KR101341962B1 - Segment-in-series type sofc sub-module, preparation method thereof and segment-in-series type sofc module using the same - Google Patents

Abstract

The present invention relates to a segment type solid oxide fuel cell sub-module, a method for producing the same, and a segment type solid oxide fuel cell sub-module using the same. The segment type solid oxide fuel cell sub-module of the present invention can present high-power output, and have increased resistance to heat cycles by using porous scaffold supporter with higher gas permeability than the conventional technique and excellent mechanical strength.

Description

Segmented Solid Oxide Fuel Cell Submodule, Manufacturing Method Thereof and Segmented Solid Oxide Fuel Cell Module Using The Same

The present invention relates to a segmented solid oxide fuel cell submodule exhibiting improved gas permeability and mechanical strength compared to the prior art, a method of manufacturing the same, and a segmented solid oxide fuel cell module using the same.

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

Since the electrolyte and the electrode are in a solid state, the SOFC can be manufactured in various types of cells such as a plate type or a cylindrical type, and can be classified into an anode support type and an air cathode support type and an electrolyte support type according to a support of a fuel cell do.

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

Cylindrical SOFCs are evaluated as SOFC designs closest to commercialization because they do not require gas sealing, have excellent mechanical strength, and have been tested for reliability in various test items. However, the cylindrical SOFC has a disadvantage of high internal resistance and low power density because of a long current path. In addition, since the voltage output from the module, which is a collection of cells, is low, the power conversion loss during operation is large, and as a result, there is a weakness in efficiency.

Currently, SOFC systems for power generation above 20 kW are mostly adopting stacks using cylindrical or improved cylindrical cells, and in the case of 20 kW or lower, flat cells are also adopted.

On the other hand, the segment-in-series type SOFC is one of the most advantageous and economical types of the improved cell type to compensate for the shortcomings of the conventional SOFC cell type for power generation. The cell is composed of nodes made of several cells. Since the segmented SOFC cell is a module in which unit cells are connected in series, it is possible to generate high efficiency with a high voltage and low current output, reduce the volume of the stack, and simplify the system. In addition, segmented SOFC cells can reduce stack manufacturing costs, apply low-cost wet coating processes that can be mass-produced, and minimize gas sealing problems by only gas sealing the edges of cylindrical cells. There is an advantage in that large area is easy through increasing the length of the cell support.

The present invention is a segmented solid oxide fuel cell submodule comprising a porous tubular support, a fuel electrode, an electrolyte layer, an air electrode, and a connecting member formed on the outer surface of the porous tubular support in Korea Patent Publication No. 2012-0034508, the porous tubular support is uniform And a paste prepared by kneading a mixture of powdered calcia stabilized zirconia (CSZ) and activated carbon powder, a binder, and distilled water, by extrusion, drying, heat treatment, and sintering. Starting a module.

Porous tubular supports used in segmented solid oxide fuel cell submodules must have mechanical and thermal stability and have a porous structure.

Segmented solid oxide fuel cell submodules generate power through electrochemical reactions in cells coated in series with a connecting material on the surface of the porous tubular support. For this reason, as the fuel permeation rate increases through the porous tubular support, high power generation is achieved, so the porosity increases. However, as the porosity increases, the mechanical properties are weakened. Therefore, the pore-forming agent must be determined and optimized in consideration of mechanical strength.

The present inventors have repeatedly studied to improve the segmented solid oxide fuel cell disclosed in the prior art, and as a result, it has been found that the present invention can be optimized by developing and applying a porous tubular support having improved gas permeability and mechanical strength. Came to complete.

Accordingly, an object of the present invention is to provide a segmented solid oxide fuel cell submodule having improved physical properties, a method of manufacturing the same, and a segmented solid oxide fuel cell module using the same.

In order to achieve the above object, the present invention is a segmented solid oxide fuel cell submodule comprising a porous tubular support, a fuel electrode, an electrolyte layer, an air electrode and a connecting member formed on the outer surface of the porous tubular support, the porous tubular support is uniform and powdered Segmented solid oxide fuel, characterized in that the paste prepared by kneading a mixture of oxidized 3 mol% yttria stabilized zirconia and activated carbon powder, a plasticizer, a lubricant, a binder and distilled water is subjected to extrusion, drying, heat treatment and sintering. Provides a battery submodule.

