JPH01128366A - Solid electrolyte type fuel cell - Google Patents

Abstract

PURPOSE:To simplify the structure and assembling, and to reduce the manufacture cost by laminating alternatively zilconia thin plates and hollow ceramics plates, and furnishing flow ways to stream in and to discharge gases for operation in the laminated layer surfaces. CONSTITUTION:Hollow ceramics plates 2, 4, 6, and 8 and zilconia thin plates 3, 5, and 7 are laminated alternatively, and an upper lid 1 and a lower lid 9 are furnished at the upper side and at the lower side of them. Through pipes linking from the upper lid 1 to the lower lid 9, penetrating the laminated layers, are provided separately for the sorts of operation gas respectively. Oxygen flows through holes 11, 21, 24, 32, 42, 51, 61, 64, 72, 82, and 92, while the fuel gas and its reaction gas flow through holes 12, 22, 41, 44, 52, 62, 71, 81, 84, and 91. Since such a structure is simple and assembled easily, and it can be processed in the phase of green sheet, it is unnecessary to use a large scale of manufacturing process such as the EVD method, and the fuel cell can be manufactured at a low cost.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to fuel cells, and particularly to so-called third generation solid electrolyte fuel cells.

[Prior Art] A fuel cell is a battery that uses chemical substances commonly used as fuel, such as hydrogen, carbon monoxide, and hydrocarbons, as an active material. This is a device that electrochemically performs the oxidation reaction of fuel and directly converts the change in free energy during the oxidation process into electrical energy, and in principle can be expected to have high energy conversion efficiency.

Fuel cells can be classified into first generation (phosphoric acid type, low temperature type) and second generation (I-fused carbonate type,
It is divided into three generations (medium-temperature type) and third generation (solid electrolyte type, high-temperature type), and to date, development has focused on the first and second generations.

Meanwhile, research and development is also progressing domestically and internationally on third-generation solid oxide fuel cells, which are said to be able to generate electricity with higher efficiency. Currently, the specific cell structures of third generation solid oxide fuel cells include (i) bell spigot type, (if) disc type, (iii) circular tubular type, and (iv) cell on a base tube. A type that serially integrates (V
) - a structure in which a single tube is used as a single cell, (vi) a monolithic cell type, etc. are being considered. "About various battery manufacturing technologies" Electronic Technology Research Institute, Vol. 51, No. 4, pp. 59-71).

[Problems to be solved by the invention] By the way, in the conventional solid oxide fuel cell, 100
In order to operate at temperatures below 0° C. while keeping internal resistance low, it was necessary to form the electrolyte as thin as possible. However, conventional methods for manufacturing such electrolyte thin films include methods such as CVD and EVD that require large-scale equipment, and these methods have the problem of high costs.

In addition, electrolytes obtained using conventional thin film technologies such as the CVD method and EVD method described above contain many pores inside and cannot fully demonstrate the conductivity that the electrolyte matrix has. It was difficult to say that it was necessarily sufficient for use as an electrolyte in fuel cells.

Furthermore, since they are based on thin film technology or thermal spraying technology, they require a strong, porous base (generally called a backbone or reinforcing material), and many have complex structures, such as cylindrical shapes. - Also, a method has been developed to mold the electrolyte into a corrugated thin plate and incorporate it into the battery, but the structure is too complex and it is not possible to sufficiently and reliably seal the oxygen passage and the fuel passage during co-firing. There was a problem.

SUMMARY OF THE INVENTION In view of the problems of the conventional type described above, an object of the present invention is to provide a solid oxide fuel cell that has a simple structure, does not require complicated equipment, is easy to assemble, and is low cost. shall be.

[Means and effects for solving the problems] In order to achieve the above object, the solid oxide fuel cell according to the present invention includes a thin zirconia plate having a fuel electrode formed on one side and an oxygen electrode formed on the other side. In a solid oxide fuel cell, which has a multilayer cell structure in which layers and hollow ceramic plates are alternately stacked and has a sealed fuel chamber and an oxygen chamber alternately, a through hole for introducing fuel gas into the fuel chamber is provided. , a through hole for discharging unconsumed fuel gas and reaction-produced gas from the fuel chamber; a through hole for introducing oxygen into the oxygen chamber; and a through hole for discharging unconsumed oxygen from the oxygen chamber. The present invention is characterized in that through-holes are formed in the thin plate and the ceramic plate.

Due to the simple configuration of providing such a through hole, fuel and oxygen can be quickly introduced into and discharged from the fuel chamber and the oxygen chamber.

