JP2010282817A - Method of fabricating flat solid oxide fuel battery cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of fabricating a flat oxide fuel battery cell, the method reducing warping of a single cell. <P>SOLUTION: The method includes: a step of forming a green laminate 10 by laminating an electrolyte sheet 3' on an electrode support body 2' formed in a sheet shape; and a step of forming a half cell composed of a sintered body by calcining the green laminate 10. The calcining step of the half cell includes a temperature elevating step and a temperature lowering step, and in the whole calcining step from the temperature elevating step to the temperature lowering step, a first load is added to the half cell. In the temperature lowering step, a second load is added to the half cell in addition to the first load. In the temperature lowering step, a temperature range in which the load is added to the half cell is decided as a range between the highest calcining temperature and at least a temperature in the vicinity of an operating temperature of the fuel battery cell by cooling down. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing an electrode-supported flat-type solid oxide fuel cell, and more particularly to a flat-type solid oxide fuel in which warpage of a single cell is reduced and reliability and output characteristics are improved. The present invention relates to a method for manufacturing a battery cell.

A fuel cell is a highly efficient power generator that directly extracts electrical energy from the chemical reaction between fuel and oxygen. In addition to environmental expectations such as CO ₂ emission reduction, the power generation liberalization and the deregulation trend have led to the distributed power generation business. It is attracting attention as a key component.

  Among various fuel cells, the solid oxide fuel cell (SOFC) uses an oxide ion conductor (ceramics) as an electrolyte as a general constituent material. Realization of high power generation efficiency is expected.

  Conventional SOFCs generally operate near 1000 ° C. Operation at high temperature is advantageous in terms of easy reaction and utilization of exhaust heat, and as a result, high power generation efficiency is expected. On the other hand, however, there are restrictions on the materials constituting the system due to the high temperature.

  Therefore, in recent years, new materials having ion conductivity and electron conductivity comparable to or higher than those of conventional electrolytes and electrodes have been vigorously developed even when the operating temperature is lowered, and the operating temperature is set to 700 to 800 ° C. SOFC is becoming mainstream. In addition, SOFC single cells have a wide variety of structures such as cylindrical, flat, and composite types, but they are easy to systematize and can be used to reduce electrical loss by thinning the electrolyte. A flat plate cell is common (for example, Non-Patent Document 1, p. 12 to 13).

JP 2007-194170 A

Development of fuel cell power generation technology Elemental research on expanding R & D applicability of solid oxide fuel cells (research on thermal shock-resistant flat plate cells and stacks), FY 2003-2004 NEDO commissioned business results report, Tokyo Gas Co., Ltd. Company, p. 12-13, p. 44-45, 2005

  The generated voltage of a single cell (hereinafter also simply referred to as a cell) used for SOFC is about 1 V at most. For this reason, in order to obtain electric power of a practical scale, a large number of single cells and interconnectors (separators) are alternately stacked to form a stack electrically connected in series to generate power. However, a single cell, which is a ceramic sintered body, is formed by co-sintering materials with different thermal expansion coefficients, so usually “warping” occurs, and if this becomes large, the cell and interconnector are good. As a result, the electrical contact cannot be ensured, and as a result, the output is reduced or the sintered body is cracked (for example, see Patent Document 1). In addition, the warpage of a single cell not only makes it impossible to fully draw out the capacity of the cell, but also causes problems related to operational stability and reliability due to power concentration due to uneven current paths and accumulation of mechanical distortion during stack assembly. May cause.

  In general, an electrode-supported flat solid oxide fuel cell has a fuel electrode or an air electrode as an electrode support, and laminates the electrode support and an electrolyte sheet to form a stacked green body (green stack). The green laminate is integrally sintered using a co-sintering method to prepare a half cell, and then a sheet serving as a counter electrode is laminated on the electrolyte and sintered. In the co-sintering method, different materials are fired at the same time, and a dense electrolyte and a porous electrode are mixed, so that it is extremely difficult in principle to obtain a flat single cell. Actually, in a practical cell shape, warpage of the order of several mm occurs (see Non-Patent Document 1, pages 44 to 45). Since such cell warpage tends to increase as the cell size increases, the influence is particularly significant in the production of a large-sized cell having a practical size. Therefore, it is essential to reduce warpage for the development of a large-capacity system (Non-patent Document 1, p. 12-13).

