JP2003183891A - Production method for ceramics layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method for a ceramics layer capable of easily producing a high-quality ceramics layer on a porous member. <P>SOLUTION: A pair of positive and negative electrodes 3A and 3B are set in a suspension 9 containing YSZ particles 8 dispersed therein. At the circumference of the inner-side electrode 3A, a circular cylindrical fuel pole 10 is arranged. When a potential difference is given between both the electrodes 3A and 3B, the YSZ particles 8 move toward the inner-side electrode 3A by electrophoresis. Since the fuel pole 10 is arranged at the vicinity of the inner-side electrode 3A, the YSZ particles 8 coming toward the inner-side electrode 3A at this time deposit on the surface of the fuel pole 10, forming a solid electrolyte layer 11. Thus, a dense solid electrolyte layer 11 with a uniform thickness is directly formed on the surface of the fuel pole 10, facilitating the formation of a high-quality solid electrolyte layer 11. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for manufacturing a ceramic layer.

[0002]

2. Description of the Related Art Generally, a high temperature solid oxide fuel cell is
As shown in FIG. 6, for example, a fuel electrode 102 made of cermet of nickel oxide and stabilized zirconia and an air electrode 103 made of lanthanum strontium manganite are laminated via a solid electrolyte layer 104. There is. In the production of such a high temperature solid oxide fuel cell 101, one of the useful methods for forming the solid electrolyte layer 104 is, for example, the electrophoresis method disclosed in Japanese Patent Application Laid-Open No. 9-283161. This method is a molding method in which particles of an electrolyte material dispersed in a dispersion medium are deposited on an electrode by a DC electric field.

The solid electrolyte layer 104 is formed by the electrophoresis method through the following process (FIG. 7). First, a suspension 111 is prepared by dispersing yttria-stabilized zirconia (YSZ) particles 113 as an electrolyte material in a dispersion medium such as ethanol. YSZ particles 113
Is charged due to factors such as adsorption of ions by the dispersion medium and a difference in dielectric constant between the dispersion medium and the YSZ particles 113.
In this suspension 111, a pair of electrodes 112A, 112B
When a DC voltage is applied to both electrodes 112A and 112B to generate a predetermined potential difference, the charged YSZ particles 11
3 moves to one of the electrodes 112 under the influence of the electric field. In this way, Y that has moved onto the electrode 112
The SZ particles 113 are brought into an electrically neutral state and the electrode 1
Deposit and deposit on 12. Then, the solid electrolyte layer 104 is obtained by sintering the formed YSZ particle 113 layer.

At this time, the electrode 112A or 112B
By using the anode 102 or the cathode 103 as the solid electrolyte layer 104 directly on these surfaces.
Can be formed.

[0005]

However, in the electrophoretic method, it is necessary to apply a DC voltage to the pair of electrodes 112A and 112B to generate an electric field. Therefore, a conductive material must be used for the electrode 112. I won't. However, the fuel electrode 102 is generally formed of a material having no conductivity such as cermet of nickel oxide and stabilized zirconia. Therefore, the solid electrolyte layer 1 is formed on the fuel electrode 102.
In order to form 04, the fuel electrode 102 is subjected to reduction treatment, or as disclosed in Japanese Patent Laid-Open No. 10-284093, nickel is plated on the surface of the fuel electrode 102 in advance to make it conductive. It is necessary to impart conductivity by forming a thin film. Therefore, the process must be complicated.

Further, the fuel electrode 102 and the air electrode 103
Are generally porous and have numerous voids. When electrophoresis is performed using such a porous member as an electrode, the electrophoretic particles are only deposited on the surface of the porous member, and it is difficult to fill the voids with the electrophoretic particles. Therefore, as shown in FIG. 8, 3 is formed at the interface between the fuel electrode 102 or the air electrode 103 and the solid electrolyte layer 104.
A three-dimensional network structure is not formed, resulting in a structure having few active sites in the electrode reaction. Therefore, there is a limit to improving the performance of the fuel cell.

