KR101117351B1 - Electrolyte for solid oxide fuel cell and manufacturing method of the electrolyte and cell having the electrolyte and manufacturing method of the cell - Google Patents

Abstract

Disclosed is a unit cell, an electrolyte, and a manufacturing method of a solid oxide fuel cell using cerium-added scandium stabilized zirconia powder of nanoparticles. Method for preparing a cerium-added scandium stabilized zirconia powder, zirconium oxychloride (Zirconium Oxychloride, ZrOCl2), scandium oxide (Scandium Oxide, Sc2O3), cerium oxide (Cerium Oxide, Ce2O3) is mixed with distilled water to form a mixed solution, the Mixing and precipitating a precipitant in a mixed solution, filtering the precipitate in the mixed solution, hydrothermal synthesis of the filtered precipitate, drying the precipitate having completed hydrothermal synthesis, and drying the precipitated precipitate. The heat treatment is performed to prepare cerium-dopped Scandium Stabilized Zirconia (CeScSZ) powder.

Solid oxide fuel cell, SOFC, electrolyte, tape-casting, cerium-dopped Scandium Stabilized Zirconia (CeScSZ)

Description

ELECTROLYTE FOR SOLID OXIDE FUEL CELL AND MANUFACTURING METHOD OF THE ELECTROLYTE AND CELL HAVING THE ELECTROLYTE AND MANUFACTURING METHOD OF THE CELL

The present invention relates to a solid oxide fuel cell, an electrolyte for a solid oxide fuel cell using a cerium-dopped scandium stabilized zirconia (CeScSZ), a method for producing the same, and a unit cell of a solid oxide fuel cell It is for providing the manufacturing method.

A fuel cell is defined as a cell that has the ability to produce direct current by converting the chemical energy of fuel (hydrogen) directly into electrical energy, and through the oxide electrolyte, oxidant (eg oxygen) and gaseous fuel (eg For example, as an energy conversion device for producing direct current electricity by electrochemically reacting hydrogen), unlike the conventional battery, it is characterized by continuously producing electricity by supplying fuel and air from the outside.

Fuel cell types include molten carbonate fuel cells (MCFCs), solid oxide fuel cells (SOFCs) operating at high temperatures, and phosphoric acid fuel cells operating at relatively low temperatures. Cell, PAFC), Alkaline Fuel Cell (AFC), Proton Exchange Membrane Fuel Cell (PEMFC), Direct Methanol Fuel Cells (DEMFC).

Here, the solid oxide fuel cell may include a solid state structure, adaptability of multiple fuels, and high temperature operability. Due to the characteristics of such a solid oxide fuel cell, a solid oxide fuel cell has the potential to be a high performance, clean and efficient power source, has been developed for various power generation applications.

The solid oxide fuel cell is formed of a multilayer stack of unit cells composed of a cathode, an anode, and an electrolyte. A typical unit cell of the solid oxide fuel cells, yttria stabilized zirconia (Yttria Stabilized Zirconia, YSZ) is used, and the air electrode is broken the strontium-doped lanthanum nitro (Lanthanum Strontium Manganite, LSM) as the electrolyte (La _{0 .8} Sr _{0 .2} MnO ₃₎ is used, and the fuel electrode is nickel oxide (nickel oxide, NiO) and YSZ a meth (cermet) mixed standing (NiO / YSZ) is used.

Here, the conventional YSZ electrolyte is manufactured using commercially available CeScSZ powders having a particle diameter of about 1.0 μm or more and having a surface area of about 4 to 8 cm 2 / g, and expensive manufacturing such as CVD (chemical vapor deposition) or plasma spray. It is manufactured using the apparatus.

