KR101685386B1 - Anode Supported Solid Oxide Fuel Cell by using low temperature co-firing and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an anode-supported solid oxide cell and a method for manufacturing the same, wherein an oxide layer having a large sintering shrinkage ratio and a laminate including a mixed layer for alleviating a difference in stress between layers are simultaneously sintered to improve the density of the electrolyte layer According to the present invention, it is possible to simplify the process of manufacturing a single cell by simultaneously sintering at a low temperature, to ensure the flexibility of the fuel electrode composition and to enable the use of the fuel electrode substrate having a high shrinkage ratio, And it is possible to prevent the thermal stress concentration phenomenon at the interface by the introduction of the mixed layer to prevent the warping of the cell and the destruction of the cell after the simultaneous sintering so that the anode supporting solid body having improved electrochemical performance and long- Oxide cell can be provided and commercialized.

Description

Technical Field [0001] The present invention relates to an anode-supported solid oxide cell and a method for manufacturing the anode-supported solid oxide cell by low-temperature co-

More particularly, the present invention relates to a fuel electrode substrate layer having a high sintering shrinkage ratio and a multilayer body including a mixed layer for alleviating the difference in stress between the anode and the cathode, Thereby improving the denseness of the electrolyte layer, and a method of manufacturing the solid oxide fuel cell.

A solid oxide fuel cell (SOFC) is a highly efficient, environmentally friendly electrochemical power generation technology that directly converts the chemical energy of a fuel gas into electrical energy. The solid oxide fuel cell uses an ionic conductive solid oxide as an electrolyte.

There are various types of designs in SOFC. Among them, in the anode-supported design, by decreasing the thickness of the electrolyte layer having the lowest electrical conductivity among the various components, the resistance of the whole cell is reduced. .

The single cell is composed of an electrolyte having oxygen ion conductivity, and a fuel electrode and an air electrode provided on both sides of the electrolyte. The electrolyte and the electrode, which are the basic elements constituting the electrolyte, and the electrode are all made of ceramics having excellent heat resistance. It has superior efficiency and performance as compared with the low temperature type fuel cell and the electrolytic cell. However, there is a problem that various deterioration phenomena which are caused by exposure to a high temperature for a long time during the manufacture and operation of a unit cell, that is, a chemical reaction between a cathode layer and an electrolyte layer forms an insulator reactant at the interface to increase the resistance and decrease the performance of the cell There was a difficulty in commercialization. In order to suppress such a chemical reaction, a ceria-based reaction preventing layer such as Gadolinia doped ceria (GDC) and Samaria doping ceria (SDC) is introduced between the electrolyte layer and the air electrode layer (Patent Document 1).

In a conventional process for manufacturing an anode-supported single cell, a Yttria-Stabilized Zirconia (YSZ) electrolyte layer is coated on a nickel oxide-yttria stabilized zirconia (NiO-YSZ) The anode and the electrolyte layer were simultaneously sintered, and then the cerium-based reaction-preventing layer was coated on the electrolyte layer, and the reaction-preventing layer was formed by post-sintering at 1200-1250 ° C.

However, the above-described manufacturing process has a disadvantage in that a plurality of sintering processes are performed, which complicates the process, increases the process cost, and consumes a lot of time for manufacturing a single cell.

In addition, since the fuel electrode and the electrolyte are sintered simultaneously at a high temperature, it is difficult to change the anode composition, that is, the NiO-YSZ composition, which is a composition that can improve the electrochemical performance and increase resistance to carbon deposition, sulfur poisoning, GDC and NiO-SDC react with YSZ electrolyte at high temperature of 1250 ℃ or higher to form a reactant with high electrical resistance. Therefore, it is impossible to utilize it as an anode material in a high-temperature sintering process at 1400 ° C. .

Accordingly, in order to solve the above-mentioned problems, it is necessary to develop a low-temperature co-sintering technique for simplifying the manufacturing process and ensuring flexibility in fuel electrode composition by simultaneously sintering the fuel electrode, the electrolyte layer and the reaction-

Korean Patent Publication No. 10-2013-0099704

The first problem to be solved by the present invention is to provide a fuel electrode supporting solid oxide cell which can reduce the stress difference between layers by introducing a large anode substrate and a mixed layer capable of sintering at a low temperature simultaneously and improving the density of the electrolyte layer .