Further, when an aqueous solvent is used as the dispersion medium, when the applied voltage exceeds the electrolysis voltage value of the solvent, water is electrolyzed and bubbles are generated on the electrode 112. Therefore, when the YSZ particles 113 are deposited, there is a possibility that the bubbles may be caught. In order to avoid such a situation, a method of using an organic solvent which is not easily electrolyzed as a dispersion medium and further adding iodine for imparting conductivity to the solvent can be considered. However, from the viewpoint of environmental load, such a method is not very preferable.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a method of manufacturing a ceramics layer which can easily manufacture a good quality ceramics layer on a porous member.

[0009]

Means for Solving the Problems The inventors of the present invention have earnestly studied to develop a method for manufacturing a ceramics layer capable of easily manufacturing a good quality ceramics layer on a porous member, and have found the following findings. .

A pair of positive and negative electrodes are placed in a suspension in which ceramic particles are dispersed, and a potential difference is applied between the two electrodes. Then, due to the electrophoretic phenomenon, the ceramic particles move toward either of the electrodes. At this time, since the porous member is provided on the path of the ceramic particles in the suspension, the ceramic particles moving in the suspension should adhere and deposit on the surface of the porous member. Becomes As a result, it has been found that even a non-conductive porous member can directly deposit ceramic particles on the surface thereof.

Further, instead of using the porous member itself as an electrode, by providing a porous member between a pair of electrodes,
The ceramic particles preferentially enter and adhere to the voids existing in the surface layer of the porous member during migration. It has been found that this makes it possible to form a three-dimensional network structure at the interface between the porous member and the ceramics layer and improve the adhesion between the two.

The method for producing a ceramic layer of the present invention is based on such a new finding, and a pair of positive and negative electrodes are provided in a suspension obtained by dispersing ceramic particles in a dispersion medium, A method of depositing the ceramic particles by an electrophoretic phenomenon by applying a potential difference between these two electrodes to form a ceramic layer, wherein the dispersion medium is provided in the suspension on the path of the ceramic particles. Is provided while restricting the passage of the ceramic particles, and the ceramic layer is formed on the surface of the porous member.

The material of the electrode used in the present invention may be any conductive material usually used in electrophoresis, and examples thereof include copper, platinum, stainless steel and nickel. Of these materials, platinum is preferable. Further, when water is used as the dispersion medium and when bubbles (hydrogen or oxygen) are remarkably generated in the vicinity of the electrode, it is preferable to use a hydrogen storage alloy such as palladium or palladium-silver.

It is desirable to use an electrode having a shape that conforms to the shape of the porous member, and a mesh-shaped or wire-shaped electrode may be used if necessary.

The ceramic particles used in the present invention are not particularly limited, but for example, alumina, silica,
Examples include magnesia, titania and hydroxyapatite. The concentration of ceramic particles in the suspension is
1% to 2% by weight is preferred.

The present invention is particularly preferably applicable to the production of a solid oxide fuel cell in which the adhesion between the fuel electrode or the air electrode and the solid electrolyte layer is required. That is,
By using the air electrode or the fuel electrode as the porous member and the solid electrolyte particles forming the solid electrolyte layer as the ceramic particles, it is possible to form the solid electrolyte layer with good quality on the fuel electrode or the air electrode. it can.
Examples of solid electrolyte particles that can be used in this case include stabilized zirconia to which yttrium or scandium is added, lanthanum gallate-based materials, and the like.

The porous member used in the present invention is
Since it is not necessary to use it as an electrode, it is not limited to a conductive air electrode, and a non-conductive fuel electrode can also be used. Further, the shape of the porous member is not particularly limited, and various shapes such as a rectangular tube, a cylindrical shape such as a cylinder, and a flat shape may be used according to the purpose. it can.

The phrase "permitting passage of the dispersion medium while restricting passage of the ceramic particles" does not necessarily mean that the ceramic particles do not pass at all, but the ceramic particles are not deposited on the surface by electrophoresis. It means that it is porous enough to be laminated.

In particular, when the voids present in the porous member are very large and the surface irregularities are large, the ceramic particles easily flow into the voids, but are unlikely to adhere to the convex portions. However, the surface of the ceramic layer may not be uniform. Particularly, in the case of a thin ceramic layer, such an adverse effect is likely to occur.