The present invention also provides a method for preparing a porous tubular support using a paste comprising a mixture of homogenized and powdered 3 mol% yttria stabilized zirconia and activated carbon powder, a plasticizer, a lubricant, a binder and distilled water (S1); Forming a fuel electrode on the porous tubular support (S2); Forming an electrolyte layer on the anode (S3); Forming an air electrode on the electrolyte layer (S4); And forming a connection material for electrical connection (S5).

The present invention provides a segmented solid oxide fuel cell submodule capable of high output, increased starting speed and thermal cycle resistance by using a porous tubular support having high gas permeability and excellent mechanical strength compared to the prior art, and a method of manufacturing the same. It provides a segmented solid oxide fuel cell module.

1 (A) to (E) is a homogenization step for controlling the particle size of the raw material powder (A) during the process for producing a porous tubular support according to the present invention, (B) a kneading step for uniform mixing of the support powder, (C) A photograph of the paste-kneaded step for extrusion, (D) extrusion of the paste, and (E) rolling drying to improve the straightness of the support.
Figure 2 is a graph showing the results of measuring the state change according to the temperature of the pore-forming agent and the additive of the porous tubular support prepared in Example 1 according to the present invention using TGA.
3 is a graph showing the plasticization conditions of the porous ceramic support in consideration of the combustion of activated carbon and a binder in Example 1 according to the present invention.
FIG. 4 is a SEM photograph of a specimen prepared by extruding a porous tubular support of CSZ and 3YSZ to which different amounts of pore-forming agents (activated carbon) were added in Test Example 1 according to the present invention.
Figure 5 is a SEM photograph taken on the outer surface and the inner surface of the porous tubular support of 3YSZ added 10 parts by weight of activated carbon in Test Example 1 according to the present invention.
Figure 6 is a graph of the pore distribution measured for the porous tubular support of 3YSZ and CSZ according to Example 1 and Comparative Example 1 in Test Example 2 according to the present invention.
Figure 7 is a graph of the porosity measured for the porous tubular support of 3YSZ and CSZ according to Example 1 and Comparative Example 1 in Test Example 2 according to the present invention.

Hereinafter, a segmented solid oxide fuel cell submodule of the present invention, a manufacturing method thereof, and a segmented solid oxide fuel cell module using the same will be described in detail.

In addition, Korean Patent Publication No. 2012-0034508 of the present inventors is incorporated in its entirety by reference to the present invention.

The present invention is a segmented solid oxide fuel cell submodule comprising a porous tubular support, a fuel electrode, an electrolyte layer, an air electrode, and a connection member formed on the porous tubular support.

The porous tubular support is prepared by extrusion, drying, heat treatment and sintering of a paste prepared by mixing a mixture of homogenized and powdered 3 mol% yttria stabilized zirconia and activated carbon powder, a plasticizer, a lubricant, a binder, and distilled water. It is characterized by using a thing.

In the segmented solid oxide fuel cell submodule, the porous tubular support serves as a flow path of fuel / reactant while forming a frame of a cell, and is composed of a material having no electrical conductivity because it connects two or more unit cells.

The porous tubular support used in the segmented solid oxide fuel cell submodule of the present invention is prepared using a paste containing a mixed powder of homogenized and powdered 3 mol% yttria stabilized zirconia and activated carbon as a pore former. And high gas permeability and excellent mechanical strength as compared to porous tubular supports prepared using powdered calcia stabilized zirconia (CSZ) and activated carbon.

The segmented solid oxide fuel cell submodule according to the present invention is manufactured by sequentially forming a fuel electrode, an electrolyte layer, an air electrode, and a connecting material on the porous tubular support.

The anode is manufactured using a slurry prepared by mixing nickel oxide (NiO) powder, yttria stabilized zirconia (YSZ) powder, a binder, a homogeneous agent, a dispersant, a plasticizer and a solvent.

The electrolyte layer is formed by coating a slurry prepared by mixing yttria stabilized zirconia (YSZ) powder, a binder, a homogeneous agent, a dispersant, a plasticizer and a solvent on the anode.

