JP3917717B2 - Solid electrolyte type electrolytic cell and method for producing the same - Google Patents

Description

[0001]
[Technical field to which the invention belongs]
The present invention relates to a solid electrolyte electrolytic cell excellent in power generation performance and inexpensive and a method for manufacturing the same.
[0002]
[Prior art]
In a solid electrolyte type electrolytic cell of a fuel cell, a porous ceramic fuel electrode and a porous ceramic air electrode are arranged on both sides of a ceramic electrolyte layer. Electricity is generated when fuel gas such as methane gas that has permeated the porous fuel electrode and reached the electrolyte layer reacts with oxygen gas in the air that has permeated the porous air electrode and reached the electrolyte layer. It is taken out from the fuel electrode and the air electrode.
[0003]
Conventionally, a solid electrolyte type electrolytic cell has been produced by printing or vapor-depositing porous ceramic electrodes on both sides of a ceramic electrolyte layer obtained by firing a ceramic green sheet.
Since it is expensive to form a porous electrode by a printing method or a vapor deposition method, a technique for forming both electrodes from a green sheet has been developed (JP-A-4-101360, JP-A-5-144463, etc.) . In this technique, a second green sheet serving as a porous ceramic fuel electrode and a third green sheet serving as a porous ceramic air electrode are laminated on both sides of a first green sheet serving as a ceramic electrolyte layer, and the laminate is fired. Thus, a solid electrolyte electrolytic cell is obtained. That is, in this technique, since the solid electrolyte electrolytic cell is obtained by only one firing without printing, the energy cost can be reduced.
[0004]
[Problems to be solved by the invention]
Improvement in power generation performance is also an important issue in a fuel cell using a solid electrolyte electrolytic cell. Further, in practical use, it is important to have an advantage over the power generation cost of other power generation systems. For that purpose, reduction of manufacturing cost is an important issue.
[0005]
Therefore, an object of the present invention is to manufacture a solid electrolyte electrolytic cell having high power generation performance with good productivity and at low cost.
[0006]
[Means for Solving the Problems]
In order to solve the above problems, a method for producing a solid electrolyte type electrolytic cell according to the present invention includes a second green sheet serving as a porous ceramic fuel electrode on one surface of a first green sheet serving as a ceramic electrolyte layer, and 50% of ceramic particles constituting the first green sheet in the method of obtaining a solid electrolyte type electrolysis cell by firing a laminate formed by laminating a third green sheet serving as a porous ceramic air electrode on the other surface. The particle size is 0.1 to 0.5 μm, the 90% particle size is 1 μm or less, the ceramic particles constituting the second green sheet have a 50% particle size of 0.5 to 10 μm, and a 90% particle size of 1.5 to 20 μm. And the ceramic particles constituting the third green sheet have a 50% particle size of 0.3 to 10 μm, a 90% particle size of 1 to 30 μm, and the first 10~300μm the thickness of the lean sheet, in advance by adjusting the thickness of the entire laminate 100 to 1000 [mu] m, the thickness of the laminate, made of a material which does not form a solid solution with the green sheet a fired ceramic sheet It is characterized by being stacked and fired in multiple stages through an intermediate sheet of 0.1 to 2 mm .
[0007]
The resulting solid oxide electrolysis cell in the manufacturing process, a thickness of the electrolyte layer is 5 to 250 microns, so a thin, high power generation efficiency. In the solid electrolyte type electrolytic cell, the thickness of the entire cell is 50 to 8000 μm, and the thickness of the electrolyte layer is compensated by the thickness of both electrodes to increase the mechanical strength. When the ceramic mixed conductor layer is disposed between the fuel electrode and the electrolyte layer and between the air electrode and the electrolyte layer, these thicknesses are also added to the total thickness. According to the above manufacturing method, it can be obtained with good productivity and at low cost.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The preferred embodiments of the present invention will be described below. The present invention is not limited to the following embodiment.