In such a case, first, a porous member is provided on the path of the ceramic particles in the suspension,
Ceramic particles are deposited in the voids present in the surface layer of this porous member. Next, ceramic particles are further deposited using this porous member as one electrode. By thus forming the ceramic layer through the two-step process, the surface of the porous member is completely covered.
It is possible to form a uniform and dense ceramic layer. When this method is applied, it is necessary that the porous member has conductivity.

The dispersion medium used in the present invention is not particularly limited as long as it is a solvent usually used for electrophoresis, and for example, water, ethanol, acetylacetone or the like or a mixture thereof can be used. In addition to the dispersion medium, acrylic emulsion, water glass,
Binders such as polyvinyl alcohol and vinyl acetate, polyacrylic acid-based, sodium phosphate, polycarboxylic acid-based, lignin sulfonic acid-based peptizers, acid or alkali for adjusting the pH of the suspension, etc. You may add suitably in order to carry out the lamination | stacking of the ceramic particle | grains by migration smoothly.

The current-carrying conditions of the electrophoresis of the present invention vary depending on the arrangement of the electrodes and porous members used, the type of ceramic particles and the dispersion medium, and are not particularly limited,
When ethanol is used as the dispersion medium and the stabilized zirconia particles are used as the ceramic particles, the voltage is 500 to 10
It is preferable that the voltage is about 00V and the energization time is about 2 to 4 minutes.

According to the method for producing a ceramic layer of the present invention, a dense ceramic layer can be formed on the entire surface of the porous member. However, when further quality assurance is required, the ceramic layer after firing is required. It is effective to dip the same into a sol of homogeneous material. Alternatively, such a sol may be used for further electrophoresis. Thereby, the densification of the ceramic layer can be made more complete.

[0024]

According to the invention of claim 1, even if the porous member is a non-conductive member, the ceramic is directly subjected to no reduction treatment or formation of a conductive thin film. The particles can be laminated. This allows
The conventional conductive thin film coating process can be omitted, and the process can be simplified. Further, since a conductive thin film is unnecessary, a pure ceramic layer can be obtained, and the thickness can be easily controlled, so that an extremely thin layer can be formed. Further, the ceramic particles preferentially enter and adhere to the voids existing in the surface layer of the porous member during migration. This can improve the adhesion between the porous member and the ceramic layer.

In addition, since the porous member on which the ceramics layer is formed is not used directly as an electrode, even if a bubble is generated on the electrode due to electrolysis of water, the bubble is caught in the ceramics layer. There is no. Therefore, it is possible to use an aqueous solvent having a small environmental load as the dispersion medium. This eliminates the need for a large-scale device or the like for preventing adverse effects on the environment, and simplifies production equipment. In addition, since it is not necessary to add the conductivity-imparting material to the water-based solvent, the manufacturing cost can be reduced.

According to the second aspect of the invention, a porous member is provided on the path of the ceramic particles in the suspension, and the first laminating step of depositing the ceramic particles on the surface of the porous member; Using the porous member as one of the electrodes, a ceramic layer is formed through a second laminating step of depositing ceramic particles on the surface of the porous member. As a result, even if the voids present in the surface layer of the porous member are very large and the surface irregularities are large, a dense ceramic layer that fills the voids with ceramic particles and covers the surface of the porous member is formed. be able to.

According to the inventions of claims 3 and 4,
Adhesion between the fuel electrode or the air electrode and the solid electrolyte layer can be improved, and many three-phase interfaces of the fuel electrode (air electrode) -solid electrolyte layer-gas ideal for the electrode structure of the fuel cell can be formed. it can. As a result, it is possible to provide a solid oxide fuel cell having a large number of active sites due to electrode reactions and having good performance. Moreover, since a uniform and dense solid electrolyte layer can be formed, a solid oxide fuel cell with stable voltage can be provided.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION <First Embodiment> A first embodiment of the present invention will be described below with reference to FIGS. 1 and 2.
The details will be described.

In this embodiment, a method for forming the solid electrolyte layer 11 on the surface of the fuel electrode 10 of the high temperature solid oxide fuel cell will be described as an example of the production of the ceramic layer.