A second problem to be solved by the present invention is to provide a method of manufacturing the anode-supported solid oxide cell.

In order to solve the first problem,

A fuel cell-supported solid oxide cell comprising a fuel electrode substrate layer, a fuel electrode functional layer, an electrolyte layer, and a reaction layer formed in this order, wherein the stack is formed between the anode functional layer and the electrolyte layer, A first mixed layer for alleviating the first mixed layer; And a second mixed layer formed between the electrolyte layer and the reaction preventive layer to alleviate the stress difference between the layers, and is formed by simultaneous sintering.

According to an embodiment of the present invention, the fuel electrode substrate layer and the anode electrode functional layer may be respectively formed of a mixture of nickel oxide (NiO) and gadolinia doping ceria (GDC) And may be formed by a tape casting method. The pore precursor may be carbon black, graphite or polymethylmethacrylate (PMMA).

According to another embodiment of the present invention, the fuel electrode substrate layer and the anode electrode functional layer may each be formed of a mixture of nickel oxide (NiO) and samarium doped ceria (SDC), and the anode electrode layer further includes a pore precursor And may be formed by a tape casting method. The pore precursor may be carbon black, graphite or polymethylmethacrylate (PMMA).

According to another embodiment of the present invention, the electrolyte layer may be formed of yttria-stabilized zirconia (YSZ).

According to another embodiment of the present invention, the reaction preventing layer may be formed of Gadolinia doping ceria (GDC), Samaria doped ceria (SDC), or a mixture thereof.

According to another embodiment of the present invention, the first mixed layer and the second mixed layer may be formed of a mixture of yttria-stabilized zirconia (YSZ) and gadolinia doped ceria (GDC).

According to another embodiment of the present invention, the first mixed layer and the second mixed layer may be formed of a mixture of yttria stabilized zirconia (YSZ) and samarium doped ceria (SDC).

The electrolyte layer according to the present invention promotes sintering under a compressive stress from the lower fuel electrode substrate layer and the upper reaction preventive layer having a high degree of shrinkage during the simultaneous sintering of the layered product and at the same time the shrinkage ratio And the thermal stress due to the difference is alleviated.

In order to solve the second problem,

(a) fabricating a fuel electrode substrate layer by tape casting; (b) forming a layered product in which the anode functional layer, the first mixed layer, the electrolyte layer, the second mixed layer, and the anti-reaction layer are coated in this order on the prepared fuel electrode substrate layer; And (c) simultaneously sintering the laminate to produce a fuel electrode-supported type of reversed biosensor.

During the simultaneous sintering in the step (c) of the present invention, the electrolyte layer is subjected to compressive stress from the lower fuel electrode substrate layer and the upper reaction preventive layer having a large shrinkage rate, and sintering is promoted, and the first and second mixed layers And the thermal stress due to the difference in shrinkage percentage is alleviated.

According to an embodiment of the present invention, the step (c) comprises the steps of: (i) heating at 150-250 ° C for 1-7 hours, at 300-400 ° C for 3-4 hours and at 500-700 ° C for 3-4 hours Respectively; (Ii) heat treatment at 800-900 占 폚 for 1-2 hours; And (iii) annealing at 1150-1250 ° C for 4-5 hours.

According to the present invention, it is possible to simplify the process of manufacturing a single cell by simultaneously sintering at a low temperature, to secure flexibility of fuel electrode composition and to enable use of a fuel electrode substrate having a high shrinkage ratio, thereby improving the density of the electrolyte layer . In addition, since the introduction of the mixed layer can relieve the thermal stress concentration phenomenon at the interface and prevent the flexural appearance, crack and cell breakage of the cell after the simultaneous sintering, it is possible to improve the electrochemical performance and long- And commercialization.