As shown in FIG. 1, the solid electrolyte type electrolytic cell according to the present invention has a fuel electrode 2 and an air electrode 3 arranged on both surfaces of an electrolyte layer 1, and such a configuration is a ceramic electrolyte layer. It is obtained by producing a laminate in which a second green sheet serving as a porous ceramic fuel electrode and a third green sheet serving as a porous ceramic air electrode are laminated on both sides of one green sheet and firing this laminate. . This is the same as the conventional one, but in the solid electrolyte type electrolytic cell according to the present invention, the thickness t of the electrolyte layer 1 obtained from the first green sheet is 5 to 250 μm, and the total thickness T of the cell is 50 to 50 μm. It is characterized by being 800 μm. The thickness t of the electrolyte layer is preferably 20 to 200 μm, more preferably 30 to 100 μm. The thickness T of the entire cell is preferably 150 to 500 μm.
[0009]
In the solid electrolyte electrolytic cell, the thermal expansion coefficients of the fuel electrode 2 and the air electrode 3 are within ± 50% (1000 ° C.), preferably within ± 30% (1000 ° C.) of the thermal expansion coefficient of the electrolyte layer 1. Is preferred. Since the solid electrolyte type electrolytic cell repeats a high temperature state and a low temperature state during use, peeling is likely to occur between the electrolyte layer 1 and the electrodes 2 and 3. If such consideration is given to the coefficient of thermal expansion of each of the layers 1, 2, and 3, the above peeling can be prevented. As a specific example of the thermal expansion coefficient satisfying such requirements, the thermal expansion coefficient of the material Ni0 / 8YSZ fuel electrode 2 is 11.0 × 10 ⁶ / ° C., and the thermal expansion coefficient of the material 8YSZ electrolyte 1 is 10 × 10 6. ^When the material is La _0.96 Sr _0.05 MnO ₃ , the thermal expansion coefficient of the air electrode 3 is 11.7 × 10 ⁶ / ° C.
[0010]
The method for manufacturing a solid electrolyte type electrolytic cell according to the present invention is characterized in that a green sheet laminate is prepared as shown in FIG. 2, and the laminate is stacked and fired in multiple stages as shown in FIG. And Furthermore, a green sheet laminate 10 as shown in FIG. 2 is prepared, and as shown in FIG. 3, this laminate 10 is an intermediate sheet (also referred to as a spacer) made of a material that does not dissolve in the green sheet. .) Is stacked in multiple stages via 20 and fired. In FIG. 3, numeral 30 represents a support such as a mortar. The intermediate sheet 20 may be placed at the uppermost position for the purpose of weighting or covering, and may be placed at the lowermost position for the purpose of improving gas escape from the lowermost layered product 20. The laminate 10 includes a second green sheet 12 that becomes a porous ceramic fuel electrode 2 and a third green sheet 13 that becomes a porous ceramic air electrode 3 on both sides of a first green sheet 11 that becomes a ceramic electrolyte layer 1. The thickness of the first green sheet is adjusted to 10 to 300 μm, and the thickness of the entire laminate is adjusted to 100 to 1000 μm.
[0011]
The intermediate sheet is preferably a ceramic sheet, and the particle size of the ceramic particles is preferably larger than the particle size of the ceramic particles constituting the fuel electrode and the air electrode. This is because the degree of porosity of the intermediate sheet is increased, gas can be easily released during firing, and firing efficiency can be achieved.
The intermediate sheet will be described more specifically. The material is appropriately selected, but ceramic is preferable as described above. Although a dense structure may be used, a porous structure is preferable in order to improve gas escape from the laminate 10. The intermediate sheet usually has an area larger than that of the green sheet (preferably 1.0 to 1.5 times, more preferably 1.0 to 1.2 times), and shrinkage due to heating for firing the green sheet The porous sheet is preferably 5% or less (more preferably 0.1% or less) and has a bulk density of 30 to 85% (more preferably 45 to 65%) with respect to the theoretical density. The intermediate sheet is used for support correction at the time of firing the green sheet, and is sandwiched so that the peripheral edge of the green sheet laminate does not protrude between them. If it does so, the outstanding surface correction effect of a porous sheet will be exhibited effectively, and a degreasing effect and discharge of decomposition gas will be performed smoothly.