  Conventionally, in electrode-supported flat solid oxide fuel cells, the generation of warpage in the firing process is suppressed by applying a constant load during the half cell firing process, that is, from the start to the end of sintering. It was. However, when heating of the half cell is started from the green state and sintering is started in the vicinity of the firing temperature, both the electrolyte and the electrode support contract. In this process, scratches are generated on the surface of the sintered body due to friction generated between the surface of the electrolyte or the electrode support and the heavy stone that applies the load. In particular, since the electrolyte is thinner than the electrode support, it may lead to the generation of through-holes from the electrolyte surface to the electrode that significantly impair the cell characteristics, separation of the electrolyte and the electrode support, and damage to the half cell. On the other hand, if firing is performed without applying a load in order to avoid such a problem, the warpage cannot be suppressed, and the warpage of the order of several millimeters that can be visually confirmed with a general cell material and configuration. It was common to occur.

Therefore, as a result of earnestly examining the method of applying the load, the present inventors conducted various experiments in which the method of applying the load was changed by dividing the firing step into the temperature raising step and the temperature lowering step, resulting in the temperature raising step. If the load applied in the temperature lowering process is changed to be larger than the load applied in the temperature increasing process, the warpage will be significantly larger than the conventional load method in which a constant load is applied from the start to the end of sintering. It was found that it can be reduced. Specifically, a ceramic sheet containing a mixed powder obtained by mixing a zirconia-based oxide powder with a nickel oxide powder is used as a sheet with a fuel electrode as an electrode support, and a zirconia-based oxide is used as an electrolyte sheet. A ceramic sheet containing the powder of the product was used. As examples of the zirconia-based oxide, yttria-stabilized zirconia or scandia-stabilized zirconia Zr (Sc) scandia stabilized zirconia doped with O ₂ or a metal oxide (Zr (Sc, R) in O _2, R is Al ₂ O ₃ , CeO ₂ , or Y ₂ O ₃ ) was used, and in the temperature lowering process from the highest firing temperature to room temperature, at least the temperature near the operating temperature of the fuel cell (700 to 800 ° C.) When the second load (for example, 10 to 60 g / cm ² ) is applied in addition to the first load (for example, 40 to 50 g / cm ² ) applied in the temperature raising step until cooling, the warp of the half cell It was confirmed that can be suppressed to about several tens of μm. The physical reason why the warp can be reduced is not yet clear, but the temperature at the so-called warp inflection point at which the warp gradually changes from viscoelastic deformation to mainly elastic deformation is caused by the electrode support and the electrolyte. This is considered to be due to the fact that it matches the temperature near the operating temperature of the fuel cell depending on the material. Strictly speaking, the firing step is a process in which the temperature is gradually raised from room temperature to a maximum firing temperature of about 1300 ° C. (temperature raising step) and then maintained at that temperature for a predetermined time (usually about 2 hours) ( There is a constant temperature holding step), and then the temperature is gradually lowered to room temperature. Therefore, in the following description, the temperature lowering step will be described as including a constant temperature holding step at the maximum firing temperature.

  The present invention has been made based on the above-described conventional problems and examination results, and an object of the present invention is to provide a method for producing a flat oxide fuel cell capable of suppressing or reducing cell warpage. .

  In order to achieve the above object, a method for producing a flat plate type oxide fuel cell according to the present invention comprises producing a flat plate type solid oxide fuel cell comprising an electrolyte sandwiched between a fuel electrode and an air electrode. A method of forming a green laminate by laminating an electrolyte sheet on an electrode support formed in a sheet shape from a constituent material of either the fuel electrode or the air electrode; and the green laminate And forming a half cell made of a sintered body, and the half cell firing step includes a temperature raising step and a temperature lowering step including a constant temperature holding step at the highest firing temperature. A temperature at which the first load is applied to the half cell, the second load is applied to the half cell in addition to the first load in the temperature lowering step, and the second load is applied to the half cell. Circumference is characterized in that between the maximum firing temperature to be cooled to a temperature of at least near the operating temperature of the fuel cell.

  Moreover, the present invention is characterized in that, in the above-mentioned invention, a temperature in the vicinity of an operating temperature of the fuel cell is 700 to 800 ° C.

Moreover, the present invention is characterized in that, in the above invention, the first load applied to the half cell is 40 to 50 g / cm ² , and the second load is 10 to 60 g / cm ² .

  Further, the present invention is characterized in that, in the above invention, after reaching a temperature near the operating temperature of the fuel cell, the first load is continuously applied to the half cell until it is cooled to room temperature. .