1 is a view showing a structure of a half-cell fabricated according to an embodiment of the present invention.
2 is a graph comparing sintering shrinkage behaviors of NiO-GDC produced by YSZ, GDC, tape casting method and NiO-GDC produced by compaction molding according to Experimental Example 1. FIG.
3 is a photograph of the sintered solid oxide cell produced according to the comparative example.
4 is a photograph of a solid oxide cell manufactured according to an embodiment of the present invention after sintering.
5 is a scanning electron microscope (SEM) photograph of a cross section of a cell fabricated in accordance with an embodiment of the present invention.
FIG. 6 is a graph plotting the conditions of the simultaneous sintering process optimized (temperature and time) in the method of producing the solid oxide cell according to the present invention.

Hereinafter, the present invention will be described in more detail.

In a general anode-supported single cell manufacturing process, a Yttria-Stabilized Zirconia (YSZ) electrolyte layer is coated on a nickel oxide-yttria stabilized zirconia (NiO-YSZ) fuel electrode substrate, And an electrolyte layer were simultaneously sintered. Then, a ceria-based reaction preventive layer was coated on the electrolyte layer, and the reaction inhibition layer was formed by sintering at 1200-1250 ° C.

However, the above-described manufacturing process has a disadvantage in that a plurality of sintering processes are performed, which complicates the process, increases the process cost, and consumes a lot of time for manufacturing a single cell.

In addition, since the fuel electrode and the electrolyte are sintered simultaneously at a high temperature, it is difficult to change the anode composition, that is, the NiO-YSZ composition, which is a composition that can improve the electrochemical performance and increase resistance to carbon deposition, sulfur poisoning, GDC and NiO-SDC react with YSZ electrolyte at high temperature of 1250 ℃ or higher to form a reactant with high electrical resistance. Therefore, it is impossible to utilize it as an anode material in a high-temperature sintering process at 1400 ° C. .

Accordingly, the inventors of the present invention have made it possible to simultaneously sinter the fuel electrode, the electrolyte layer, and the reaction preventive layer by introducing a fuel electrode substrate layer capable of sintering at a low temperature and having a high sintering shrinkage ratio, In order to alleviate the concentration of thermal stress due to the difference in shrinkage ratio, the present invention was derived by optimizing the composition and process conditions of each layer while introducing a mixed layer.

The anode-supported solid oxide cell according to the present invention includes a cathode layer formed on the upper reaction preventing layer and including a half-cell made of a laminate formed in the order of a fuel electrode substrate layer, an anode functional layer, an electrolyte layer, and an anti-reaction layer.

The laminate is formed by simultaneous sintering and is formed between the electrolyte layer and the reaction prevention layer formed between the anode functional layer and the electrolyte layer to alleviate the stress difference between the layers and mitigates the stress difference between the layers And a second mixed layer for providing a second mixed layer.

FIG. 1 is a view illustrating a structure of a half cell fabricated according to an embodiment of the present invention. Referring to FIG. 1, a half cell 100 constituting an anode-supported solid oxide cell of the present invention includes a fuel electrode substrate layer 10, The functional layer 20, the electrolyte layer 40 and the reaction preventing layer 60. The first mixed layer 30 is further provided between the anode functional layer 20 and the electrolyte layer 40 as described above, And a second mixed layer 50 is further formed between the electrolyte layer 40 and the reaction preventing layer 60.

The fuel electrode substrate layer 10 and the anode electrode functional layer 20 serve to facilitate the battery chemical reaction and the reaction of the fuel and to transfer the charge and are chemically stable and have a thermal expansion coefficient similar to that of the material forming the electrolyte layer 40 Is preferably used. In a conventional anode-supported solid oxide cell, a mixture (NiO-YSZ) of nickel oxide (NiO) and yttria-stabilized zirconia (YSZ) as a material of the fuel electrode substrate layer 10 and the anode function layer 20 (NiO-GDC) or nickel oxide (NiO) as a material having enhanced electrochemical performance and improved resistance to carbon deposition, sulfur poisoning, etc. as a material of nickel oxide (NiO) and gadolinia doped ceria (NiO-SDC) of NiO and Samarium Doped Ceria (SDC) was replaced with a material of the anode substrate layer 10 and the anode electrode functional layer 20. At this time, the fuel electrode substrate layer 10 and the anode electrode functional layer 20 may further include a solvent, a plasticizer, a dispersant, and the like, and the composition thereof is the same. However, And a pore precursor was formed at the time of formation so that the gas reaction inside the fuel electrode could sufficiently occur after sintering. At this time, it is preferable that the pore precursor is carbon black, graphite or polymethylmethacrylate (PMMA).

