JP3326470B2 - A method for producing a solid oxide sintered membrane for a solid oxide fuel cell. - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a solid oxide fuel.
The present invention relates to a method for producing a solid oxide sintered film for a battery .

[0002]

BACKGROUND ART In a fuel cell, a solid oxide fuel cell is known. In the case of this battery, the air electrode, the electrolyte, and the fuel electrode, which are the three materials constituting the battery, are all made of a solid oxide film. Therefore, when the solid oxide fuel <br/> charge batteries, the development of technology is important to be able to produce high quality solid oxide film economically and efficiently.

[0003]

SUMMARY OF THE INVENTION The present invention relates to a solid oxide.
It is an object of the present invention to provide a method for economically producing a high-quality solid oxide membrane used for a fuel cell .

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, (1) a solid oxide fuel cell is formed on a surface of a graphite molded body as a base material.
An electrodeposition step of depositing the solid oxide particles to be used in a film form by electrophoretic electrodeposition, and firing the graphite molded body having a solid oxide particle film obtained in the electrodeposition step on its surface in the air to form the solid. to form the oxide particle film on the sintered film, the solid comprising a firing step of oxidizing and removing the graphite
A method for producing a solid oxide sintered membrane for an oxide fuel cell is provided. Further, according to the present invention, (2) the front as a substrate
An electrodeposition step in which solid oxide particles used for a solid oxide fuel cell are deposited in a film form on a surface of the solid oxide sintered film obtained by the method (1) by electrophoretic deposition; solid laminated structure comprising a firing step of firing the solid oxide sintered film having a solid oxide particle film obtained in Chakukotei the surface
A method for producing a solid oxide sintered membrane for an oxide fuel cell is provided. Furthermore, according to the present invention, (3)
A first electrodeposition step in which first solid oxide particles used for a solid oxide fuel cell are deposited in a film form on the surface of the solid oxide sintered film obtained by the method (1) by electrophoretic deposition. When,
A solid oxide on the surface of the electrodeposit obtained in the first electrodeposition step;
Comprising a second electrodeposition step in which the second solid oxide particles used in the fuel cell are adhered in a film by electrophoretic deposition, and a firing step in which the electrodeposit obtained in the second electrodeposition step is fired. A method for producing a solid oxide sintered membrane for a solid oxide fuel cell having a structure is provided.

[0005]

DETAILED DESCRIPTION OF THE INVENTION According to the present invention, a solid oxide fuel cell
In order to manufacture a solid oxide sintered film used for a pond , first, a graphite molded body is used as a base material,
Solid oxide particles used in a solid oxide fuel cell are deposited in a film by electrophoretic deposition. The electrophoretic deposition method in this case is a method in which charged solid oxide particles dispersed in an organic solvent are deposited on an electrode substrate by applying a DC voltage. The solid oxide particles on graphite molded body on the surface to be deposited by electrophoretic deposition method, the solid oxide particles in an organic solvent (electrodeposition bath) in dispersed graphite molded body of the electrode and its counter electrode ( For example, a DC voltage is applied between the first and second electrodes. In this case, a graphite molded body is used as a cathode. As a result, the charged solid oxide particles migrate in the direction of the graphite molded body, and adhere and deposit thereon, thereby forming a solid oxide particle film.

The average particle diameter of the solid oxide particles is 0.2 to
It is 40 μm, preferably 0.2 to 2 μm. As a medium for an electrodeposition bath for dispersing the solid oxide particles, an organic solvent such as acetone, acetylacetone, and 2-propanol is used. In this case, iodine can be added to the organic solvent as needed. The concentration of the solid oxide particles in the electrodeposition bath was 0.1 to 100 ml of the organic solvent.
The proportion is 1 to 5 g, preferably 0.5 to 1.0 g.
The DC voltage is 40 to 400 V, and the application time is 1 to
60 minutes. The thickness of the solid oxide particle film (electrodeposited film) formed on the surface of the graphite molded product is 1 to 1000 μm.
m, preferably 10 to 600 μm.

Next, the graphite molded body having the solid oxide particle film formed on the surface as described above is fired in the air. The firing temperature in this case may be a temperature at which the oxide particles are sintered, and is usually 1150 ° C. or higher, preferably 1250 ° C. or higher.
It is about 400 ° C. By this firing, the solid oxide particle film becomes a sintered film, while the graphite molded body is oxidized (burned) and removed. As a result, a high quality solid oxide sintered film is obtained.