  Further, in the present invention according to the above-mentioned invention, the electrode support sheet is composed of at least one ceramic sheet including a mixed powder obtained by mixing a zirconia-based oxide powder with a nickel oxide powder. It is characterized by.

In the present invention, the zirconia-based oxide may be yttria-stabilized zirconia, scandia-stabilized zirconia Zr (Sc) O _2, or scandia-stabilized zirconia doped with a metal oxide (Zr (Sc, R)). O ₂ and R is any one of Al ₂ O ₃ , CeO ₂ , and Y ₂ O ₃ ).

  The present invention is also characterized in that, in the above invention, the electrode support sheet is composed of at least one ceramic sheet containing a lanthanum perovskite oxide powder.

  Furthermore, the present invention is characterized in that, in the above invention, the electrolyte sheet is a ceramic sheet containing zirconia-based oxide powder.

According to the present invention, in the temperature lowering process at the time of firing the half cell, the first load applied during the temperature raising process is added to the first load applied during the temperature raising process until the temperature is cooled to at least the temperature near the operating temperature of the fuel cell. Since the load of 2 is applied to the half cell, the warpage can be dramatically reduced or reduced compared to the conventional firing method in which a constant load is applied in the entire process of the firing process, and the damage on the electrolyte surface is also reduced. By avoiding this, a cell can be manufactured with a high yield. This is presumably because the temperature range applied to the half cell coincides with the temperature of the inflection point of the warp, and the warp change is moderated.
For example, if a disk-shaped cell having a diameter of 120 mm is taken as an example, the warpage that was about 100 μm to several hundred μm in the conventional firing method aiming to suppress warpage is reduced to about 10 to several tens μm, which is not a practical problem. I was able to. As a result, the flatness of the cell is greatly improved, whereby the current collection state in the cell stack is improved, and as a result, the output characteristics can be greatly improved. In addition, the reliability of the cell stack can be improved because the occurrence of breakage during stack fabrication and the occurrence of unnecessary geometric distortion can be suppressed.
If the first load applied to the half cell is 40 g / cm ² or less, the effect of applying the load decreases, which is not preferable. When the maximum load applied to the half cell is 110 g / cm ² or more in combination of the first weight and the second weight, the reduction in warpage is alleviated, so there is no point in applying more load. A more preferable load is 50 to 100 g / cm ² in total of the first load and the second load.
Further, after reaching a temperature near the operating temperature of the fuel cell, the warp can be further reduced by applying a first load (less than 50 g / cm ² ) until it is cooled to room temperature. it can.

1 is a front view showing a first embodiment of a flat plate type solid oxide fuel cell according to the present invention. It is a figure which shows the installation condition of the green laminated body at the time of baking in embodiment of this invention. It is a schematic diagram of the cross section of the baking furnace used in order to implement this invention. It is a figure which shows the curvature of a half cell. It is a figure which shows the relationship between the curvature of a to-be-sintered body, a baking furnace temperature, and baking elapsed time.

[First Embodiment]
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
In FIG. 1, a flat solid oxide fuel cell 1 has a fuel electrode 2 formed to be thick to form an electrode support, an electrolyte 3 formed thereon, and an air electrode 4 serving as a counter electrode thereon. Thus, a fuel electrode support type cell is formed. In such a single cell 1, a fuel cell 2 and an electrolyte 3 sheet are laminated to form a green laminate, and the green laminate is fired to produce a half cell made of a sintered body. The sheet is laminated on the electrolyte 3 and the sheet is fired.

As a constituent material of the half cell, for example, NiO having an average particle diameter of 1.8 to 5.0 μm and a specific surface area of 0.8 to 1.5 m ² / g is used for the fuel electrode 2 constituting the electrode support. 3, for example, yttria-stabilized zirconia (YSZ) having an average particle size of 0.1 to 0.5 μm and a specific surface area of 7 to 17 m ² / g is used. The thickness of the electrolyte 3 after firing was 5 to 15 μm, for example, and the thickness of the fuel electrode 2 was 1 to 2 mm.

  In producing the half cell, NiO and yttria-stabilized zirconia are each made into a ceramic sheet by a doctor blade method, and then a required number of layers are laminated and bonded together to produce a laminated sheet (green laminate) having a predetermined thickness. Next, the green laminate is cut into a circle having a diameter of about 150 mm and fired to produce a half cell.