A solid oxide fuel cell having the above configuration is made by, for example, forming holes in a zirconia green sheet formed by a doctor blade method to form through holes for supplying and discharging gases to be consumed and gases produced by reaction. Holes are formed in the electrolyte green sheet and the insulating ceramic green sheet molded using the doctor blade method that does not allow oxygen ions to pass through, as well as through holes for supplying and discharging gases consumed and gases produced by reaction. It can be manufactured by alternately laminating green sheets for an insulating board with holes formed therein and firing them under predetermined conditions.

Furthermore, as another manufacturing method, a thin plate for electrolyte is produced by drilling holes in a zirconia green sheet formed by a doctor blade method to form through holes for supplying and discharging consumed gas and reaction-generated gas, and then firing. Insulation made by drilling holes in an insulating ceramic green sheet molded using the doctor blade method and impermeable to oxygen ions to form hollow parts and through holes for supplying and discharging gases consumed and reaction products, and then fired. It can also be manufactured by applying a bonding agent to the sealing portion of the plates, stacking them alternately, and firing them under predetermined conditions.

By forming a zirconia green sheet using the doctor blade method as described above, it is possible to easily and inexpensively produce a thin plate for electrolytes with a thickness of 0.1 mm or less, which is strong enough to be used as a single plate of a certain size. You can get it.

Examples of zirconia used in the electrolyte thin plate of the solid oxide fuel cell according to the present invention include ittria, calcia,
Zirconia stabilized or partially stabilized with magnesia or ceria can be used. Further, alumina or the like is preferable for the insulating plate.

In addition, by inserting ceramic tubes into the through holes for introducing gas from the outside and the through holes for discharging gas to the outside in the stack of green sheets, and firing and sealing them, a nozzle for supplying and discharging gas can be easily formed. It is.

Next, the configuration of the solid oxide fuel cell according to the present invention will be explained in detail using the drawings.

FIG. 1 is an external view showing the configuration of a solid oxide fuel cell according to the present invention. This figure shows the state immediately before laminating the electrolytic trade green sheet, the insulating board green sheet, and the upper and lower covers. Note that although the layers are stacked vertically in this example, this is for convenience of explanation, and the stacking direction may be any direction (for example, horizontal direction, etc.).
But that's fine.

In the figure, 1 is a green sheet that serves as the top lid;
A through hole 11 for introducing oxygen (air) and a through hole 12 for introducing fuel are opened. 2 is a green sheet for an insulating plate, which includes a through hole 21 for introducing oxygen, a hollow part 23 punched out to form an oxygen chamber, a through hole 24 for guiding oxygen further to the oxygen chamber below, and a through hole 24 for introducing oxygen into the oxygen chamber below. It has a through hole 22 leading to the chamber.

The green sheet 1 serving as the top cover and the green sheet 2 for the insulating plate are ceramic green sheets that are insulating and do not allow oxygen ions to pass through. 3 is an electrolyte green sheet made of stabilized or partially stabilized zirconia, and has through holes 31 through which fuel passes and through holes 32 through which oxygen passes. As described later, the upper surface of this electrolytic purchasing green sheet 3 (the side of the green sheet 2)
An oxygen electrode is formed on the bottom surface (green sheet 4 side), and a fuel electrode is formed on the bottom surface (the green sheet 4 side).

4 is a green sheet for an insulating board manufactured in the same manner as green sheet 2, and has a through hole 41 for introducing fuel.
, a hollow portion 43 serving as a fuel chamber, a through hole 44 that leads fuel to the fuel chamber further below, and a through hole 42 that leads oxygen to the oxygen chamber below. 5 is green sheet 3
This is an electrolyte green sheet made of zirconia similar to the above, and has through holes 51 through which oxygen passes and through holes 52 through which fuel passes. As will be described later, a fuel electrode is formed on the upper surface of the green sheet 5, and an air electrode is formed on the lower surface.

Reference numeral 6 designates an insulating green sheet manufactured in the same manner as the green sheets 2 and 4, which includes a through hole 61 for introducing oxygen, a hollow portion 63 that serves as an oxygen chamber, a through hole 64 for allowing oxygen to pass further downward, and a through hole 64 for passing fuel downward. It has a through hole 62 leading to the fuel chamber. 7 is an electrolytic green sheet made of zirconia similar to green sheet 3.5, and has through holes 71 for passing fuel and through holes 72 for passing oxygen. As will be described later, an air electrode is formed on the upper surface of this green sheet 7, and a fuel electrode is formed on the lower surface.

8 is an insulating green sheet manufactured in the same manner as green sheet 2.4.6, which includes a through hole 81 for introducing fuel, a hollow portion 83 that becomes a fuel chamber, a through hole 84 for allowing fuel to pass further downward, and an oxygen It has a through hole 82 through which it passes downward. 9 is a green sheet that serves as the lower lid, and contains unreacted fuel and reaction products (for example, H2O, Co
A through hole 91 for discharging oxygen (2, etc.) and a through hole 92 for discharging unreacted oxygen, etc. are opened.