Apparatus 1 for manufacturing a ceramics layer of this embodiment
(Hereinafter, it is abbreviated as "manufacturing apparatus 1".) Is shown in FIG. The manufacturing apparatus 1 includes a container 2 capable of storing a suspension 9 in which YSZ particles 8 (corresponding to the solid electrolyte particles of the present invention) are dispersed in ethanol 7 (corresponding to the dispersion medium of the present invention), It is provided with a pair of positive and negative electrodes 3A and 3B which can be immersed in the suspension 9 in the container 2.

The container 2 of the manufacturing apparatus 1 is formed of, for example, acrylonitrile-styrene-butadiene resin (ABS resin) in a bottomed cylindrical shape, and the suspension 9 is contained therein.
Can be stored. A stirrer 6 for stirring the suspension 9 is placed at the bottom of the container 2.

Inside the container 2, the inner electrode 3A and the outer electrode 3
B and the fuel electrode 10 are installed.

The fuel electrode 10 is used for a high temperature solid oxide fuel cell, and is made of, for example, a cermet of nickel oxide and stabilized zirconia, and has an outer diameter of 10 mm,
It is a porous member formed into a cylindrical shape having an inner diameter of 6 mm.
The pore diameter of the fuel electrode 10 is set to an average pore diameter that allows the passage of the ethanol 7 while restricting the passage of the YSZ particles 8. The fuel electrode 10 is held by a support arm (not shown) provided near the upper edge of the container 2 and hangs down at a central position in the container 2.

The inner electrode 3A is a wire made of stainless steel having substantially the same length as that of the fuel electrode 10.
It is inserted inside 0. The upper end thereof is held by a support arm (not shown) like the fuel electrode 10.

The outer electrode 3B is formed of a stainless net into a cylindrical shape having an inner diameter of 20 mm. The outer electrode 3B is positioned so as to be coaxial with the fuel electrode 10, and is installed in the container 2 so as to surround the entire circumference of the fuel electrode 10.

The inner electrode 3A and the outer electrode 3B are connected to the negative side terminal and the positive side terminal of the DC power source 5 by the wiring 4, respectively.

1% by weight to 3% of YSZ particles 8 in ethanol 7 is placed in the container 2 of the manufacturing apparatus 1 configured as described above.
The suspension 9 uniformly suspended so as to have a weight% is poured in so that the entire fuel electrode 10 is immersed.

Next, the container 2 is placed on a stirrer (not shown), the stirring bar 6 is rotated and the suspension 9 is stirred, and the DC power supply 5 is turned on to switch both electrodes 3A and 3B.
A voltage of 500 V is applied between them. As a result, the YSZ particles 8 move toward the inner electrode 3A due to the electrophoretic phenomenon,
Deposit on the surface of the fuel electrode 10.

After the voltage application operation is completed, the fuel electrode 10 on which the YSZ particles 8 have been deposited is pulled up and sintered at 1400 ° C. for 10 hours to obtain the solid electrolyte layer 11. The state of the cross section of the fuel electrode 10 and the solid electrolyte layer 11 at this time is shown in FIG. As is clear from this figure, YS
The Z particles 8 are also filled in the voids 10A existing on the surface of the fuel electrode 10, and the formed solid electrolyte layer 11 has a three-dimensional network structure at the interface with the fuel electrode 10.
The structure had good contact with the fuel electrode 10. Further, the solid electrolyte layer 11 had a very dense and uniform thickness over the entire length and circumference, and had good quality with almost no pinholes.

If it is desired that the solid electrolyte layer 11 be completely densified, dipping may be performed on the zirconia sol after firing.

As described above, according to the present embodiment, even with the non-conductive fuel electrode 10, the solid electrolyte layer 11 is directly formed without performing reduction treatment or formation treatment of the conductive thin film. be able to. This makes it possible to simplify the process and to form a very dense layer having a uniform thickness. Furthermore, YSZ particles 8
Preferentially enters and adheres to the voids 10A existing in the surface layer of the fuel electrode 10 during migration. As a result, the adhesion between the fuel electrode 10 and the solid electrolyte layer 11 can be improved, and many three-phase interfaces of the fuel electrode 10-solid electrolyte layer 11-gas can be formed. As a result, a solid oxide fuel cell having stable voltage and good performance can be provided.