[0012]
The material and manufacturing method of the porous sheet having a bulk density to be the intermediate sheet are not particularly limited, and the green sheet using a slurry containing the same inorganic powder, binder and solvent as exemplified later as a raw material for producing the ceramic green sheet And can be obtained by firing so as to be in a suitable bulk density range. At this time, if a powder having an average particle diameter of 2 to 100 μm, more preferably 30 to 80 μm is used as the inorganic powder, the above-described bulk density range can be easily obtained. The bulk density of the porous sheet can be adjusted depending on the firing conditions, and can also be adjusted by changing the average particle size of inorganic fine powder, the type of binder, or the amount of sintering aid added. is there.
[0013]
As described above, the porous sheet used as the intermediate sheet exhibits a degreasing promotion, a decomposition gas release promotion, and a surface straightening action, and a preferable thickness thereof is 0.1 to 2 mm, and more preferably 0. The preferred weight is 0.01 to 1 g / cm ² . If the intermediate sheet is too thin, the handleability will be reduced due to insufficient strength and the surface correction effect will be difficult to be exhibited effectively, and if it is too light, the function as a weight will be difficult to be effectively demonstrated and warping and undulation will occur. The prevention effect is insufficient. On the other hand, if it is too thick and heavy, or if it is too heavy, the friction between the green sheet laminate and the intermediate sheet will increase when the green sheet is fired, and the sheet surface will be easily damaged, and the green sheet will shrink. Is difficult to proceed uniformly, and there is a risk of causing distortion or cracking.
[0014]
In the method of the present invention, the intermediate sheet 20 is preferably made of a material that is the same as or similar to the material of each electrode. Further, as shown in FIG. 4, each side surface 20 a, 20 b can be made of the same material as or similar to each material of the fuel electrode 2 and the air electrode 3. That is, one surface 20 a is made of the same or similar material as that of the fuel electrode 2, and the other surface 20 b is made of the same or similar material as that of the air electrode 3. If it becomes like this, when stacking the laminated bodies 10... In the multi-stage as described above, the laminated body 10 and the intermediate sheet 20 are turned upside down for each stage, respectively. The surface 20a made of the same or similar material as the fuel electrode 2 may be directed to the fuel electrode green sheet 12 side, and the surface 20b made of the same or similar material to the air electrode 3 may be directed to the air electrode green sheet 13 side. it can. This is because, if the material is too different between the intermediate sheet and the green sheet in contact with the intermediate sheet, foreign electrodes (mixing of impurities) are likely to occur, but this can be avoided.
[0015]
When manufacturing a solid electrolyte type electrolytic cell, it is preferable that the powder constituting each green sheet is calcined at a temperature of 1000 ° C. or higher and a firing temperature (eg, 1300 ° C.) or lower. This is because the shrinkage difference between the green sheet serving as the electrolyte layer and the green sheet serving as the electrode is reduced during the main firing, and peeling between the layers is unlikely to occur.
When the manufacturing method of the solid electrolyte type electrolytic cell concerning this invention also has the process of obtaining the said laminated body, it is preferable to make it laminate | stack after cutting each green sheet to a desired dimension at this process. There is also a method in which the green sheets for each layer are stacked and cut, but the green sheet waste generated by cutting is a mixed product of three layers and cannot be returned to the green sheet raw material and reused. On the other hand, when the green sheet for each layer is cut out, the generated green sheet waste is a single item and can be recycled.
[0016]
The cut-out shape of the green sheet can be a square, a rectangle, a circle as well as a polygon or an ellipse such as a triangle or a pentagon as necessary. It may be something with
In the step of obtaining the laminate, lamination is preferably performed under a reduced pressure of 50 torr or less. The pressing conditions for the laminate are preferably set to a temperature of 50 ° C. or lower and a pressure of 50 kgf / cm ² or lower. This is because the conditions for obtaining the laminate are mild, the dimensional stability is high, and air can be prevented from entering the laminate interface. When the thickness of each layer is reduced, it is necessary to avoid the intrusion of air.
[0017]
The firing temperature and time of the laminate are about 1300 to 1500 ° C. and about 2 to 5 hours. In addition, it is preferable that the temperature is raised at 0.1 to 0.5 ° C./min up to 400 ° C., sufficiently debindered at 400 ° C., and then heated up to 1300 to 1500 ° C. at 0.5 to 5 ° C./min .
Below, it demonstrates in detail about manufacture of a green sheet.