FIG. 2 is a cross-sectional view of the laminate shown in FIG. 1. here,
Electrodes not shown in FIG. 1 are illustrated.

In the figure, 101 to 107 are interconnectors, which constitute the negative electrode of the battery from which electrons are led out. The electrodes connected to these interconnectors 101-107 are fuel electrodes 34°54.74. On the other hand, interconnectors 111 to 117 constituting the positive electrode of the battery are connected to the oxygen electrode 33°53.73. In addition, in the same figure, an interconnector is provided to connect each cell battery in parallel, but
It is also possible to connect each cell in series by appropriately arranging similar interconnectors.

FIG. 3(a) is a top view of the upper M1, and FIG. 3(b) is a top view of the clean sheet 2. Although these green sheets are cut into a square shape, the shape is not limited to this and may be any shape as long as it can be laminated to form a multilayer cell structure. Moreover, the hollow part 23 is shown in the same figure (
Although a concave punch is shown as shown in b), this shape can also be changed as appropriate.

FIG. 3(C) is a top view of the electrolyte green sheet 3, and FIG. 3(d) is a bottom view thereof. In the same figure (C), the shaded part is the electrode 33 which is an oxygen electrode, and this electrode 33 is connected to the interconnector 113. Similarly, on the lower surface of the green sheet 3, the shaded area in FIG. In addition, Fig. 3 (al
-A-A cross sections in (d) are shown as the cross sections of the corresponding members in FIG. 2, respectively.

As shown in FIG. 1.2, by stacking these members and closely adhering each member, a sealed fuel chamber and an oxygen chamber are formed, and the fuel cell according to the present invention is constructed.

[Example] Hereinafter, the present invention will be explained based on examples.

Example 1 Green sheet, electrode and interconnector (connection)
By preparing and simultaneously firing the following materials, a fuel cell having the configuration shown in FIGS. 1 to 3 described above was assembled.

■ First, use the electrolyte green sheet 3.5 as shown below.
．． I prepared 7.

An electrolyte green sheet having a thickness of 0.1 mm or less after firing was formed by a doctor blade method.

Ittria-stabilized zirconia was used as the electrolyte ceramic. 100m from this green sheet
Three m-square sheets were cut out.

These sheets were appropriately perforated to obtain a base material of Green Sea for Electrolyte 1-3.5.7. That is, for example, the base material that becomes the green sheet 3 is the above-mentioned 100+ nm square sheet as shown in FIG. 3(C).

As shown in (d), through holes 31 for interconnectors 103 and 113 and through holes for fuel and oxygen.
32 is opened using a press punch. green sheet 5.7
Holes are similarly drilled as shown in Figure 1.2.

Further, an air electrode paste was applied to one side of the sheet with holes formed in this way, and a fuel electrode paste was applied to the other side by screen printing. At the same time, these pastes were printed to fill in the through-holes for the interconnectors, thereby forming the electrodes and interconnectors in one piece. The printing paste for the fuel electrode is made by pulverizing nickel zirconia cermet powder to a particle size of 50 μm or less, mixing it with a cellulose binder, and making it into a paste with an organic solvent. In addition, the printing paste for the oxygen electrode is made by similarly pulverizing the oxide conductor powder to a particle size of 50 μm or less, mixing it with a cellulose-based binder, and making it into a paste with an organic solvent.

(2) Next, green sheets 2, 4, and 6°8 for insulating plates were prepared as follows.

A green sheet of alumina was formed using the doctor blade method to obtain the insulating plates that form the sealed chambers that serve as the fuel and oxygen chambers (air chambers). The thickness of the green sheet was 1 mm. 10 from this green sheet
Four sheets of 0 mm square size were cut out.

These sheets were appropriately perforated to obtain base materials for green sheets 2, 4, and 6.8 for insulating plates. That is, for example, the base material that becomes the green sheet 2 is the above-mentioned 100 mm square sheet with an interconnector 102 as shown in FIG. 3(b).
, 112, the through holes 21, 22.24 through which fuel and oxygen pass, and the hollow portion 23 connected to the through holes 21.24 are punched out by press punching. The green sheets 4, 6.8 are also perforated in the same manner as shown in FIG. 1.2. Note that the reason why the hollow portion 23 is formed into a concave shape is to allow gas to flow into the chamber, but the shape is not limited to this.

Furthermore, a conductive paste to be used as an interconnector was printed to fill in the through-hole portions of these insulator green sheets for interconnectors. This conductive paste is made by pulverizing tungsten powder to a particle size of 50 μm or less, mixing it with a cellulose binder, and making it into a paste with an organic solvent. In addition to tungsten, oxides having a perovskite structure or a Red3 structure can be used.