When manufacturing a unit cell of a solid oxide fuel cell, the anode material and the electrolyte material have different coefficients of thermal expansion, and even if firing at a similar firing temperature, bending or cracking may occur when the anode and the electrolyte are fired at the same time. When the electrolyte is peeled off or warped, the unit cell may not be overcome and the unit cell may be broken. In particular, the warpage or crack of the unit cell increases as the area of the unit cell increases. Conventionally, there is a method of manufacturing a unit cell by firing the anode, the electrolyte, and the cathode, or by firing the anode serving as the support first, followed by coating the electrolyte on the anode, followed by baking the cathode.

However, the conventional unit cell manufacturing method requires firing the anode, the electrolyte, and the cathode, respectively, which not only complicates the manufacturing process of the unit cell but also makes it difficult to continuously perform the manufacturing process, requiring a lot of time and manpower when manufacturing the unit cell. Production cost increases. In addition, as the area of the unit cell increases, it is difficult to coat the electrolyte thinly and uniformly, and thus there is a problem in that performance is reduced when the unit cell is manufactured.

Embodiments of the present invention for solving the above problems are to provide a manufacturing method capable of manufacturing a thin film electrolyte and a unit cell.

In addition, embodiments of the present invention is to provide a method for manufacturing an electrolyte and a unit cell that the manufacturing process is simple and can reduce the production cost.

According to the embodiments of the present invention for achieving the above object of the present invention, the method of manufacturing a cerium-added scandium stabilized zirconia powder, zirconium oxide (Zirconium Oxychloride, ZrOCl ₂ ) and scandium oxide (Scandium Oxide, Sc ₂ O ₃ ), mixing cerium oxide (Cerium Oxide, Ce ₂ O ₃ ) in distilled water to form a mixed solution, the step of precipitating by mixing a precipitant in the mixed solution, filtering the precipitate in the mixed solution, the filtered precipitate Hydrothermal synthesis, drying the precipitate having completed the hydrothermal synthesis, and heat treating the dried precipitate to prepare cerium-dopped Scandium Stabilized Zirconia (CeScSZ) powder. .

For example, the CeScSZ powder has a particle size of 1 to 10 nm and a surface area of 100 to 300 cm 2 / g. In addition, the mixed solution is zirconium oxychloride (ZrOCl ₂ ~ 8H ₂ O) and scandium nitrate (Scandium Nitrate, Sc (NO ₃ ) _{3 ~} 6H ₂ O) and cerium nitrate (Cerium Nitrate, Ce (NO ₃ ) _{3 ~} 6H ₂ O) can be mixed and formed.

On the other hand, according to the embodiments of the present invention for achieving the above object of the present invention, the unit cell manufacturing method of a solid oxide fuel cell, a step of forming a first slurry by mixing nickel oxide (NiO) and YSZ, Forming a cathode support layer sheet using the first slurry, mixing a NiO and YSZ to form a second slurry, forming a anode reaction layer sheet using the second slurry, and CeScSZ powder of nanoparticles Forming a CeScSZ slurry using the CeScSZ slurry, forming an electrolyte sheet using the CeScSZ slurry, and sequentially laminating and laminating the anode reaction layer sheet and the electrolyte sheet on the anode support layer sheet. Forming a step, a calcination step for removing the solvent and the binder from the laminate, and the calcination is completed Sintering the layer.

Here, the CeScSZ powder is formed by a coprecipitation method and a hydrothermal synthesis method, has a particle size of 1 to 10 nm, and a specific surface area of 100 to 300 m 2 / g. The electrolyte sheet may be formed to a thickness of 5 to 10 μm, and the electrolyte may be formed by stacking one sheet of the electrolyte sheet on the anode reaction layer sheet.

In addition, the unit cell of the solid oxide fuel cell forms an LSCF / GDC slurry in which lanthanum strontium cobalt ferrite (LSCF) and gadolinium doped ceria (GDC) are mixed. The forming of the cathode using the LSCF / GDC slurry on the electrolyte in the calcined laminate, and calcining the laminate and the cathode are performed.

Here, the cathode may be mixed with the LSCF and the GDC in a weight ratio of 60:40.