The cathode is formed of a multilayer structure cathode in which an LSM-YSZ layer, an LSM layer, and an LSCF layer are sequentially formed.

The segmented solid oxide fuel cell submodule is electrically connected by a connecting member after a plurality of unit cells including a fuel electrode, an electrolyte layer, and an air electrode are formed on the porous tubular support.

The connecting member is formed in the segmented solid oxide fuel cell submodule to electrically connect the anode of the unit cell and the cathode of another unit cell.

 In one embodiment of the present invention, the connecting material may be formed using silver-glass paste, but may be used without limitation, materials commonly used in the art to which the present invention pertains.

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

First, a porous tubular support is prepared using a paste comprising a mixture of homogenized and powdered 3 mol% yttria stabilized zirconia and activated carbon powder, a plasticizer, a lubricant, a binder and distilled water (S1).

In the present invention, 3 mol% yittria stabilized zirconia powder is used as a main raw material for preparing a porous tubular support, and active carbon powder is used as a pore forming agent, and 3 mol% or less is used. 5-15 parts by weight of activated carbon is mixed with 100 parts by weight of tria stabilized zirconia.

A mixture of 3 mol% yttria stabilized zirconia and activated carbon powder mixed according to the above-mentioned contents of use is prepared in a slurry state and homogenized by ball milling. At this time, ethanol is used as a solvent, and since ethanol is fast drying, the work can be performed quickly when dried in a dryer after ball milling. Ball milling is performed for two weeks using high-purity zirconia balls, making it possible to make the mixture of 3 mol% yttria stabilized zirconia and activated carbon powder as uniform as possible (see FIG. 1A).

Subsequently, the mixture of homogenized 3 mol% yttria stabilized zirconia and activated carbon powder is dried in a hot plate and then ground to powder.

Then, based on 100 parts by weight of the mixture of powdered 3 mol% yttria stabilized zirconia and activated carbon powder, 7 to 8 parts by weight of plasticizer, 6 to 7 parts by weight of lubricant, 17 to 18 parts by weight of binder, and 20 to 30 parts by weight of distilled water are added. And kneading to form a paste (see Figs. 1B and 1C). As the binder, YB-131D, which is a comprehensive binder, may be used, and YB-131D is widely known as an organic binder including methyl cellulose and hydroxypropyl methyl cellulose, a plasticizer and a lubricant. The binder serves to bind the powdered mixture and to form pores with the activated carbon.

Next, the paste formed according to the above-described process is extruded into the porous tubular support using the extruder shown in FIG. 1 (D), and it is preferable to undergo a process of refrigeration so that the moisture of the paste is evenly distributed before extrusion.

Since the extruded porous tubular support is formed in a tubular shape, there is a fear that warpage or cracking may occur due to evaporation of the solvent during drying. Therefore, to prevent this, a metal bar (not shown) such as a steel bar (steel bar) is inserted into the tube of the porous tubular support and dried at room temperature while rolling in a rolling dryer as shown in FIG.

Thereafter, the dried porous tubular support is subjected to a process of completely burning the binder and the activated carbon component added to the porous tubular support. That is, the temperature and the temperature are increased to 0.67 ℃ / minute to 200 ℃ slowly burned the remaining moisture and additives, and maintained for 3 to 5 hours at 200 ~ 300 ℃ to burn the binder slowly, and heated to 1 ℃ / minute to 600 ℃ After that, it is maintained for 3 to 5 hours to completely burn the activated carbon.

Finally, the porous tubular support heat treated as described above is heated to 1.67 ° C./min up to 1400 ° C. to be calcined for 3 hours to complete the porous tubular support.

The porous tubular support manufactured according to the above-described method exhibits higher gas permeability and excellent compressive strength than the conventional porous tubular support, so that when used in a segmented solid oxide fuel cell submodule and a module using the same, high output power and start-up are possible. Segmented solid oxide fuel cell submodules with increased speed and thermal cycle resistance and modules using the same can be manufactured.

Next, a fuel electrode is formed on the porous tubular support, an electrolyte layer is formed on the fuel electrode, and an air electrode is formed on the electrolyte layer (S1 to S4).