The electrolyte layer 40 should have a high density so that air and fuel are not mixed with each other, have high oxygen ion conductivity and low electron conductivity. Since there is a very large oxygen partial pressure difference on both sides of the electrolyte layer, It is necessary to maintain physical properties. For this, the material constituting the electrolyte layer 40 is preferably a zirconia-based metal oxide generally used in the related art, and more preferably is yttria-stabilized zirconia (YSZ).

The reaction preventive layer 60 prevents the chemical reaction occurring when the electrolyte layer 40 and the cathode layer are in contact with each other to prevent deterioration of performance and thermomechanical stability of the unit cell. It is preferable that the metal oxide is Gadolinia doped ceria (GDC), Samaria doped ceria (SDC), or a mixture thereof.

The first mixed layer 30 and the second mixed layer 50 are introduced to minimize the concentration of thermal stress due to the difference in shrinkage ratio between the upper and lower layers of the electrolyte layer 40, And serves as a buffer between the electrolyte layer 40 and the reaction preventive layer 60 to prevent the shrinkage rate from rapidly varying, thereby preventing thermal stress from concentrating on the interface. At this time, the material constituting the first mixed layer 30 and the second mixed layer 50 may be a mixture of yttria stabilized zirconia (YSZ) and gadolinia doped ceria (GDC) or yttria stabilized zirconia (YSZ) Ceria (SDC). In order to maximize the buffering function, it is most preferable that the composition ratio is 1: 1.

In the case of a half-cell including the stacked body in which the above-described constitution is sequentially formed, the stacked body is formed by the simultaneous sintering process at a low temperature of 1250 캜 or less, which simplifies the process. In addition, the present invention uses a fuel electrode substrate layer produced by a tape casting method, which has a high sintering shrinkage ratio, to cause compressive stress to be applied from the anode electrode substrate and the reaction preventive layer above the electrolyte layer in the simultaneous sintering, Is improved. Also, a mixed layer was introduced as described above in order to prevent warpage and cracking and destruction of the cell due to a large thermal stress gradient between the layers.

That is, the electrolyte layer 40 according to the present invention is subjected to compressive stress from the lower fuel electrode substrate layer 10 and the upper reaction preventing layer 60 having a large shrinkage ratio during simultaneous sintering of the laminate, The first mixed layer 30 and the second mixed layer 50 are characterized in that the thermal stress due to the difference in shrinkage ratio between layers is relaxed.

Further, the anode-supported oxide cell according to the present invention is manufactured by applying a cathode layer on the reaction preventing layer 60 constituting the above-described reversal paper 100 and then sintering it.

At this time, the material of the cathode layer is not particularly limited as long as it can be generally used in the related art, for example, a metal oxide having a perovskite structure can be used. The metal oxide of the perovskite structure is a mixed conductor material having both ionic conductivity and electron conductivity and has a high oxygen diffusion coefficient and a charge exchange rate coefficient so that the electrochemical reaction occurs not only at the three- The electrode activity at low temperature is excellent and can contribute to lowering the operating temperature of the solid oxide cell. The anode-supported solid oxide cell according to the present invention can use a perovskite-type metal oxide containing lanthanum (La), cobalt (Co) and iron (Fe) as a material of the cathode layer, It is preferable to have porosity.

The present invention also relates to a method of manufacturing the anode-supported solid oxide cell described above, which comprises the following steps.