[0018]
The material for the electrolyte layer is at least selected from the group consisting of powders mainly composed of zirconia and ceria (preferably about 80% by weight or more), rare earth elements such as Y and Ce; and alkaline earth elements such as Ca and Mg. One metal oxide is mixed (preferably about 20% by weight or less) and used. If necessary, alumina, titania or the like may be mixed with the raw material powder. Examples of the material for the fuel electrode include nickel / yttria-stabilized zirconia, nickel oxide / yttria-stabilized zirconia, and the like, and one or more of these are used. The air electrode _material, there may be mentioned LaMnO 3, LaNiO ₃ and LaCoO Perobukasukaito type composite oxide of lanthanum system such as _3, it is used alone or in combination.
[0019]
The ceramic particles constituting the electrolyte layer have a 50% particle size of 0.1 to 0.5 μm and a 90% particle size of 1 μm or less, and the ceramic particles constituting the fuel electrode have a 50% particle size of 0.5 to 10 μm and a 90% particle size. The ceramic particles constituting the air electrode 3 preferably have a 50% particle size of 0.3 to 10 μm and a 90% particle size of 1 to 30 μm. This is because the electrolyte layer 1 becomes dense, and on the other hand, both electrodes become porous, and the power generation efficiency is increased.
[0020]
In the above configuration, as shown in FIG. 1, it is preferable that the ceramic mixed conductor layer green sheet 4 is disposed between the electrode green sheets 2 and 3 and the electrolyte layer green sheet 1. This is because the extraction of electricity generated in the electrolyte layer 1 proceeds favorably. In this case, the ceramic particles constituting the mixed conductor layer green sheet 4 preferably have a 50% particle size of 0.1 to 5 μm and a 90% particle size of 1 to 20 μm.
[0021]
The above particle size (50% particle size: average particle size, 90% particle size: 90% volume particle size) is a value measured by a laser diffraction particle size distribution analyzer SALD-1100 manufactured by Shimadzu Corporation.
The above ceramic raw material powder is mixed with a binder and a solvent to form a slurry. There is no special restriction | limiting in the kind of binder, The organic binder used conventionally and an inorganic binder can be selected suitably, and can be used. Examples of organic binders include ethylene copolymers, styrene copolymers, acrylate copolymers, methacrylate copolymers, vinyl acetate copolymers, maleic acid copolymers, vinyl butyral resins, vinyl acetals. Examples thereof include cellulose resins, vinyl formal resins, vinyl alcohol resins, waxes, and celluloses such as ethyl cellulose. Of these, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, lauryl are known in terms of green sheet moldability and strength, thermal decomposition during firing, and the like. In addition to alkyl methacrylates having an alkyl group having 20 or less carbon atoms such as methacrylate and cyclohexyl methacrylate, aminoalkyl (meth) acrylates such as dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate are preferably used. These organic binders can be used alone or in combination of two or more as necessary. As these number average molecular weights, 20,000 to 200,000 are preferable, and 50,000 to 100,000 are more preferable. As the inorganic binder, zirconia sol, silica sol, alumina sol, titania sol and the like can be used alone or in admixture of two or more.
[0022]
In the method of the present invention, the green sheet binder preferably contains a copolymer having a methacrylic acid ester as a main component and a methacrylic acid ester having a basic nitrogen atom in the molecule as a subcomponent. This is because the preferred glass transition point of the copolymer is 5 ° C. or less, the internal plasticity (tackiness) imparted by the binder is good, and the thermal decomposability of the binder is good.
[0023]
The use ratio of the ceramic raw material powder and the binder is preferably 5 to 30 parts by weight, more preferably 10 to 20 parts by weight with respect to 100 parts by weight of the former. If the amount of binder used is insufficient, the strength, flexibility and adhesiveness of the green sheet will be insufficient, and if it is too much, it will be difficult to adjust the viscosity of the slurry, and the binder components will be decomposed and released more frequently during firing. It is difficult to obtain a homogeneous green sheet.