Finally, to form a connection for electrical communication of the segmented solid oxide fuel cell submodule (S5).

In one embodiment of the present invention, the connecting material may be formed by coating a silver-glass paste.

The method of forming the anode, the electrolyte layer, the cathode and the connecting member on the porous tubular support prepared as described above according to the present invention is the same as that disclosed in Korean Patent Laid-Open No. 2012-0034508, which is incorporated herein by reference.

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

The embodiments and drawings described in the present specification are preferred embodiments of the present invention and are not intended to represent all of the technical ideas of the present invention, so that various equivalents and modifications may be substituted for them at the time of application of the present invention.

Example  One

3 mol% yttria stabilized zirconia powder (3YSZ powder), the main raw material, was used as a pore-forming agent for preparing a porous tubular support. 15 parts by weight was mixed and quantified. After ethanol was added, the mixed powder was uniformly subjected to wet ball milling for 2 weeks using high purity zirconia balls, and then dried in a hot box at 80 ° C. for 24 hours. After drying, the mixture was ground using a sieve having a size of 100 and 200 µm to obtain a mixed powder in which the support powder and the pore-forming agent were uniformly mixed.

To the prepared mixed powder, an aqueous composite binder (YB-13D, SERANDER, .CO. Japan), a plasticizer, a lubricant, a solvent (distilled water) are added to the ingredients shown in Table 1, materials and contents thereof. To produce an extrusion paste. In the kneading process, first, the mixed powder and the water-based binder were mixed in a powder state for 30 minutes, and then a liquid solution mixed with a plasticizer, a lubricant, and distilled water was made and added uniformly. The 3YSZ supporter prepared a paste for extrusion to achieve a smooth extrusion by controlling the content of the distilled water at a ratio of 1: 1 by the ratio of the pore-forming agent and the distilled water. The prepared extrusion paste was refrigerated for 24 hours so that the solvent was evenly distributed, and then the extruded porous tubular support.

[Table 1]

The steel bar was inserted into the inside of the center of the porous tubular support prepared above, and dried at room temperature for 48 hours in a rolling dryer. The dried tubular support was presintered at 1100 ° C. for 3 hours to remove the additives and impart the strength required for the coating process.

In order to prevent the occurrence of defects due to the combustion gas, the state change with temperature of the pore-forming agent and the additive was measured using TGA (Thermo Gravimetric Analysis) and the results are shown in FIG. 2. At this time, the temperature raising condition was 5 ° C / min, N ₂ gas as the protective gas, air was injected into the active gas. Referring to FIG. 2, the mass decrease occurs due to the combustion of the binder at 200 to 300 ° C., and the mass decrease occurs due to the combustion of the activated carbon at 550 to 600 ° C.

The sintering conditions of the porous ceramic support in consideration of the combustion of activated carbon and a binder are shown in FIG. 3. 3, the temperature was raised to 0.67 ° C / min per hour up to 200 ℃ and slowly burned the remaining water and additives, and maintained at 200 ~ 300 ℃ for 5 hours each to slowly burn the binder. After heating up to 1 ° C./min up to 600 ° C., the mixture was kept for 5 hours to completely burn the activated carbon. Finally, the temperature was raised to 1.67 ° C./min to 1100 ° C., followed by sintering for 3 hours to prepare a porous ceramic support used in the present invention.

Comparative Example  One

Instead of 3 mol% yttria stabilized zirconia powder, which is the main raw material, calcia stabilized zirconia (CaO-stabilized ZrO ₂ : CSZ) powder is used, and the ratio of pore-forming agent and distilled water is 1: 2, and the components, materials and Except that the content was used as shown in Table 2 by extrusion molding in the same manner as in Example 1 to prepare a porous tubular support.

[Table 2]

Test Example 1 Surface Characterization of Porous Tubular Support Prepared by Different Presintering Process Conditions

After extruding the porous tubular support of CSZ (Comparative Example 1) and 3YSZ (Example 1) to which 5, 10, and 15 parts by weight of pore-forming agent (activated carbon) were added, it was calcined at 1100 ° C. for 3 hours, and then 1400 ° C. The specimen sintered for 5 hours was produced. The microstructure of the surface is shown in FIG. 4 using SEM.