On the other hand, according to embodiments of the present invention for achieving the above object of the present invention, the anode support type electrolyte for a solid oxide fuel cell, the anode support layer formed of NiO / YSZ cermet mixed with NiO and YSZ, NiO / YSZ standing The anode support layer, the anode reaction layer, and the electrolyte are formed of CeScSZ of nanoparticles formed by using the anode reaction layer and the co-precipitation method, which are formed on the anode support layer, and are stacked on the anode reaction layer. The electrolyte is cofired.

For example, the CeScSZ powder is a powder having a particle size of 1 to 10 nm, specific surface area of 100 to 300 m 2 / g by coprecipitation method and hydrothermal synthesis, and the electrolyte is formed to a thickness of 1 to 5㎛ Can be.

On the other hand, according to the embodiments of the present invention for achieving the above object of the present invention, the unit cell of the solid oxide fuel cell, the anode reaction in which the NiO / YSZ sheet is laminated on the anode support layer in which the NiO / YSZ sheet is laminated A cathode support type electrolyte formed by co-firing an electrolyte formed by laminating a CeScSZ sheet of nanoparticles formed by using a layer and a tape casting on the anode reaction layer, and an LSCF / GDC cermet mixed with LSCF and GDC, and the anode support type It consists of an air electrode laminated on an electrolyte.

For example, the anode support layer is formed by stacking 30 to 60 sheets of NiO / YSZ sheets having a thickness of 35 to 45 μm, and the anode reaction layer is formed by stacking one sheet of NiO / YSZ sheets having a thickness of 10 to 30 μm. Can be. The cathode may be mixed with the LSCF and the GDC in a weight ratio of 60:40.

As described above, according to the embodiments of the present invention, first, a thin film electrolyte may be manufactured using CeScSZ powder of nanoparticles, and the performance of a unit cell may be improved.

In addition, a unit cell may be manufactured by using a tape casting method.

In addition, the anode and the electrolyte may be manufactured using a continuous tape casting method and co-fired to manufacture an anode-supported electrolyte, thereby reducing process time and cost and improving productivity.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, but the present invention is not limited to or limited by the embodiments. In describing the present invention, a detailed description of well-known functions or constructions may be omitted for clarity of the present invention.

Hereinafter, an electrolyte, a unit cell, and a manufacturing method for a solid oxide fuel cell according to an embodiment of the present invention will be described in detail with reference to FIGS. 1 to 6. For reference, FIG. 1 is a flowchart illustrating a method of preparing cerium-dopped Scandium Stabilized Zirconia (hereinafter, referred to as 'CeScSZ') powder according to an embodiment of the present invention, and FIG. 3 is a flowchart illustrating a method of manufacturing a cathode support-type electrolyte, and FIG. 3 is a flowchart illustrating a method of manufacturing a unit cell. 4 is a schematic cross-sectional view for explaining the structure of a unit cell formed by the above-described manufacturing method, and FIGS. 5 and 6 are images of CeScSZ powders formed by the above-described manufacturing method.

The solid oxide fuel cell is formed by stacking a plurality of unit cells composed of an anode, an electrolyte, and a cathode. Here, the unit cell of the solid oxide fuel cell will be described with reference to FIG. 4, and for the convenience of description, reference numerals are used as shown in FIG. 4. The unit cell 1 is formed by sequentially stacking the anode 10, the electrolyte 20, and the cathode 30 serving as a support, and the anode 10 is the anode support layer 11 and the anode reaction layer 12. Is done.

Here, in the unit cell 1, the fuel electrode 10 is NiO / mixed with nickel oxide (hereinafter referred to as 'NiO') and zirconia (Yttria Stabilized Zirconia, hereinafter referred to as 'YSZ') It is formed of YSZ cermet, the electrolyte 20 is formed of CeScSZ of nanoparticles, the air electrode 30 is a lanthanum strontium cobalt ferrite (hereinafter referred to as "LSCF"). ) is mixed _{(La 0.6 Sr 0.4 Co 0.2 Fe} 0.8 O 3) , and gadolinium (Gd and La), the ceria (gadolinium doped ceria, hereinafter, 'GDC' doped) (Gd _{0 0 .8 .2} Ce ₂ O) It is formed of LSCF / GDC cermet.