According to the present invention , used for a solid oxide fuel cell
When manufacturing a solid oxide sintered film to be formed, the film shape is related to the shape of the graphite molded body used as an electrode, when the molded body is a plate-shaped body, a plate-shaped sintered film is obtained, On the other hand, in the case of a cylindrical shape, a cylindrical sintered film is obtained. In the production of the solid oxide sintered film by the present invention, by using plural kinds of particles as the solid oxide particles which is a raw material, to obtain a solid oxide sintered film comprised of a plurality of kinds of solid oxide By forming another solid oxide particle film in the same manner on the solid oxide particle film formed on the graphite molded body, a solid oxide sintered film composed of a plurality of solid oxide layers is obtained. be able to. The thickness of this sintered film is 50-2000μ
m, preferably 100 to 1000 μm.

[0009] The solid oxide particles include a composition for a fuel cell.
Any one is selected according to the desired sintered film as a material. For example, often in the case of obtaining an empty Kikyoku may be used lanthanum manganite (LaMnO ₃₎ particles (powder), in the case of obtaining the solid electrolyte, the use of the particles of zirconia or YSZ (yttria stabilized zirconia) In the case of obtaining a fuel electrode, mixed particles composed of nickel carbonate particles and YSZ particles may be used.

In the present invention, by using the solid oxide sintered film itself obtained as described above as the base electrode thereof, a solid oxide sintered film having a laminated structure used in a solid oxide fuel cell can be obtained. Can be obtained. In this case, the shape of the solid oxide sintered film used as the electrode substrate can be various shapes such as a plate shape and a cylindrical shape. In order to manufacture a solid oxide sintered film having such a laminated structure (multilayer structure), solid oxide particles are electrodeposited on the surface of the solid oxide sintered film as a base material, and the electrodeposit is fired. I just need. Thereby, a solid oxide sintered film having a two-layer structure can be obtained. In the case where a solid oxide sintered film having a laminated structure is manufactured as described above, the solid oxide type
By using a plurality of solid oxide particles used for a fuel cell and adopting an electrodeposition process corresponding to each solid oxide particle, a solid oxide firing having a multilayer structure corresponding to the number of the electrodeposition processes is performed. A conjunctiva can be obtained. For example, after solid oxide particles are electrodeposited on a solid oxide sintered film as a substrate, the second solid oxide particles are electrodeposited on the surface of the electrodeposit using the electrodeposit. Then, by firing the electrodeposit thus obtained, on the solid oxide sintered film,
A solid oxide sintered film having a three-layer structure in which the first solid oxide sintered film and the second solid oxide sintered film are sequentially formed can be obtained.

[0011]

Next, the present invention will be described in more detail with reference to examples. Example 1 (Formation of Lanthanum Manganite Sintered Film) Lanthanum manganite (LaMnO ₃ ) (hereinafter simply referred to as L
1 g of particles (abbreviated as M) (average particle size: 2 μm) was added to a mixture of 100 ml of acetone and 20 mg of iodine to prepare an electrodeposition bath. Next, a graphite rod (diameter: 0.5 mm) and a spiral stainless steel wire as its counter electrode were placed in the electrodeposition bath, and the graphite rod was used as a cathode at an electrodeposition voltage of 100 V for 1 minute. After electrodeposition, the graphite rod had a thickness of about 2
A 00 μm LM particle film was formed. Next, the graphite rod having the LM particle film was placed in air for 1300 hours.
After calcination at 5 ° C. for 5 hours, the graphite rod was oxidized and removed to obtain a cylindrical LM sintered film (thickness: about 160 μm). This was a porous membrane having sufficient strength.

Example 2 In Example 1, 2-propanol 10 was used as an electrodeposition bath.
An experiment was carried out in the same manner as above except that 0 g of LM was added to 1 g of LM and the electrodeposition time was 30 minutes. As a result, a cylindrical LM sintered film having a thickness of about 500 μm was obtained.

EXAMPLE 3 An electrodeposition bath was prepared by adding 1 g of YSZ (yttria-stabilized zirconia) particles (average particle size: 0.3 μm) to 100 ml of 2-propanol. Next, using this electrodeposition bath,
Electrodeposition treatment was performed under the conditions of 100 V for 30 minutes in the same manner as in Example 1 to form a YSZ particle film on a graphite rod. Next, the graphite rod having the TSZ particle film thus obtained was used as an electrode, and 0.535 g of nickel carbonate particles (average particle size: 0.7 μm) and YSZ particles 0 in 100 ml of acetylacetone were used as an electrodeposition bath. Using a mixture obtained by dispersing a mixture with 0.2529 g,
Electrodeposition was performed at 40 V for 5 minutes in the same manner as in Example 1 to form a mixed particle film made of nickel carbonate and YSZ. Next, the electrodeposit thus obtained was calcined in air at 1380 ° C. for 5 hours to oxidize and remove the graphite. As a result, a dense YSZ layer (thickness: 10
0 μm) on which a mixture layer of nickel oxide (NiO) and YSZ (thickness: 50 μm) was formed to obtain a two-layer cylindrical film.