  FIG. 2 is a diagram showing the installation state of the green laminate during firing. 10 is a green laminate comprising a NiO sheet 2 'and a yttria-stabilized zirconia sheet 3', 11 is an alumina plate, and 12 is an alumina setter. The green laminate 10 cut out in a circle is sandwiched between two alumina plates 11, set on an alumina setter 12, with the upper side serving as an electrolyte and the lower side serving as an electrode support, and then loaded into a firing furnace (FIG. 3). The half cell 30 (FIG. 4) which consists of a sintered compact is produced by baking. The upper alumina plate 11 is applied to the half cell as a first load when the half cell is fired. The weight of the alumina plate 11 is less than 40 to 50 g.

FIG. 3 is a cross-sectional view of the firing furnace showing a state during firing of the half cell, 20 is a firing furnace, and 21 is a pressurizing mechanism 21 for pressurizing the half cell. The pressurizing mechanism 21 includes a screw 22 that moves up and down by rotating the upper plate of the firing furnace 20 and a weight 23 attached to the lower end of the screw 22, thereby raising and lowering the half cell firing process. Among them, in the temperature lowering process, a second load is applied to the half cell in addition to the first load. The second load is a load including the weight of the upper alumina plate 11 and is 10 to 60 g / cm ² . That is, the total load applied to the half cell is 50 to 110 g / cm ² . A small observation window 24 is provided on the wall surface of the firing furnace 21 for visually confirming the behavior of the half cell during firing from the outside. Reference numeral 25 denotes a transparent quartz fitted in the observation window 24.

  As the firing conditions of the half cell by the firing furnace 20, the temperature is raised from room temperature at a rate of 100 ° C./hour, held at the highest firing temperature (about 1300 ° C.) for 2 hours (temperature raising step), and then the rate of 100 ° C./hour. To cool to room temperature (temperature lowering step). In addition, a second load is applied to the half cell 30 by the pressurizing mechanism 21 from the time when the firing maximum temperature is reached until the temperature is cooled to a predetermined temperature. The predetermined temperature is about 700 to 800 ° C. near the operating temperature of the fuel cell.

The second load is 10-60 / cm ² . It is not preferable that the total load applied to the half cell is 50 g / cm ² or less because warping increases and the effect of applying the load decreases. When the total load is 110 g / cm ² or more, the reduction in warping tends to be relaxed. For this reason, a more preferable total load is 50-100 g / cm < ² >. Further, after reaching a temperature near the operating temperature of the fuel cell, the third load is the same as the first load until the end of cooling, that is, a load of less than 50 g / cm ² , more preferably 40 g / cm ² is applied to the half cell. Although it is desirable to continue to be applied, warping can be reduced even when the load is switched to a no-load state.

  Thus, according to the present invention, in the temperature lowering process from the highest firing temperature to room temperature, the first temperature applied in the temperature increasing process is at least until the fuel cell is cooled to a temperature (700 to 800 ° C.) near the operating temperature. As a result, the half cell warpage can be suppressed to several tens of μm compared to the conventional load method in which a constant load is applied from the start to the end of sintering. It was confirmed. The physical reason that warpage can be reduced is that the temperature at the so-called inflection point where the warpage gradually changes from viscoelastic deformation to mainly elastic deformation depends on the electrode support and the electrolyte material. This is considered to be due to the fact that the temperature is substantially the same as the temperature near the temperature.

  FIG. 4 shows that when firing is performed without applying a load other than the weight of the alumina plate 11 through the firing process, the warpage of the sintered body (half cell) after reaching the temperature of 800 ° C. after the start of the temperature rise. FIG. 4 is a diagram showing the results of measurement, wherein the left vertical axis is the warp of the sintered body, the right vertical axis is the firing furnace temperature, the horizontal axis is the firing elapsed time, and the curve A is the temperature of the sintered body along the time axis. The change, curve B, shows the warpage of the sintered body that changes with time.

  As can be easily inferred from the examples reported so far, first, the shrinkage of the electrolyte 3 (YSZ), that is, the sintering starts, and accordingly, the object to be sintered protrudes downward as shown by the curve B. Then, the warping gradually decreases as the electrode support (fuel electrode 2) starts to contract from around 900 ° C. At the stage where the firing at the highest firing temperature (1300 ° C.) is finished, the change in warpage is almost finished and converges to a constant warpage value determined depending on the shrinkage rate of the electrolyte 3 and the fuel electrode 2 alone. Thereafter, when the cooling is started, the upwardly warping gradually decreases, and eventually the downwardly convex warping is started. It can be seen that in the region of 900 ° C. or lower, the warpage increases monotonously as the temperature decreases. This is considered that viscoelastic deformation in a temperature region of 900 ° C. or higher mainly turns into elastic deformation and exhibits a pie metal model-like behavior. The warpage of the half cell 30 (FIG. 5) obtained by this sintering process was about 320 μm.