(a) manufacturing an anode substrate layer by a tape casting method,

(b) fabricating a layered product in which the anode functional layer, the first mixed layer, the electrolyte layer, the second mixed layer, and the reaction inhibiting layer are coated in this order on the prepared fuel electrode substrate layer,

(c) simultaneously sintering the laminate to produce anode supporting type reversed semi-

(d) applying an air electrode on the upper reaction preventing layer of the anode supporting type of the reverse electrode and then sintering.

The fuel electrode substrate layer is prepared by a tape casting method to improve the sintering shrinkage ratio. The stacked body is coated on the anode substrate layer in the order of the anode functional layer, the first mixed layer, the electrolyte layer and the reaction preventive layer, .

At this time, the coating is performed by a thin film coating method selected from among screen printing, chemical vapor deposition, electrochemical vapor deposition and sputtering, and a series of operations consisting of coating and drying from the anode substrate layer to the air electrode layer are successively performed Go ahead.

In the simultaneous sintering, the laminate is sintered, and the electrolyte layer is subjected to compressive stress from the lower fuel electrode substrate layer and the upper reaction preventive layer having a large shrinkage ratio, and sintering is promoted. At the same time, the first mixture layer and the second mixture layer The thermal stress due to the difference in shrinkage rate between the layers is relaxed.

Specifically, the simultaneous sintering process includes: (i) heat-treating at 150-250 ° C for 1-7 hours, at 300-400 ° C for 3-4 hours, and at 500-700 ° C for 3-4 hours; (Ii) heat treatment at 800-900 占 폚 for 1-2 hours; And (iii) heat treatment at 1150-1250 ° C for 4-5 hours.

At this time, the organic material contained in the half-cell is removed through step (i), and heat treatment is performed for about 1-2 hours through step (ii) in the vicinity of 800 ° C where initial shrinkage of the fuel electrode substrate layer produced by the tape- It can circulate interfacial stress between layers and prevent interfacial peeling. The final sintering temperature is set at 1230 ° C, which is the result of the interfacial reaction between YSZ and GDC at a temperature of 1250 ° C or higher, impairing performance and thermomechanical stability. .

In addition, since the interface between the respective layers must have a sufficient bonding force, the stress generated between the adjacent layers can be easily transferred, so that it is preferable to perform an additional pressing process so that mutual penetration of the powder particles in the adjacent layer can occur.

Therefore, when various conditions of the embodiments to be described later are satisfied, the effect to be realized by the present invention can be derived.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments and the like. It will be apparent to those skilled in the art, however, that these examples are provided for further illustrating the present invention and that the scope of the present invention is not limited thereto.

Example  1. According to the invention Anode  Of the support type solid oxide cell Half  Produce

First, a tape casting process was used to produce a fuel electrode substrate having a high electron conductivity and high sintering shrinkage ratio while serving as a mechanical support for a unit cell. The composition of the anode substrate layer is shown in Table 1 below. NiO powder, Gadolinium doped ceria powder and pore precursor powder (PMMA 5 탆) were used for slurry preparation. In order to prevent agglomeration between powders, relatively small GDC NiO, and PMMA, and then ball milled. At this time, the pore precursor was added to form pores in the fuel electrode substrate layer to facilitate gas movement. In addition, the dispersant was added together with different amounts of the particles according to the size of the particles, and the mixture was subjected to ball milling for 24 hours, followed by addition of a plasticizer and a binder, followed by further mixing for 24 hours Respectively. Using the slurry thoroughly mixed through the above process, a tape having a thickness of about 120 탆 is prepared and laminated to finally have a thickness of about 1.2 mm. For lamination, they were pressed at 80 캜 and 15 MPa for about 3 minutes.

Then, the anode active layer (NiO-GDC), the first mixed layer (YSZ-GDC), the electrolyte layer (YSZ), the second mixed layer (YSZ-GDC) (GDC) are sequentially coated by a screen printing process. The compositions are shown in the following Tables 2 to 5 (Table 2 shows the anode functional layer, Table 3 shows the first and second mixed layers, and Table 4 shows the electrolyte layer , Table 5 shows the reaction inhibition layer).