In order to manufacture the unit cell 1, first, a process of manufacturing CeScSZ powder of nanoparticles is performed to form the electrolyte 20. The CeScSZ powder is prepared using a co-precipitation method and a hydro thermal synthesis method. In addition, the manufacturing process of the unit cell 1 includes a process of forming a cathode support-type electrolyte composed of the anode 10 and the electrolyte 20 and a process of forming the cathode 30 on the anode support-type electrolyte. Is done. Here, the anode support type electrolyte is formed by continuously forming and simultaneously baking the anode 10 and the electrolyte 20 using a tape casting method. The unit cell 1 is formed by forming and firing the cathode 30 on the anode support-type electrolyte formed as described above.

First, with reference to FIG. 1, the manufacturing method of CeScSZ powder of nanoparticles is demonstrated.

First, zirconium oxychloride (Zirconium Oxychloride, ZrOCl ₂ ), scandium oxide (Scandium Oxide, Sc ₂ O ₃ ) and cerium oxide (Cerium Oxide, Ce ₂ O ₃ ) are mixed with distilled water to form a mixed solution (S11). For example, the mixed solution is zirconium oxychloride _{(Zirconium Oxychloride Formula, ZrOCl 2?} 8H 2 O) 89mole% nitric acid scandium _{(Scandium Nitrate, Sc (NO 3} ) 3? 6H 2 O) 10mole% and cerium nitrate (Cerium Nitrate , Ce (NO ₃ ) _{3 ~} 6H ₂ O) 1mole% is mixed in a fixed amount of distilled water and stirred to mix well.

Next, in order to form a precipitate in the mixed solution by adding a precipitating agent (S12) to precipitate (S13). As the precipitant, ammonium hydroxide (NH ₄ OH) or sodium hydroxide (NaOH) may be used. For example, ammonium hydroxide is prepared by diluting it five times in distilled water, and adding to the stirred mixture to stir to form a precipitate.

Next, the precipitate is recovered from the second mixed liquid in the mixed liquid in which the precipitate is formed as described above (S14). In this example, a filtration method was used to recover the precipitate. The mixed solution in which the precipitate is formed is poured into a reactor equipped with filter paper, and the filter paper is passed through the filter paper. Here, the container is washed by putting distilled water 5 to 6 times in the container containing the mixed solution, wherein the degree of cleaning of the container is a small amount of silver nitrate solution (silver nitrate) to the sample collected through the filter paper solution, AgNO ₃ ) After the addition of silver chloride (AgCl) precipitation reaction does not occur, the washing is completed.

Next, the filtered precipitate is subjected to hydro thermal synthesis (S15). The hydrothermal synthesis was stirred for about 18 hours at a speed of 120 rpm at 180 ° C.

Next, to dry the precipitate, the hydrothermal synthesis is completed (S16). For example, the precipitate is dried for about 6 hours at 100 to 120 ℃.

And the dried precipitate is heat treated at about 550 ~ 950 ℃ for 2 hours to check the structure and physical properties of the CeScSZ powder.

CeScSZ powder prepared by performing co-precipitation and hydrothermal synthesis at the same time as described above, as shown in Figures 5 and 6, the particle size of 1 to 10nm, specific surface area of 250 to 300 cm 2 / g Powders can be prepared.

Next, a method of forming the anode support-type electrolyte using the CeScSZ powder of the nanoparticles prepared as described above will be described with reference to FIG. 2.