[0024]
Examples of the solvent include water, alcohols such as methanol, ethanol, 2-propanol, 1-butanol and 1-hexanol, ketones such as acetone and 2-butanone, fatty hydrocarbons such as pentane, hexane and heptane, benzene, Aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, and acetates such as methyl acetate, ethyl acetate, and butyl acetate are listed. These are used alone or in combination. The amount of the solvent used should be adjusted in consideration of the viscosity of the slurry when forming the green sheet. Although not particularly limited, the slurry viscosity is preferably 10 to 100 poise, more preferably 10 to 50 poise.
[0025]
In preparing the slurry, if necessary, in order to promote peptization and dispersion of the ceramic raw material powder, polymer electrolytes such as polyacrylic acid and ammonium polyacrylate, organic acids such as citric acid and tartaric acid, isobutylene and styrene In addition to the addition of dispersants such as copolymers of ammonium and maleic anhydrides, ammonium salts and amine salts of these, copolymers of butadiene and maleic anhydride, and ammonium salts thereof, the green sheet is given flexibility and tackiness. In order to do so, add phthalates such as dibutyl phthalate and dioctyl phthalate, plasticizers such as glycols and glycol ethers such as propylene glycol, and also add surfactants and antifoaming agents. be able to.
[0026]
In the method of the present invention, it is preferable that at least one of the green sheets other than the electrolyte layer contains a sublimable organic material such as melamine cyanurate. Since these green sheets are required to become porous by firing, conventionally, organic powders such as fluororesins and polyamide resins have been added. Since the organic powder generates heat during firing, it tends to cause warpage and distortion in the solid electrolyte electrolytic cell. On the other hand, the sublimable organic material does not generate such heat.
[0027]
The slurry obtained as described above is applied to a smooth substrate by a doctor blade method or the like with a predetermined thickness, dried, and the solvent is removed by volatilization to obtain a green sheet. The drying temperature and time are not particularly limited, but are about 60 to 120 ° C. and about 10 to 60 minutes.
[0028]
【Example】
Example 1
Production of first green sheet A zirconia powder containing 8 mol% of yttria was pulverized using a jet mill to obtain a powder having a 50% particle size of 0.3 m and a 90% particle size of 0.7 m. The thermal expansion coefficient as an electrolyte was 10.1 × 10 ⁶ / ° C.
[0029]
For 100 parts by weight of this powder, as a binder, a copolymer (number average molecular weight 50,000, glass transition temperature 2 ° C.) consisting of 5% dimethylaminoethyl methacrylate, 80% n-butyl methacrylate and 15% 2-ethylhexyl acrylate. A slurry was prepared by a pole mill using 15 parts by weight, 3 parts by weight of dibutyl phthalate as a plasticizer, and 50 parts by weight of a mixed solvent of toluene and ethyl acetate.
[0030]
After adjusting the viscosity of the slurry to 20 p, the slurry was molded by a doctor blade method and dried at 100 ° C. for 1 hour to obtain a first green sheet. The thickness of this green sheet was about 50 μm.
Production of second green sheet 30 parts by weight of zirconia powder (50% particle size 0.3 μm, 90% particle size 0.7 μm) containing 8 mol% yttria, nickel oxide powder (50% particle size 1.6 μm, Using 90 parts by weight of mixed powder of 70 parts by weight of 90% particle size 11 μm and 30 parts by weight of melamine cyanurate (MC-410: manufactured by Nissan Chemical Industries, Ltd.), 20 parts by weight of binder and 1 part by weight of plasticizer A second green sheet was obtained in the same manner as in the production of the first green sheet except that. The thickness of this green sheet was about 200 μm. The mixed powder had a 50% particle size of 1.2 μm and a 90% particle size of 8.0 μm, and the thermal expansion coefficient as an electrode was 11.0 × 10 ⁶ / ° C.
Production of third green sheet Powder having thermal expansion coefficient of 11.7 × 10 ⁶ / ° C. and composition of La _0.8 Sr _0.2 MnO ₃ (50% particle size 3 μm, 90% particle size 8.5 μm) ) Using 100 parts by weight, a third green sheet was obtained in the same manner as the second green sheet. The thickness of this green sheet was about 100 μm.