In preparing the pastes of the anode function layer, the electrolyte layer, the reaction preventive layer and the mixed layer having the compositions shown in Tables 2 to 5, only the solvent and the dispersant are added first and then milled for one hour to dissolve the powdery dispersant in the solvent. At this time, α-terpineol was used as a solvent, and the amount of the dispersant was determined based on the particle size of the powder, and 2-3 wt% of the powder was added. When the solvent in which the dispersant is melted is completely dissolved, the powder is added. To prevent agglomeration of the powder, initially 50% of the total amount is added and 25% is added at intervals of 2 hours. The resulting solution is thoroughly mixed for 12 hours, then the binder and plasticizer are added and mixed thoroughly for 24 hours.

The paste prepared by the above method was screen-printed on the anode substrate layer in order, and the cells that had been screen-printed were dried in an oven at 60 ° C.

Next, the laminate formed in the above order was sintered by the simultaneous sintering process designed as shown in Fig.

First, heat treatment was performed at 200 ° C, 350 ° C, and 600 ° C for 6 hours, 3 hours, and 3 hours, respectively, in order to remove the organic substances contained in the secondary battery.

Next, as shown in FIG. 2, since the initial shrinkage of the anode substrate layer produced by the tape casting method starts at about 800 DEG C, in order to alleviate the interface stress between the constituent layers and prevent the interface delamination from occurring, Lt; / RTI > for 1 hour to allow slow shrinkage to occur.

Next, at a high temperature of 1250 ° C. or higher, the performance and thermomechanical stability owing to the interfacial reaction between YSZ and GDC may be lowered. Therefore, the final sintering temperature is set at 1230 ° C. and the upper and lower layers of the electrolyte layer In order to accelerate the densification of the electrolyte layer by using compressive stress, the holding time was given for 4 hours. During cooling, slow cooling was performed to minimize microcracks and thermal shock due to difference in thermal expansion coefficient between the respective interfaces.

Slurry composition Content (g) NiO 69.50 GDC 65.35 PMMA 15.16 Ethanol 51.83 Toluene 37.92 Dispersant 3.68 Plasticizer 12 Binder 13.5

Electrode composition Content (g) NiO 25.7 GDC 24.3 alpha-terpineol 25 Dispersant One Plasticizer 2 bookbinder One

Electrode composition Content (g) YSZ 10 GDC 12.01 alpha-terpineol 16 Dispersant 0.44 Plasticizer 0.88 bookbinder 0.44

Electrode composition Content (g) YSZ 97 Nano YSZ 3 alpha-terpineol 75 Dispersant 3 Plasticizer 8 bookbinder 4.5

Electrode composition Content (g) GDC 50 alpha-terpineol 36.15 Dispersant 2 Plasticizer 4 bookbinder 2

Example  2. According to the present invention Anode  Preparation of Supported Solid Oxide Cells

An anode was screen-printed on the upper reaction preventing layer of the semi-conductive paper prepared in Example 1, and then heat-treated to prepare the anode-supported solid oxide cell according to the present invention.

Comparative Example . Excluding the mixed layer Anode  Preparation of Supported Solid Oxide Cells

An anode-supported solid oxide cell was produced by the same method and sintering conditions as in Examples 1 and 2, except that the first mixed layer and the second mixed layer were not introduced.

Experimental Example  One. YSZ , GDC , A tape casting method NiO - GDC  And Compaction  Molded NiO - GDC Confirmation of sintering shrinkage behavior of

2 is a graph comparing sintering shrinkage behavior of NiO-GDC produced by YSZ, GDC, tape casting method and NiO-GDC produced by compaction molding.

As a result, it can be seen that the sintering shrinkage ratio of the NiO-GDC anode substrate is significantly increased when the NiO-GDC anode substrate is produced by the tape casting method, rather than when it is produced by the compaction molding. Also, it can be seen that the shrinkage ratio of the GDC reaction preventing layer formed on the YSZ electrolyte layer is higher than that of the YSZ electrolyte layer.

Therefore, when the NiO-GDC anode substrate manufactured by the tape casting method is used to simultaneously sinter the electrode according to the present invention, the NiO-GDC anode substrate and the upper GDC reaction preventive layer having a large shrinkage ratio in the YSZ electrolyte layer generate compressive stress The sintering is promoted and the density of the electrolyte layer can be improved.