First, NiO and YSZ are mixed to form a first NiO / YSZ slurry, and the first NiO / YSZ slurry is tape cast to form a sheet for a fuel electrode support (NiO / YSZ / CB) (S21). The first NiO / YSZ slurry is formed by mixing NiO and YSZ at 60:40, adding 10 wt% of carbon black as a pore agent, and adding a solvent, a dispersant, and a binder. The anode support sheet is formed to a thickness of 35 to 45㎛.

Next, NiO and YSZ are mixed to form a second NiO / YSZ slurry, and the second NiO / YSZ slurry is tape cast to form a cathode reaction layer sheet (NiO / YSZ) having a thickness of 10 to 30 μm. (S22). The second NiO / YSZ slurry is formed by adding 10 wt% carbon black, a solvent, a dispersant, and a binder as a pore agent to NiO and YSZ, similar to the first NiO / YSZ slurry, except that the second NiO The / YSZ slurry is formed by mixing NiO and YSZ in a ratio of 55:45, unlike the first NiO / YSZ slurry.

Next, in order to form the electrolyte 20, a CeScSZ slurry of nanoparticles is formed (S23). Herein, the particles of the nano CeScSZ powder are manufactured by coprecipitation and hydrothermal synthesis, have a particle size of 1 to 10 nm, and a specific surface area of 100 to 300 m 2 / g. The CeScSZ slurry is formed by mixing a solvent, toluene, ethanol, a dispersant, and a binder in CeScSZ powder of nanoparticles. In addition, the CeScSZ slurry may be stirred and prevented from agglomeration of CeScSZ particles by using a ball mill and an ultrasonic wave.

Next, the CeScSZ slurry is tape cast to form an electrolyte sheet (S24). For example, the electrolyte sheet may be formed to a thickness of 5 to 10㎛.

Next, the anode support layer sheet, the anode reaction layer sheet, and the electrolyte sheet are sequentially stacked and laminated (S25). For example, 30 to 60 sheets of the anode support layer sheet are laminated so that the anode support layer 11 is formed to 1 to 2 mm, one sheet of anode reaction layer sheet is laminated on the anode support layer, and the anode reaction layer sheet is formed. One sheet of electrolyte is laminated on the substrate. The lamination step is to press the laminated stack as described above at a predetermined temperature to ensure that the sheets are adhered to each other to prevent peeling from each other, in particular, the fuel electrode 10 and the electrolyte 20 is peeled off each other. prevent. For example, the lamination step pressurizes the laminate at a load of 400 kg _f / cm 2 at a temperature of 60 to 90 ° C. (eg, 70 ° C.) for approximately 30 minutes.

Next, a calcination step is performed to remove components such as solvent, binder, pore agent and dispersant from the laminate having completed lamination (S26). Here, the calcination step may be carried out step by step according to the characteristics of each component contained in the slurry. For example, in order to remove the solvent, binder and carbon, the temperature is gradually raised to 1000 ° C., and heat-treated at 1000 ° C. for 3 hours to remove carbon black, which is a pore agent. In this case, when the calcination is performed at 1000 ° C. or less, breakage is likely to occur due to poor plasticity, and when the calcination temperature is higher than 1000 ° C., the bending of the laminate occurs severely in the calcination step, so that 1000 is performed in the calcination step. At a temperature near < RTI ID = 0.0 >

Next, by firing the laminate in which the calcination step is completed to form a fuel cell support electrolyte (S27). For example, the laminate is fired at about 1350 ° C. Here, in order to prevent defects such as warpage and cracks from occurring in the firing step, firing is performed in a pressurized state by applying a predetermined load to the laminate. For example, pressure may be applied by placing a pressing body having a constant size and weight on the upper and lower portions of the laminate. The pressurized body may pressurize the laminate at 35 to 40 kg _f / cm 2. Here, the press body is stable so as not to chemically react with the laminate in the firing step, the press body is formed of a material that does not cause physical or chemical deformation, it may be formed of a ceramic material such as zirconia. In addition, the press body may have a flat plate or block shape corresponding to the laminate so as to uniformly press the laminate.