<Second Embodiment> Hereinafter, a second embodiment of the present invention will be described in detail with reference to FIGS. 3 and 4.

The main difference between the method of manufacturing the solid electrolyte layer 21 of this embodiment and the method of manufacturing of the first embodiment is that the air electrode 20 is provided on the path of the YSZ particles 8 in the suspension 9 and A first lamination step of depositing the YSZ particles 8 on the surface of the air electrode 20, and a second lamination step of depositing the YSZ particles 8 on the surface of the air electrode 20 using the air electrode 20 as one electrode. To form the solid electrolyte layer 21. In the present embodiment, the same components as those in the first embodiment are designated by the same reference numerals and the description thereof will be omitted.

In this embodiment, an air electrode 20 is installed in the container 2 instead of the fuel electrode 10 in the manufacturing apparatus 1 having the same structure as the first embodiment. The air electrode 20 of the present embodiment is used for a high temperature solid oxide fuel cell, and is made of, for example, lanthanum strontium manganite, and is a porous member formed into a cylindrical shape having an outer diameter of 10 mm and an inner diameter of 6 mm. Therefore, the void 20A is larger than the size of the deposited YSZ particles 8. The air electrode 20 has conductivity and can be used as an electrode.

The air electrode 20 is held by a support arm (not shown) provided near the upper edge of the container 2 as in the first embodiment, and hangs down in the center of the container 2.

In the first laminating step, the inner electrode 3A is inserted inside the air electrode 20 as in the first embodiment. And these inner electrode 3A and outer electrode 3B
Are respectively connected to the negative side terminal and the positive side terminal of the DC power supply 5 by the wiring 4.

1% by weight to 3% of YSZ particles 8 in ethanol 7 is placed in the container 2 of the manufacturing apparatus 1 configured as described above.
A suspension 9 uniformly suspended so as to have a weight% is poured in so that the entire air electrode 20 is immersed (FIG. 3).
A).

Next, the container 2 is placed on a stirrer (not shown), the stirring bar 6 is rotated to stir the suspension 9, and the DC power source 5 is turned on to switch both electrodes 3A and 3B.
A voltage of 500 V is applied between them. As a result, the YSZ particles 8 move toward the inner electrode 3A due to the electrophoretic phenomenon,
Deposit on the surface of the air electrode 20.

Here, in the air electrode 20 of this embodiment, the void 20A is larger than the size of the YSZ particles 8. Therefore, the YSZ particles 8 easily flow into the voids 20A, and the YSZ particles 8 are concentratedly deposited inside the voids 20A (FIG. 3B). On the other hand, particles 20B forming the air electrode 20
The YSZ particles 8 are unlikely to adhere to the protruding portions. Therefore, the formed solid electrolyte layer 21 may have irregularities or pinholes 22.

Next, the second laminating step is performed. Second
In the laminating step, the inner electrode 3A is removed, and the negative wiring 4 of the DC power supply 5 is directly connected to the air electrode 20 (FIG. 4A). That is, the air electrode 20 itself is used as the cathode.

In this state, while rotating the stirrer 6 to stir the suspension 9, the DC power source 5 is turned on to apply a voltage of 500 V between the air electrode 20 and the electrode 3B. As a result, the YSZ particles 8 are moved to the air electrode 2 due to the electrophoresis phenomenon.
It moves toward 0 and accumulates on the surface of the cathode 20 (FIG. 4).
B). As a result, the YSZ particles 8 are deposited while filling the irregularities and the pinholes 22 remaining on the surface of the solid electrolyte layer 21 formed in the first stacking step. As a result, a uniform and dense solid electrolyte layer 21 that completely covers the surface of the air electrode 20 is formed.