Referring to FIG. 4, as the activated carbon content increased, the pores increased, which is considered to be pore formation by the combustion gas. In addition, as the content of the pore-forming agent increases, the particle filling rate of the green body is lowered, and thus the microstructure after sintering shows a porous structure. The microstructure of the outer surface and inner surface of the porous tubular support of 3YSZ to which 10 parts by weight of activated carbon was added is shown in FIG. 5. Referring to FIG. 5, it can be seen that the pores are uniformly dispersed at the interface without a large difference between the outer surface and the inner surface. It is thought that the permeation of the fuel gas is smooth when the pores are continuously connected and used as a support of the segmented solid oxide fuel cell submodule.

Test Example 2: Pore Distribution and Porosity of Porous Tubular Supports According to Pore Formant Content

The pore distribution and porosity were analyzed by mercury penetration method after sintering the porous tubular supports of 3YSZ and CSZ according to Example 1 and Comparative Example 1 for 5 hours at 1400 ° C. in FIGS. 6 and 7, respectively. Indicated. 6 and 7, the porous tubular support of CSZ has an average pore size d ₅₀ of 0.37, 0.67, and 0.9 μm when the activated carbon content is 5, 10, and 15 parts by weight, respectively. As a result, the pore size gradually increases. Compared to 5 parts by weight, the pore size distribution was more than doubled when the activated carbon content was 15 parts by weight. When the activated carbon content is 5, 10, 15 parts by weight, the porosity tends to gradually increase to 25, 34 and 36%, respectively. The porous pore support of 3YSZ had an average pore size d ₅₀ of 0.33, 0.38, and 0.52 μm when the activated carbon content was 5, 10, and 15 parts by weight, respectively. The figure increased to 29, 39 and 43%, respectively. As the activated carbon content increased, the average pore size and porosity were confirmed. It can be seen that the pore-forming agent content affects the pore size and porosity. When the activated carbon content is parts by weight, the average pore size d ₅₀ of the porous tubular support of CSZ is 0.9 μm and the porosity is 36%. The average pore size d ₅₀ of the porous tubular support of 3YSZ is 0.52 μm and the porosity is 43%. The porous tubular support of 3YSZ shows that the micropores with uniform distribution are 7% more pores than the porous tubular support of CSZ.

Test Example 3 Measurement of Gas Permeability of Porous Tubular Support

Gas permeability was measured using a gas permeability meter (VAC, Testo 445, Testo AG, Belgium) for porous tubular supports of 3YSZ and CSZ according to Example 1 and Comparative Example 1 having an activated carbon content of 15 parts by weight.

The gas permeability seals one end of each of the porous tubular supports of CSZ and 3YSZ of the same thickness and length, and injects H ₂ gas on the opposite side to calculate the differential pressure values between the inside of the porous tubular support and atmospheric pressure according to the following equation (1) according to darcy's law. Calculation by substitution.

 [Equation 1]

[Wherein Q is the flow rate, k is the gas permeability, H ₂ is the viscosity coefficient of the gas, P is the differential pressure, A is the surface area of the support, and L is the support thickness].

As a result, the gas permeability of the porous tubular support of CSZ having low porosity showed a value of 3.56 × 10 ⁻¹⁴ m ² , and the porous tubular support of 3YSZ showed a value of 0.92 × 10 ⁻¹⁴ m ² . The porous tubular support of 3YSZ exhibited a gas permeability that was one quarter times lower than the porous tubular support of CSZ. This result is due to the pore morphology of the support. The pore is divided into open and closed pores. The porosity measurement measures the presence of pores without the distinction between open and closed pores. However, gas permeability measurement is determined by tortuosity by open pores. Therefore, the porosity of the 3YSZ porous tubular support shows higher porosity than the CSZ porous tubular support, but the low gas permeability is determined because the pores of the 3YSZ porous tubular support consist of waste pores. The porous tubular support of 3YSZ has a lower gas permeability than the porous tubular support of CSZ but this is a testament to the higher strength of the porous tubular support of 3YSZ.

The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present invention.