The CeScSZ powder prepared by the above-described method is fine in particle size, so that the thickness of the electrolyte 20 can be thinned and the surface area is increased. Therefore, the electrolytic material 20, the anode 10, and the cathode 30 are formed. The interfacial contact area between them can be increased. This improves the output performance of the solid oxide fuel cell by reducing the resistance at the interface between the electrolyte 20, the anode 10, and the cathode 30.

Next, a method of manufacturing the cathode 30 and the unit cell 1 will be described with reference to FIG. 3. The cathode 30 is formed by firing the cathode 30 on the anode support-type electrolyte formed by the above-described method.

First, in order to form the cathode 30, a slurry is formed using an LSCF / GDC cermet in which LSCF and GDC are mixed (S31). The LSCF / GDC slurry is formed by mixing LSCF and GDC at 60:40.

Next, the LSCF / GDC slurry is coated on the electrolyte 20 in the anode support type electrolyte to form the cathode 30 (S32). Here, the cathode 30 is coated with the LSCF / GDC slurry on the electrolyte 20 using a screen printing method, for example, the cathode 30 is approximately 50㎛ thickness so that the LSCF / GDC It can be formed by printing the slurry three times.

Next, the anode support type electrolyte in which the cathode 30 is formed is fired to form a unit cell 1 (S33). For example, the unit cell 1 is fired at 1100 to 1200 ℃.

According to embodiments of the present invention, the anode 10 and the anode-supported electrolyte of the plate-type solid oxide fuel cell may be manufactured using a tape casting method. In addition, since the anode support type electrolyte is formed by the continuous tape casting method and co-firing, the firing process of the anode can be omitted, thereby reducing process time and cost and improving productivity.

In addition, the CeScSZ slurry of the nanoparticles may be formed and the thin film electrolyte 20 may be formed, thereby improving performance of the unit cell 1. As the thickness of the electrolyte 20 becomes thinner, the ohmic resistance and the polarization resistance decrease as the moving distance of oxygen ions decreases in the electrolyte 20, and the contact between the electrolyte 20 and the fuel electrode 10 is reduced. By improving the performance and reactivity, the performance of the unit cell 1 can be improved.

Hereinafter, the performance test results according to the embodiments of the present invention will be briefly described with reference to FIGS. 7 and 8. For reference, FIG. 7 is a graph showing the output of the unit cell of the solid oxide fuel cell according to an embodiment of the present invention, Figure 8 is a graph showing the resistance of the unit cell.

First, in order to evaluate the performance of a unit cell according to embodiments of the present invention, a flat unit cell was manufactured by a tape casting method using the nanoparticle CeScSZ powder according to the above-described method. In the embodiment, using a nano CeScSZ powder having a particle size of 5 to 10 nm and a specific surface area of 100 to 150 m 2 / g, the electrolyte and the anode were simultaneously baked at 1350 ° C. by a continuous tape casting method to prepare a cathode support-type electrolyte. In addition, LSCF and GDC were mixed at 60:40 on the calcined electrolyte, and a unit cell was manufactured by firing an air electrode having a thickness of approximately 50 μm at 1100 ° C. by a screen printing method.

Comparative Example 1 forms an anode-supported electrolyte in the same manner as in Example, except that the electrolyte is formed using a commercially available YSZ powder having a particle size of 150 nm or more and a specific surface area of 4 to 8 m 2 / g instead of the nano CeScSZ powder. It was formed and co-fired with the anode to form an anode support type electrolyte. The LSM and YSZ were mixed 1: 1 in the anode support-type electrolyte formed as described above to form a cathode having a thickness of about 50 μm, and then fired at 1350 ° C. to form a unit cell.

Comparative Example 2 forms a cathode support type electrolyte and a unit cell in the same manner as in Example, but forms an electrolyte using commercially available CeScSZ powder having a particle size of 150 nm or more and a specific surface area of 4 to 8 m 2 / g when forming the electrolyte. And co-fired with the anode to form a cathode support-type electrolyte. In addition, LSCF and GDC were mixed at 60:40 on the anode support-type electrolyte formed as described above to form a cathode having a thickness of about 50 μm, and then fired at 1350 ° C. to form a unit cell.