After the voltage application operation is completed, the air electrode 20 on which the YSZ particles 8 are deposited is pulled up and sintered at 1400 ° C. for 10 hours to obtain the solid electrolyte layer 21. At this time, as in the first embodiment, the YSZ particles 8 are also filled in the voids 20A existing in the surface layer of the air electrode 20, and the formed solid electrolyte layer 21 is three-dimensionally formed at the interface with the air electrode 20. It has a general network structure and has a good contact property with the air electrode 20. Further, the solid electrolyte layer 21 had a very dense and uniform thickness over the entire length and circumference, and had good quality with almost no pinholes.

As described above, according to the present embodiment, even when the void 20A existing in the air electrode 20 is very large and the surface irregularities are large, the YSZ particles 8 are filled in the void 20A and the air electrode 20A is filled. A dense solid electrolyte layer 21 can be formed on the surface of 20. Thereby, similarly to the first embodiment, it is possible to provide a solid oxide fuel cell with stable voltage and good performance.

<Third Embodiment> The third embodiment of the present invention will be described in detail below with reference to FIG.

The main difference between the manufacturing method of the solid electrolyte layer 31 of this embodiment and the manufacturing method of each of the above-mentioned embodiments is that water 33 is used as the dispersion medium of the suspension 32. In this embodiment, the same components as those in the above-mentioned respective embodiments are designated by the same reference numerals, and the description thereof will be omitted.

In this embodiment, an air electrode 30 is installed in the container 2 instead of the fuel electrode 10 in the manufacturing apparatus 1 having the same structure as that of the first embodiment. The air electrode 30 of the present embodiment is used for a high temperature solid oxide fuel cell, and is made of, for example, a composite material of lanthanum strontium manganite and stabilized zirconia, and formed into a cylindrical shape similar to that of the first embodiment. Is a porous member.

This air electrode 30 is installed in the container 2 of the manufacturing apparatus 1 as in the first embodiment. Then, a suspension 32 in which the YSZ particles 8 are uniformly suspended in water 33 to be 1% by weight is poured into the container 2 so that the entire air electrode 30 is immersed in the suspension 32. To do.

Next, as in the first embodiment, while rotating the stirrer 6 to stir the suspension 32, the DC power source 5 is turned on and a voltage of 13V to 15V is applied between the electrodes 3A and 3B. Is applied. As a result, the YSZ particles 8 move toward the inner electrode 3A due to the electrophoretic phenomenon and are deposited on the surface of the air electrode 30.

At this time, the water 33 as the dispersion medium is electrolyzed, and bubbles 34 of hydrogen are produced on the inner electrode 3A and oxygen bubbles are produced on the outer electrode 3B. However, since the air electrode 30 on which the YSZ particles 8 are deposited is not directly used as an electrode but is installed as a separate member between the electrodes 3A and 3B, air bubbles 34 are trapped during the deposition. It doesn't come out.

After the voltage application operation is completed, the air electrode 30 on which the YSZ particles 8 are deposited is pulled up and sintered at 1400 ° C. for 10 hours to obtain the solid electrolyte layer 31. Although not shown in detail, also in this embodiment, the formed solid electrolyte layer 31 has a three-dimensional network structure at the interface with the air electrode 30 and has a good contact property with the air electrode 30. Was there. In addition, the solid electrolyte layer 31 had a very dense and uniform thickness over the entire length and circumference, and had good quality with almost no pinholes. Further, entrapment of bubbles in the solid electrolyte layer 31 was not observed.

As described above, according to this embodiment, the water 33
Solid electrolyte layer 31 of bubbles 34 generated by electrolysis of
The solid electrolyte layer 31 having good quality as in the first embodiment can be formed by avoiding the involvement of the solid electrolyte layer 31.

The present invention can be modified and implemented as follows. Further, the technical scope of the present invention is not limited to these embodiments and extends to an equivalent range.

(1) In the first embodiment, the solid electrolyte layer 11 is formed on the outer surface of the fuel electrode 10. However, the solid electrolyte layer 11 is laminated inside the fuel electrode 10 by selecting appropriate conditions. You can also let it. Further, the air electrode 20 may be used instead of the fuel electrode 10 to similarly form a solid electrolyte layer inside or outside thereof.