On the other hand, firing is performed by applying a load (total load) of 50 to 100 g / cm ² to which the first load and the second load are applied while cooling from the start of temperature decrease to a temperature close to the operating temperature of the fuel cell. The results of measuring the warpage are shown in Table 1. The temperature at the start of temperature drop was the highest firing temperature (1300 ° C.), and the temperature near the operating temperature of the fuel cell was 800 ° C.

It can be seen from Table 1 that the warpage of the obtained half cell 30 is reduced by applying a second load in addition to the first load to the weight of the alumina plate 11 by the pressurizing mechanism 21. When the second load was in a load range of 10 to 60 g / cm ² , the warp decreased compared to the case of no load. In particular, when the total load is in the range of 50 to 100 g / cm ² , the warpage is greatly reduced as the load increases. However, when the load is larger than 100 g / cm ² , the reduction in warping tends to be saturated, and when the load is 200 g / cm ² or more, the half cell 30 is damaged. This is considered to be because the warpage caused by the difference in thermal expansion coefficient during the cooling process is released beyond the elastic limit by an excessive load.

[Comparative example]
Using the same green laminate and sintering temperature brofil as in the first embodiment, a load of 50 to 100 g / cm ² is applied.
(1) When added from 800 ° C. during temperature rise to 800 ° C. during temperature drop (2) When added from the start of temperature drop to room temperature (3) 800 ° C. from the start of temperature fall as in the first embodiment A comparison was made of the case where it was added while it was cooled down.

  In the case of (1), many scratches on the electrolyte surface, which are considered to be caused by friction between the alumina plate 11 and the surface of the electrolyte 3, occur during shrinkage during firing, and some of the scratches are through-holes to the fuel electrode 2. It was confirmed that From this, it can be seen that it is desirable to apply a necessary minimum load from the start of shrinkage until the sintering is sufficiently advanced.

  On the other hand, in the case of (2), although damage and defects on the electrolyte surface as seen in the case of (1) were not observed, all the half cells were broken. This is thought to be because an excessive load exceeding the elastic limit of warpage caused by the difference in thermal expansion coefficient was applied during the cooling process.

In the case of (3), it is as shown in the first embodiment.

[Second Embodiment]
In the second embodiment of the present invention, an alumina-doped scandia-stabilized zirconia (Zr (Sc, Al ₂ O ₃₎ having an average particle size of 0.4 to 0.7 μm and a specific surface area of 10 to 12 m ² / g is used as the electrolyte material. ) O ₂ , hereinafter SASZ), and a mixture of SASZ and nickel oxide (NiO) was used as the electrode support fuel electrode material. NiO is an average particle diameter 1.8～5.0Myuemu, specific surface area 0.8~1.5m ² / g or an average particle diameter of 1.0 to 3.0 m,, a specific surface area 3.0~5.05m ² / Two kinds of raw materials of g were used. Hereinafter, the former on the flight is NiO-1, and the latter is NiO-2.

The half cell has a two-layer structure in which NiO-1 is used as the fuel electrode material, NiO-2 is used as the fuel electrode material, NiO-2 is used as the fuel electrode substrate, and NiO-1 is formed in the vicinity of the electrolyte at about 100 μm. A half cell with a fuel electrode structure was fabricated. For convenience, they are referred to as Type 1 cell, Type 2 cell, and Type 3 cell, respectively. The manufacturing procedure is the same as in the first embodiment. The sintering temperature profile is also the same as that of the first embodiment, and the total load is 100 g / cm ² between the case of no load (only the load due to its own weight of the alumina plate 11) and the cooling from the start of the temperature decrease to 800 ° C. Table 2 shows the warpage when the load is applied.

  Similar to the first embodiment, when the second load is applied in addition to the first load while cooling to the temperature near the operating temperature of the fuel cell (700 to 800 ° C.) from the start of the temperature decrease. It can be seen that warpage is reduced due to large radiation. Here, for the two types of NiO, the amount of warpage of the obtained half cell is different because the sintering characteristics (shrinkage behavior) of the green laminate depends on the average particle size and specific surface area of the raw material powder, This is probably because the fuel electrode (NiO) having a smaller shrinkage rate is less warped (Patent Document 1: Japanese Patent Laid-Open No. 2007-194170).