In order to evaluate the unit cells according to Examples and Comparative Examples 1 and 2, hydrogen (H ₂ ) containing 3% water (H ₂ O) at 800 ° C. was flowed through the anode at a rate of 200 ml / min, and air was 300 ml. The current voltage (IV) curve of the unit cell was measured while flowing through the air electrode at a rate of / min, and at the same time, the ohmic resistance of the electrolyte by impedance measurement in the open circuit state was measured. The current voltage curves of the unit cells according to the example and the comparative example are shown in FIG. 7, and the ohmic resistance is shown in FIG. 8.

Referring to FIG. 7, the output performance of the unit cell according to the embodiment is 0.97W / cm 2, which is about 2 times or more than 0.46W / cm 2 of Comparative Example 1 and about 3 times or more that of 0.26W / cm 2 of Comparative Example 2 You can see that the output is high. Referring to FIG. 8, the impedance measurement result of the unit cell according to the embodiment shows that the ohmic resistance is 0.035Ωcm 2, and that the ohmic resistance is reduced compared to 0.06Ωcm 2 of Comparative Example 1 and 0.13Ωcm 2 of Comparative Example 2. have. In this embodiment, the electrolyte is formed of CeScSZ powder of nanoparticles so that the thickness of the electrolyte is thin and defects such as pin-holes or cracks in the electrolyte are prevented, and the anode (NiO / YSZ) and the cathode (LSCF / GDC) are prevented. Since the contact area is sufficiently secured at the interface with), the transfer resistance of oxygen ions from the air electrode at the interface to the electrolyte layer is significantly suppressed and the reaction field is enlarged, thereby improving output performance.

As described above, the present invention has been described by specific embodiments such as specific components and the like, but the embodiments and the drawings are provided only to help a more general understanding of the present invention, and the present invention is limited to the above-described embodiments. In other words, various modifications and variations are possible to those skilled in the art to which the present invention pertains. Therefore, the spirit of the present invention should not be limited to the above-described embodiment, and all the things that are equivalent to or equivalent to the scope of the claims as well as the claims to be described later belong to the scope of the present invention.

1 is a flow chart illustrating a method of manufacturing a cathode support type electrolyte according to an embodiment of the present invention;

2 is a flowchart illustrating a method of manufacturing a cathode support-type electrolyte according to an embodiment of the present invention;

3 is a flowchart illustrating a method of manufacturing a unit cell of a solid oxide fuel cell according to an embodiment of the present invention;

4 is a schematic cross-sectional view of a unit cell of a solid oxide fuel cell according to an embodiment of the present invention;

5 and 6 are images of CeScSZ powder prepared by the method of FIG. 1;

7 and 8 are graphs showing the performance test results of the unit cell of the solid oxide fuel cell according to an embodiment of the present invention, Figure 7 is a graph showing the output of the unit cell, Figure 8 is a resistance of the unit cell It is a graph showing.

<Explanation of symbols for the main parts of the drawings>

1: Unit cell of solid oxide fuel cell

10: anode 11: anode support layer

12: anode reaction layer 20: electrolyte

30: air electrode

Claims (13)