(2) In each of the above embodiments, the cylindrical fuel electrode 10 and the air electrode 20 are used, but the shape of the porous member is not limited to that of each of the above embodiments, and for example, a flat plate-shaped member is used. You can also

(3) In the above embodiments, the outer electrode 3B is used.
Was used as the anode, and the inner electrode 3A or the air electrode 20 was used as the cathode. However, the arrangement of the electrodes is not limited to those in each of the above-described embodiments, and electrophoresis is performed by reversing the positive and negative depending on the type of ceramic particles or dispersion medium. May be.

[Brief description of drawings]

FIG. 1 is a perspective view of a solid electrolyte layer manufacturing apparatus according to a first embodiment.

FIG. 2 is a diagram showing a cross section of a fuel electrode and a solid electrolyte layer.

3A is a cross-sectional view of a solid electrolyte layer manufacturing apparatus performing a first stacking step in the second embodiment, and FIG. 3B is an enlarged view of a circle R in FIG. 3A.

4A is a cross-sectional view of a solid electrolyte layer manufacturing apparatus performing a second stacking step in the second embodiment, and FIG. 4B is an enlarged view of a circle S in FIG. 4A.

FIG. 5 is a sectional view of an apparatus for manufacturing a solid electrolyte layer according to a third embodiment.

FIG. 6 is a perspective view of a high temperature solid oxide fuel cell.

FIG. 7 is a perspective view of a conventional apparatus for manufacturing a solid electrolyte layer.

FIG. 8 is a view showing a cross section of a fuel electrode or an air electrode and a solid electrolyte layer by a conventional manufacturing method.

[Explanation of symbols]

3A, 3B ... Electrodes 7 ... Ethanol (dispersion medium) 8 ... YSZ particles (solid electrolyte particles) 9, 32 ... Suspension 10 ... Fuel pole 11, 21, 31 ... Solid electrolyte layer 20, 30 ... Air electrode 33 ... Water (dispersion medium)

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01M 8/02 H01M 8/12 8/12 C04B 35/00 F (72) Inventor Seiji Kanemura Hachioji, Tokyo Minami Osawa 1-1 Tokyo Metropolitan University Graduate School of Engineering (72) Inventor Juichi Hamagami 1-1 Hachioji City, Tokyo Minami Osawa 1-1 Tokyo Metropolitan University Graduate School of Engineering F-term (reference) 4G030 AA12 AA17 BA03 GA17 GA20 5H026 AA06 BB00 EE13

Claims (4)

[Claims] 1. A ceramic in which a pair of positive and negative electrodes are provided in a suspension in which ceramic particles are dispersed in a dispersion medium, and a potential difference is applied between these electrodes to deposit the ceramic particles by an electrophoretic phenomenon. A method of forming a layer, wherein in the suspension, a porous member for allowing passage of the dispersion medium while restricting passage of the ceramic particles is provided on a path of the ceramic particles. The ceramic layer is formed on the surface of the porous member. 2. A ceramic in which a pair of positive and negative electrodes are provided in a suspension in which ceramic particles are dispersed in a dispersion medium, and a potential difference is applied between these electrodes to deposit the ceramic particles by an electrophoretic phenomenon. A method for forming a layer, wherein a porous member that allows passage of the dispersion medium while restricting passage of the ceramic particles is provided on a path of the ceramic particles in the suspension, and the porous member is provided. A first laminating step of depositing ceramic particles on the surface of the porous member, and using the porous member as one of the positive and negative electrodes to deposit the ceramic particles on the surface of the porous member by an electrophoretic phenomenon. And a second laminating step for allowing the ceramic layer to be manufactured. 3. The ceramic layer is a solid electrolyte layer in a solid oxide fuel cell, the porous member is an air electrode or a fuel electrode in a solid oxide fuel cell, and the ceramic particles are the air electrode or a fuel electrode. The method for producing a ceramic layer according to claim 1, wherein the solid electrolyte particles are capable of forming the solid electrolyte layer by depositing on the surface of the ceramic layer. 4. The ceramic layer is a solid electrolyte layer in a solid oxide fuel cell, the porous member is an air electrode in a solid oxide fuel cell, and the ceramic particles are deposited on the surface of the air electrode. The method for producing a ceramics layer according to claim 2, wherein the solid electrolyte particles are capable of forming the solid electrolyte layer.