Claims (9)

A segmented solid oxide fuel cell submodule comprising a porous tubular support, a fuel electrode, an electrolyte layer, an air electrode, and a connecting member formed on an outer surface of the porous tubular support,
The porous tubular support is prepared by extruding, drying, heat treating and sintering a paste prepared by mixing a mixture of homogenized and powdered 3 mol% yttria stabilized zirconia and activated carbon powder, a plasticizer, a lubricant, a binder, and distilled water.
The porous tubular support comprises mixing, homogenizing and powdering 3 mol% yttria stabilized zirconia and activated carbon;
A paste was prepared by mixing 7 to 8 parts by weight of a plasticizer, 6 to 7 parts by weight of a lubricant, 17 to 18 parts by weight of a binder, and 20 to 30 parts by weight of distilled water based on the powdered powder of 3 mol% yttria stabilized zirconia and activated carbon. Making; And
Segmented solid oxide fuel cell submodule, characterized in that manufactured by performing the step of extruding, drying, heat treatment and sintering the paste.
delete The method according to claim 1,
Segmented solid oxide fuel cell submodule, characterized in that for mixing and homogenizing and powdering 5 to 15 parts by weight of activated carbon with respect to 100 parts by weight of the 3 mol% yttria stabilized zirconia.
The method according to claim 1,
The step of heat-treating and pre-sintering the porous tubular support prepared by extruding the paste is heated to 0.67 ℃ / min per hour to 200 ℃ slowly burning the remaining water and additives, and maintained at 200 ~ 300 ℃ for 3 to 5 hours Slowly burn the binder, and after raising the temperature to 1 ℃ / min to 600 ℃, it is maintained for 5 hours to completely burn the activated carbon, heated to 1.67 ℃ / min to 1400 ℃ is carried out by pre-sintering for 3 to 5 hours Segmented solid oxide fuel cell submodule.
A segmented solid oxide fuel cell module comprising a plurality of segmented solid oxide fuel cell submodules according to any one of claims 1, 3, and 4.
Preparing a porous tubular support using a paste comprising a mixture of homogenized and powdered 3 mol% yttria stabilized zirconia and activated carbon powder, a plasticizer, a lubricant, a binder and distilled water (S1);
Forming a fuel electrode on the porous tubular support (S2);
Forming an electrolyte layer on the anode (S3);
Forming an air electrode on the electrolyte layer (S4); And
Forming a connecting material for electrical connection (S5);
Lt; / RTI >
Preparing the porous tubular support (S1),
Mixing 5 to 15 parts by weight of the activated carbon powder with respect to 100 parts by weight of the 3 mol% yttria stabilized zirconia to prepare a slurry and homogenizing by ball milling;
Pulverizing and drying the mixture of the homogenized 3 mol% yttria stabilized zirconia powder and activated carbon powder to powder;
7 to 8 parts by weight of plasticizer, 6 to 7 parts by weight of lubricant, 17 to 18 parts by weight of binder, and 20 to 25 parts by weight of distilled water to prepare a paste, followed by extrusion into a tubular support, based on 100 parts by weight of the powdered mixture. ;
Inserting a metal bar into the tube of the extruded tubular support and drying at room temperature while rolling; And
Heat-treating the dried tubular support to completely burn the binder and activated carbon component added to the tubular support; And
Sintering the heat-treated tubular support, characterized in that it comprises a segment type solid oxide fuel cell submodule manufacturing method.
delete The method of claim 6,
The step of heat-treating the dried tubular support to completely burn the binder and activated carbon components added to the tubular support, the step of sintering the porous tubular support prepared by extruding the paste remains heated to 0.67 ℃ / min per hour to 200 ℃ It is carried out by slowly burning the moisture and additives present, and slowly burning the binder by holding at 200 ~ 300 ℃ for 3 to 5 hours, the temperature is raised to 1 ℃ / min to 600 ℃, and then maintained for 5 hours to completely burn the activated carbon Method of manufacturing a segmented solid oxide fuel cell submodule, characterized in that.
The method of claim 6,
The step of sintering the heat-treated tubular support is a method of manufacturing a segmented solid oxide fuel cell submodule, characterized in that the temperature is increased to 1.67 ℃ / min to 1400 ℃ by performing a three-sintering.

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