claim 1,
Wherein the support type coupling material coating film is a multi-layer film including a reducing atmosphere stable conductive ceramic film and an oxidation atmosphere stable conductive ceramics film, wherein the first coating film and the second coating film are stacked in multiple layers and then heat-treated. Gt;
The method according to claim 1,
The step of forming the first coating layer or the step of forming the second coating layer may be performed by preparing a slurry from the conductive ceramic powder, forming the slurry into a sheet using tape casting, attaching the slurry on the support, To form a ceramic layer, and heat treating the ceramic layer to produce a coating film.
The method according to claim 1, wherein the final thickness of the support type coupling material coating film is 0.1 to 900 탆.
The method according to claim 1,
Wherein the sintered density of the support type coupling material coating film is 30% or more.
The method according to claim 1,
Wherein the thickness of the support linking material coating layer is adjusted by the number of times of forming the first coating layer or the second coating layer repeatedly or by the number of times of repeatedly applying the green sheet, .
A support-type ceramic connector comprising a support-type connector coating film produced by the method of any one of claims 1 to 7 or 9 to 16.
18. The method of claim 17,
Wherein the support is a fuel electrode support which is a mixture of NiO and YSZ,
The conductive ceramics of the first coating film may be an LST compound ((La _x Sr _1-x ) TiO ₃ (where 0 _{? X} ? 1)) or LSF (perovskite), which is a lanthanum series perovskite, ((La _x Sr _1-x ) FeO ₃ (where 0 _{? X} ? 1)),
The conductive ceramics of the second coating film may be a high conductivity ceramics LCCC ((La _x Ca _1-x ) (Co _y Cr _1-y ) O ₃ (where 0 x 1, 0 y 1 )),
Wherein the first coating layer or the second coating layer is formed of at least one compound selected from zirconia, ceria, bismuth oxide, barium-strontium citrate compound, and lanthanum strontium gallium magnesia-based oxide; The conductive ceramics; An organic binder and a solvent, and applying the slurry or paste by tape casting or by coating with at least one of slurry coating, dipping, spray coating, spin coating and screen printing, followed by heat treatment. Ceramic connector.
18. The method of claim 17,
The support is an air electrode support which is a mixture of lanthanum-based perovskite,
The conductive ceramics of the first coating film may be a high-conductivity ceramics LCCC ((La _x Ca _1-x ) (Co _y Cr _1-y ) O ₃ (where 0 x 1, 0 y 1 )),
The conductive ceramics of the second coating film may be an LST compound ((La _x Sr _1-x ) TiO ₃ (where 0 _{? X} ? 1)) or LSF (perovskite) as a lanthanum perovskite, which is a high conductivity ceramics in a reducing atmosphere, ((La _x Sr _1-x ) FeO ₃ (where 0 _{? X} ? 1)),
Wherein the first coating layer or the second coating layer is formed of at least one compound selected from zirconia, ceria, bismuth oxide, barium-strontium citrate compound, and lanthanum strontium gallium magnesia-based oxide; The conductive ceramics; An organic binder and a solvent, and applying the slurry or paste by tape casting or by coating with at least one of slurry coating, dipping, spray coating, spin coating and screen printing, followed by heat treatment. Ceramic connector.
18. The method of claim 17,
And a functional layer interposed between the first coating layer and the support to promote densification of the first coating layer.
A single cell using the supporting ceramic connecting material of claim 17 as a connecting material or separator.
22. The method of claim 21,
Wherein the unit cell is formed by combining a support-type connecting material coating film with a unit cell of an electrolytic cell or a fuel cell formed on a fuel electrode or an air electrode.
A stacking apparatus using the support-type ceramic connecting member of claim 17 as a connecting material or separator.
24. The method of claim 23,
Wherein the stacking device is a stacked device in which a supporting linking coating film is combined with an electrolyte cell or a single cell of a fuel cell formed on a fuel electrode or an air electrode.

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