Production of intermediate sheet The raw material powder used in the second green sheet and the third green sheet was fired at 1100C to prepare a raw material powder for the intermediate sheet. Each of these powders was formed into a green sheet in the same manner as the second green sheet. Further, these green sheets were cut and fired at 1200 ° C. to obtain an intermediate sheet of 10.8 cm square and 0.6 mm thickness. Hereinafter, the intermediate sheet of the second green sheet composition is referred to as an intermediate sheet (2), and the intermediate sheet of the third green sheet composition is referred to as an intermediate sheet (3).
[0031]
The density of the intermediate sheet (2) was 70% of the theoretical density, and the intermediate sheet (3) was 50%.
Production of laminated body Each of the first, second and third green sheets was cut into 10 cm square and stacked in the order of the third, first and second. This was heated to 45 ° C. and pressurized at 40 kgf / cm ² for 2 minutes while reducing the pressure to a vacuum (30 Torr) to obtain a laminate.
Firing of the laminated body An intermediate sheet (2) is placed on the alumina shelf , and the laminated body is placed thereon so that the second green sheet layer faces downward and the peripheral edge does not protrude. It was. Furthermore, four sheets of laminates, such as intermediate sheet (3), laminate with the third green sheet layer facing downward, intermediate sheet (2), laminate with the second green sheet layer facing downward, intermediate sheet (3), etc. I put it over again. An intermediate sheet (2) was placed on the top. Thus, the shelf board which set the laminated body was piled up in the electric furnace 5 steps | paragraphs through the support | pillar.
[0032]
These laminates were cooled to 0.3 ° C. up to 400 ° C., 1 deg / min up to 1000 ° C., 0.6 deg / min up to 1350 ° C., and cooled to room temperature while being held at 1350 ° C. for 2 hours. A solid electrolyte type electrolytic cell was obtained.
(Example 2)
A solid electrolyte type electrolytic cell was obtained in the same manner as in Example 1 except that the laminates were stacked and fired four by four without using an intermediate sheet.
[0033]
(Example 3)
Production of first green sheet A zirconia powder containing 8 mol% of yttria was calcined at 1000C for 2 hours and then pulverized using a jet mill to obtain a 50% particle size of 0.5 m and a 90% particle size of 0.1%. A 9 μm powder was obtained. A green sheet having a thickness of 150 μm was obtained in the same manner as in Example 1 except that this powder was used.
Production of second green sheet The mixed powder obtained in Example 1 was calcined at 1000C for 1 hour to obtain a powder having a 50% particle size of 3.2 m and a 90% particle size of 16 m. A green sheet having a thickness of 150 μm was obtained in the same manner as in Example 1 except that this powder was used.
Production of third green sheet A powder having a composition of La _0.8 Sr _0.2 MnO ₃ used in Example 1 was calcined at 1000 ° C for 1 hour to obtain a 50% particle size of 5.6 µm and a 90% particle size of 21 µm. A powder was obtained. A green sheet having a thickness of 50 μm was obtained in the same manner as in Example 1 except that this powder was used.
[0034]
Using these green sheets, a laminate was prepared and fired in the same manner as Example 1 to obtain a solid electrolyte type electrolytic cell. Note that the sheet obtained in Example 1 was used as the intermediate sheet.
Example 4
Preparation of mixed conductor green sheet Example using 50% particle size 1.2 μm and 90% particle size 4.8 μm powder in which 90 mol% of cerium oxide and 10 mol% of yttrium oxide were dissolved. In the same manner as in Example 1, a 10 μm thick green sheet was obtained.
[0035]
This green sheet and each of the green sheets obtained in Example 1 were cut into 10 cm squares, and the third green sheet, the mixed conductor green sheet, the first green sheet, and the second green sheet were stacked in this order. In the same manner as in Example 1, a laminate was prepared and fired to obtain a solid electrolyte type electrolytic cell. Note that the sheet obtained in Example 1 was used as the intermediate sheet.
[0036]
【The invention's effect】
The manufacturing method of a solid electrolyte type electrolytic cell according to the present invention is a manufacturing method that can process a laminated body by one firing, has high productivity, and is inexpensive.
Since the solid electrolyte type electrolytic cell according to the present invention can be obtained with high productivity, it is less expensive than the conventional cell.
[0037]
Solid oxide electrolysis cell according to the present invention, since the thin thickness of the electrolyte layer, a high power generation efficiency.