Example 4 An electrodeposition bath was prepared by adding 1 g of YSZ particles to 100 ml of 2-propanol. Next, the cylindrical LM sintered body obtained in Example 1 and a spiral stainless steel wire as its counter electrode were arranged in the electrodeposition bath, and the LM sintered body was used as a cathode, and an electrodeposition voltage of 40 V was used. When the electrodeposition treatment was performed under the conditions of 30 minutes and the electrodeposition time, a YSZ particle layer (thickness: 40 μm) was obtained on the surface of the LM cylinder. next,
The electrodeposit was fired in air at 1380 ° C. for 5 hours to obtain a two-layer sintered film in which a dense YSZ layer was formed on a cylindrical LM layer.

Example 5 An YSZ particle layer was formed on a cylindrical LM sintered body by performing electrodeposition in the same manner as in Example 4. Next, on this electrodeposit, Y
SZ particles (0.2529 g) and NiCO ₃ particles (0.5
A mixture of 351 g) (volume ratio of NiCO ₃ and YSZ: 4: 6) in 100 ml of 2-propanol was used as an electrodeposition bath, and subjected to electrodeposition at 40 V for 30 minutes. A particle layer made of a mixture of YSZ and NiCO ₃ was formed. Next, when the electrodeposit obtained above was co-sintered in air at 1380 ° C. for 5 hours, a dense YSZ layer and a mixture layer of porous NiO and YSZ were sequentially formed on the porous cylindrical LM layer. The obtained cylindrical sintered body having a three-layer structure was obtained. In this case, the content of NiO in the mixture layer of NiO and YSZ is about 47 vol%.

[0016]

According to the present invention, a solid oxide fuel cell is provided.
It is possible to obtain a solid oxide sintered film of any shape such as a flat plate shape and a cylindrical shape used in the above. In the case of the present invention, since the solid particle film forming apparatus includes only the electrodeposition bath, the electrodes, and the DC power supply, the solid oxide particles can be formed economically. According to the present invention, single-layer and multiple-layer solid acids
The present invention particularly provides an air electrode (lanthanum manganite), an electrolyte (zirconia, YSZ), and a fuel electrode (solid oxide fuel cell) because a solid oxide sintered film for a compound fuel cell can be obtained. This is a preferable method for producing nickel (YSZ cermet) or the like. Then, by using the sintered membrane obtained in the present invention, a portable small fuel cell can be manufactured.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Harumi Yokokawa 1-1-1, Higashi, Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology, Referee, Yoshio Ishii, Judge, Naoto Noda, Judge Mitsuo Karato (56) JP-A-4-93201 (JP, A) JP-A-1-110102 (JP, A) JP-A-8-78275 (JP, A) JP-A-3-501587 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B28B 1/00 C25D 1/00-1/18 C04B 41/80-41/91

Claims (7)

(57) [Claims] 1. An electrodeposition step in which solid oxide particles used for a solid oxide fuel cell are deposited in a film form on a surface of a graphite molded body as a substrate by electrophoretic deposition, and obtained by the electrodeposition step. the solid oxide particle film graphite molded body having a surface with and fired in air to form the solid oxide particle film on the sintered film, the solid oxide comprising a firing step of oxidizing and removing the graphite A method for producing a solid oxide sintered membrane for a fuel cell . 2. The method according to claim 1, wherein the solid oxide sintered film is a cylindrical film. 3. The method according to claim 1, wherein said solid oxide sintered film is made of lanthanum manganite. 4. A solid oxide particle to be used in a solid oxide fuel cell is formed on the surface of the sintered solid oxide film obtained in claim 1 as a substrate by electrophoretic deposition. Solid oxide for a solid oxide fuel cell having a laminated structure, comprising: an electrodeposition step of adhering to the substrate; and a firing step of firing a solid oxide sintered film having a surface of the solid oxide particle film obtained in the electrodeposition step. Method of manufacturing a sintered product film. 5. The method according to claim 4, wherein the solid oxide sintered film obtained in claim 1 as the substrate is a cylindrical lanthanum manganite sintered film. 6. A method according to claim 1, wherein the first solid oxide particles used in the solid oxide fuel cell are electrophoretically deposited on the surface of the solid oxide sintered film obtained in claim 1 as a substrate. A first electrodeposition step of attaching the film in the form of a film, and a second solid oxide particle used for a solid oxide fuel cell formed on the surface of the electrodeposited material obtained in the first electrodeposition step by electrophoretic deposition. A method for producing a solid oxide sintered film for a solid oxide fuel cell having a laminated structure, comprising: a second electrodeposition step of adhering to the substrate; and a firing step of firing the electrodeposit obtained in the second electrodeposition step. 7. The method according to claim 6, wherein the solid oxide sintered film as the base material is made of lanthanum manganite, the first solid particles are made of YSZ, and the second solid particles are made of a mixture of nickel carbonate and YSZ.