Mixing zirconium oxychloride (Zirconium Oxychloride, ZrOCl ₂ ), scandium oxide (Scandium Oxide, Sc ₂ O ₃ ), and cerium oxide (Cerium Oxide, Ce ₂ O ₃ ) in distilled water to form a mixed solution; Mixing and precipitating the precipitant in the mixed solution; Filtering the precipitate out of the mixture; Hydrothermal synthesis of the filtered precipitate; Drying the precipitate in which the hydrothermal synthesis is completed; And Heat treating the dried precipitate to prepare cerium-dopped Scandium Stabilized Zirconia (CeScSZ) powder; Cerium-added scandium stabilized zirconia powder manufacturing method comprising a. The method of claim 1, The CeScSZ powder is a cerium-added scandium stabilized zirconia powder having a particle size of 1 to 10nm, surface area of 100 to 300cm 2 / g. The method of claim 1, The mixed solution is zirconium oxychloride (ZrOCl ₂ ~ 8H ₂ O), scandium nitrate (Scandium Nitrate, Sc (NO ₃ ) _{3 ~} 6H ₂ O) and cerium nitrate (Cerium Nitrate, Ce (NO ₃ ) _{3 ~} 6H ₂ O) Method for producing a cerium-added scandium stabilized zirconia powder formed by mixing. Mixing nickel oxide (NiO) and YSZ to form a first slurry; Forming a anode support layer sheet using the first slurry; Mixing NiO and YSZ to form a second slurry; Forming a cathode reaction layer sheet using the second slurry; Claim 1 to claim 3 to form a CeScSZ slurry using the CeScSZ powder prepared by the manufacturing method according to any one of claims; Forming an electrolyte sheet using the CeScSZ slurry; Sequentially stacking and laminating the anode reaction layer sheet and the electrolyte sheet on the anode support layer sheet to form a laminate; Calcination step for removing the solvent and binder from the laminate; And Firing the laminate in which the calcining is completed; Unit cell manufacturing method of a solid oxide fuel cell comprising a. 5. The method of claim 4, The CeScSZ powder has a particle size of 1 to 10 nm, a specific surface area of 100 to 300 m 2 / g unit cell manufacturing method of a solid oxide fuel cell. The method of claim 5, The electrolyte sheet is formed to a thickness of 5 to 10㎛, the electrolyte is a unit cell manufacturing method of a solid oxide fuel cell in which one sheet of the electrolyte sheet is laminated on the anode reaction layer sheet. 5. The method of claim 4, Forming an LSCF / GDC slurry mixed with lanthanum strontium cobalt ferrite (LSCF) and gadolinium doped ceria (GDC); Forming an air electrode using an LSCF / GDC slurry on an electrolyte in the calcined laminate; And Firing the laminate and the air electrode; Unit cell manufacturing method of a solid oxide fuel cell further comprising. The method of claim 7, wherein The cathode is a unit cell manufacturing method of a solid oxide fuel cell in which the LSCF and the GDC are mixed in a weight ratio of 60:40. An anode support layer formed of NiO / YSZ cermet mixed with NiO and YSZ; A cathode reaction layer formed of NiO / YSZ cermet and stacked on the anode support layer; And An electrolyte formed by using CeScSZ of the nanoparticles prepared by the manufacturing method according to any one of claims 1 to 3 and laminated on the anode reaction layer; And the anode support layer, the anode reaction layer, and the electrolyte are co-fired. 10. The method of claim 9, The CeScSZ powder is formed of a powder having a particle size of 1 to 10 nm and a specific surface area of 100 to 300 m 2 / g by coprecipitation and hydrothermal synthesis, and the electrolyte has a thickness of 1 to 5 μm for a solid oxide fuel cell. Anode support type electrolyte. A fuel cell support type electrolyte formed by the manufacturing method according to claim 9; And An air electrode formed of a LSCF / GDC cermet in which LSCF and GDC are mixed and stacked on the anode support type electrolyte; Unit cell of a solid oxide fuel cell comprising a. The method of claim 11, The anode support layer is formed of a stack of 30 to 60 NiO / YSZ sheet having a thickness of 35 to 45㎛, The anode reaction layer is a unit cell of a solid oxide fuel cell in which one sheet of NiO / YSZ sheet having a thickness of 10 to 30㎛ is laminated. The method of claim 11, The cathode is a unit cell of a solid oxide fuel cell in which the LSCF and the GDC are mixed in a weight ratio of 60:40.

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