[Third Embodiment]
A cell 1 shown in FIG. 1 was produced by forming an air electrode 4 of LaNi _0.6 Fe _0.4 O ₃ (LNF) on the electrolyte of the half cell produced in the second embodiment. The air electrode 4 was formed by applying an LNF paste onto the half-cell electrolyte 3 and firing at 1000 ° C. for 2 hours. A cell that is flat at room temperature does not have its internal stress relaxed, and when heated to a high temperature again under no load, the cell warps to relieve the internal stress. It is known that when the air electrode formation firing is performed in a no-load state, after the air electrode is formed, the amount of warpage at room temperature is greater than the amount of warpage of the half cell before the air electrode is formed. In the process of forming the air electrode, in the process of cooling from the sintering temperature of 1000 ° C. to room temperature, up to 800 ° C., a second load of 100 g / cm ² was applied in addition to the first load. The warpage of the cell was within the error range, and the warpage of the half cell shown in Table 2 was not changed.

  Although the above-described embodiment has shown an example in which the fuel electrode 2 is an electrode support, the present invention is not limited to this, and a half cell is similarly manufactured using the air electrode 4 as an electrode support. Also good. In that case, a ceramic sheet containing lanthanum perovskite oxide powder may be used as the air electrode sheet.

  DESCRIPTION OF SYMBOLS 1 ... Single cell, 2 ... Fuel electrode, 2 '... NiO sheet, 3 ... Electrolyte, 3' ... Yttria stabilization zirconia sheet, 4 ... Fuel electrode, 10 ... Green laminated body, 11 ... Alumina plate, 12 ... Alumina setter, 20 ... firing furnace, 21 ... pressurizing mechanism, 30 ... half cell.

Claims (8)

A method for producing a flat solid oxide fuel cell comprising an electrolyte sandwiched between a fuel electrode and an air electrode,
Forming a green laminate by laminating an electrolyte sheet on an electrode support formed into a sheet shape from the constituent material of either the fuel electrode or the air electrode;
A step of firing the green laminate to form a half cell made of a sintered body,
The half cell firing step includes a temperature raising step and a temperature lowering step including a constant temperature holding step at the maximum firing temperature. In the temperature raising step, a first load is applied to the half cell, and in the temperature lowering step, the first load is applied. In addition, a second load is applied to the half cell, and the temperature range in which the second load is applied to the half cell is between the highest firing temperature and at least a temperature close to the operating temperature of the fuel cell. A flat-type solid oxide manufacturing method for a fuel cell according to claim 1. In the manufacturing method of the flat type solid oxide fuel cell according to claim 1,
A method for producing a flat-plate solid oxide fuel cell, wherein the temperature in the vicinity of the operating temperature of the fuel cell is 700 to 800 ° C. In the manufacturing method of the flat type solid oxide fuel cell according to claim 1 or 2,
A method for producing a flat plate type solid oxide fuel cell, wherein the first load applied to the half cell is 40 to 50 g / cm ² and the second load is 10 to 60 g / cm ² . In the manufacturing method of the flat type solid oxide fuel cell according to any one of claims 1, 2, and 3,
After reaching a temperature near the operating temperature of the fuel cell, the first load is continuously applied to the half cell until it is cooled to room temperature. Manufacturing method. In the manufacturing method of the flat type solid oxide form fuel cell according to any one of claims 1 to 4,
The plate-type solid oxide form, wherein the electrode support sheet is composed of at least one layer of a ceramic sheet containing a mixed powder obtained by mixing a zirconia-based oxide powder with a nickel oxide powder. A method for producing a fuel cell. In the manufacturing method of the flat type solid oxide fuel cell according to claim 5,
The zirconia-based oxide is yttria-stabilized zirconia or scandia-stabilized zirconia Zr (Sc) O ₂ or scandia-stabilized zirconia (Zr (Sc, R) O ₂ ) doped with a metal oxide, and R is Al ₂ O _3. Or any one of CeO ₂ and Y ₂ O ₃ ). In the manufacturing method of the flat type solid oxide form fuel cell according to any one of claims 1 to 4,
A method for producing a flat plate type solid oxide fuel cell, wherein the electrode support sheet is composed of at least one layer of a ceramic sheet containing a lanthanum perovskite oxide powder. In the manufacturing method of the flat type solid oxide form fuel cell according to any one of claims 1 to 7,
The method for producing a flat plate type solid oxide fuel cell, wherein the electrolyte sheet is a ceramic sheet containing zirconia-based oxide powder.

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