Test Example  2. Example  2 and In Comparative Example  Image measurement of solid oxide cell

3 is a photograph of the sintered solid oxide cell produced according to the comparative example. As a result of Experimental Example 1, when the shrinkage difference between the upper and lower layers is large, a large compressive stress is applied to the YSZ electrolyte layer to promote the densification of the electrolyte layer. However, It can be seen that the cell is broken as shown in FIG.

The present invention differs from the above comparative example in that the sintering is promoted by maintaining the compressive stress applied to the YSZ electrolyte in the sintering process and the thermal stress due to the difference in shrinkage ratio between the layers is minimized, And the first mixed layer and the second mixed layer were introduced between the electrolyte layer and the reaction preventive film layer, respectively. 4 is a photograph of the solid oxide cell produced according to Example 2 after sintering. Accordingly, due to the mixed layer introduced in the present invention, it is possible to prevent a sharp difference in shrinkage rate by acting as a buffer between the anode and the electrolyte layer and between the electrolyte layer and the reaction prevention layer, It can be seen that it alleviates. As a result, according to the present invention, it can be seen that after the simultaneous sintering, the warpage of the cell is minimized and the destruction is prevented, and a successful cell can be fabricated.

Experimental Example  3. According to the present invention Anode  Identification of cross-sectional structure of supported solid oxide cell

5 is a scanning electron microscope (SEM) photograph of a cross section of a cell fabricated in accordance with an embodiment of the present invention.

As shown in FIG. 5, it can be seen that a dense electrolyte layer capable of preventing gas leakage was effectively formed through the low-temperature sintering process according to the present invention because some of the pores existing in the electrolyte layer were all isolated. In addition, the introduction of the mixed layer relaxes the difference in the thermal stress between the layers, so that the interface defect is not found, and as a result of the simultaneous sintering, the interface with strong bonding force is successfully formed.

10: fuel electrode substrate layer 20: anode electrode functional layer
30: first mixed layer 40: electrolyte layer
50: second mixed layer 60: reaction preventing layer
100: Reverse polarity

Claims (19)

delete delete delete delete delete delete delete delete delete (a) manufacturing an anode substrate layer by a tape casting method,
(b) fabricating a layered product in which the anode functional layer, the first mixed layer, the electrolyte layer, the second mixed layer, and the reaction preventive layer are coated in this order on the prepared fuel electrode substrate layer, and
(c) simultaneously sintering the laminate to produce a fuel electrode supporting type of semi-conductive material;
Wherein the anode substrate layer comprises (i) a mixture of nickel oxide (NiO) and gadolinia doped ceria (GDC) or a mixture of nickel oxide (NiO) and samarium doped ceria (SDC)
Wherein the anode functional layer comprises a mixture of nickel oxide (NiO) and gadolinia doped ceria (GDC) or a mixture of nickel oxide (NiO) and samarium doped ceria (SDC)
Wherein the electrolyte layer is formed of yttria stabilized zirconia (YSZ) and the reaction inhibition layer comprises gadolinia doped ceria (GDC), samaria doped ceria (SDC), or mixtures thereof,
(I) a mixture of yttria stabilized zirconia (YSZ) and gadolinia doped ceria (GDC) or (ii) yttria stabilized zirconia (YSZ) and samarium doped ceria (SDC). ≪ / RTI >
The step (c)
(I) heat treating at 150-250 ° C for 1-7 hours, at 300-400 ° C for 3-4 hours and at 500-700 ° C for 3-4 hours, respectively;
(Ii) heat treatment at 800-900 占 폚 for 1-2 hours; And
(Iii) heat treatment at 1150-1250 ° C for 4-5 hours. The method of manufacturing a fuel electrode-supported solid oxide cell according to claim 1, delete delete 11. The method of claim 10,
Wherein the pore precursor is carbon black, graphite, or polymethylmethacrylate (PMMA). delete delete delete delete delete delete

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