In the solid electrolyte type electrolysis cell according to the present invention, the thinness of the electrolyte layer is compensated by the overall thickness, and the mechanical strength is increased.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a solid electrolyte electrolytic cell according to the present invention.
FIG. 2 is a cross-sectional view showing a laminate used in the present invention.
FIG. 3 is a cross-sectional view showing a state in which stacked bodies are stacked in multiple stages in the method of the present invention.
FIG. 4 is a cross-sectional view showing an intermediate sheet used in the method of the present invention.
FIG. 5 is another cross-sectional view showing a state in which stacked bodies are stacked in multiple stages in the method of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Electrolyte layer 2 Fuel electrode 3 Air electrode 10 Laminate body 11 First green sheet 12 Second green sheet 13 Third green sheet 20 Intermediate sheet 30 Support body

Claims (10)

A second green sheet serving as a porous ceramic fuel electrode is laminated on one surface of the first green sheet serving as a ceramic electrolyte layer, and a third green sheet serving as a porous ceramic air electrode is laminated on the other surface. In the method of obtaining a solid electrolyte type electrolytic cell by firing the laminate,
The ceramic particles constituting the first green sheet have a 50% particle size of 0.1 to 0.5 μm, a 90% particle size of 1 μm or less, and the ceramic particles constituting the second green sheet have a 50% particle size of 0.5 μm. 10 μm, 90% particle size is 1.5-20 μm, 50% particle size of the ceramic particles constituting the third green sheet is 0.3-10 μm, 90% particle size is 1-30 μm,
The thickness of the first green sheet is adjusted to 10 to 300 μm, and the thickness of the entire laminate is adjusted to 100 to 1000 μm.
The laminated body is fired by stacking in a multi-stage through an intermediate sheet having a thickness of 0.1 to 2 mm made of a fired ceramic sheet and made of a material that does not dissolve in the green sheet .
A method for producing a solid electrolyte type electrolytic cell. A ceramic mixed conductor layer is formed between the second green sheet serving as the fuel electrode and the first green sheet serving as the electrolyte layer and / or between the third green sheet serving as the air electrode and the first green sheet serving as the electrolyte layer. placing a green sheet, the manufacturing method of the solid oxide electrolysis cell of claim 1. The method for producing a solid electrolyte electrolytic cell according to claim 2 , wherein the ceramic particles constituting the mixed conductor layer have a 50% particle size of 0.1 to 5 µm and a 90% particle size of 1 to 20 µm. The thermal expansion coefficient of the fuel electrode is within ± 30% (1000 ° C.) of the thermal expansion coefficient of the electrolyte layer, and the thermal expansion coefficient of the air electrode is within ± 30% (1000 ° C.) of the thermal expansion coefficient of the electrolyte layer. The manufacturing method of the solid electrolyte type electrolytic cell in any one of Claim 1 to 3 . Each side surface of the intermediate sheet is made of the same or similar material as the material of the fuel electrode and the air electrode, and when stacking in multiple stages, the laminate and the intermediate sheet are reversed for each stage, so that the intermediate sheet is reversed. The surface made of the same or approximate material as the fuel electrode is directed to the fuel electrode green sheet side of the laminate, and the surface made of the same or approximate material as the air electrode is directed to the air electrode green sheet side. To 4. The method for producing a solid electrolyte type electrolytic cell according to any one of items 1 to 4 . The method for producing a solid electrolyte electrolytic cell according to any one of claims 1 to 5 , wherein the powder constituting each green sheet is calcined at a temperature of 1000 ° C or higher and lower than a firing temperature. The method for producing a solid electrolyte electrolytic cell according to any one of claims 1 to 6 , wherein in the step of obtaining the laminate, each green sheet is cut out to a desired size and then laminated. As each green sheet binder, those containing a copolymer and a methacrylic acid ester auxiliary component containing a basic nitrogen atom in a molecule as a main component ester methacrylate, according to any of claims 1 to 7 Manufacturing method of solid electrolyte type electrolytic cell. The method for producing a solid electrolyte type electrolytic cell according to any one of claims 1 to 8 , wherein at least one of the green sheets other than the electrolyte layer contains a sublimable organic material. Solid oxide electrolysis cell obtained by the production method according to any one of claims 1 to 9.

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