■Next, the upper lid and lower lid were prepared as follows.

The insulating thick plates serving as the upper and lower covers of the cell were made from green sheets of the same quality as those in ■, and were cut into 100 mm square pieces. For this purpose, a punching machine was used to open through holes for air and fuel inlets and outlets.

A through hole for an interconnector was further drilled in the upper lid, and an interconnector was formed in the same manner as in ①.

■ Electrolyte green sheet with holes cut and printed as described above (electrodes are also formed on both sides) 3, 5.
7 and green sheets 2, 4, and 6.8 for insulating thick plates are stacked alternately as shown in Fig. 1.2, and green sheets 1.9, which serve as upper and lower covers, are installed on the top and bottom surfaces. They were pressed into close contact at a pressure of 10 kg/cm2 or more.

■Through holes 11, 12°91 in upper M1 and lower cover 9.
A ceramic tube was inserted into 92. This is oxygen (
Acts as an inlet/outlet nozzle for air) and fuel.

(2) The laminated green sheet thus constructed was heated and maintained at a temperature of 1200° C. or higher for 30 minutes or more in the atmosphere to be fired. When the tubes are inserted into the upper and lower lids, the surrounding green sheet shrinks during firing, creating a perfect seal.

A solid oxide fuel cell with a multilayer cell structure could be obtained by the above steps (1) to (2).

Although nickel zirconia cermet was used as the raw material for the fuel electrode, other raw materials such as chromium or cobalt zirconia cermet, nickel oxide, a mixture of cerium oxide and calcium oxide, or a mixture of cerium oxide and yttrium oxide, etc. , paste-like products can also be used in the same manner as above.

Example 2 Next, electrodes and interconnector parts were formed by printing using pre-fired ceramics as shown below, and then these members were joined and sintered into dense layers to assemble a fuel cell. .

(2) First, using the same material as in Example 1, a green sheet was cut into the shape shown in FIG. 1.2 and holes were punched. Then, these members were fired to form an electrolyte thin plate and an insulating plate. Firing at 1200℃ in the air
The test was carried out under the condition that the heating was maintained at the above temperature for 30 minutes or more.

■ Electrodes were formed on this electrolyte by a printing method.

The electrodes may be formed by a vapor deposition method or the like in addition to a printing method. In addition, the through-hole portions that will become the interconnector portions were filled in with printing to form connections for each cell. The same electrode material as in Example 1 was used.

Similarly, through-hole portions that will become interconnectors of the insulating board constructed with (■) were filled in and printed in the same manner.

(2) The upper and lower lids were formed in the same manner as in Example 1, and ceramic tubes were inserted into the through holes of these green sheets and fired.

(2) The thin electrolyte plate, insulating plate, upper cover, and lower cover prepared as described above were heat-sealed by applying a bonding agent to the sealing portions of each member and bringing them into close contact. This bonded the electrolyte and the insulator.

As the bonding agent, an oxide having a melting point of 1000° C. or higher can be used. In particular, in order to improve bondability, it is better to contain the same components as the electrolyte and the insulator. For example, if the insulator is alumina, alumina, silica, magnesia, and ittria can be used as the bonding agent. Here, an alumina-based bonding agent is used.

For bonding, a method was used in which the above bonding agent was mixed with a cellulose-based or vinyl-based binder, made into a paste with an organic solvent, and applied to the bonding surfaces. Although hand application is sufficient, for example, screen printing is preferred in order to apply uniformly to ensure complete sealing. Here, it is applied by screen printing method and then pressurized (0,1 g/c+n”)
It was in close contact. This bonding is desirably performed under reduced pressure (vacuum).

The temperature of the bonding heating may be any temperature that is higher than the operating temperature of the fuel cell and allows the electrolyte and the insulator to be sintered and adhered to each other by the bonding agent. The temperature is generally 1000 to 1400°C. In this example, heating was performed at a temperature of about 1200°C.

Through the above steps (1) to (2), a solid oxide fuel cell with a multilayer cell structure could be obtained.

[Effects of the Invention] As explained above, the present invention provides a fuel cell having a multilayer cell structure in which zirconia electrolyte thin plates and ceramic thick plates as an insulator are alternately laminated. Through-holes are formed in the electrolyte thin plate and the insulator as flow paths for this purpose, so the following effects are achieved.

(1) The battery has a simple structure and is easy to assemble.

(2) Through the through holes, fuel and oxygen can be quickly introduced into and discharged from the fuel chamber and the oxygen chamber.

(3) According to the method of forming holes in the green sheet during manufacturing, large-scale equipment such as EVD method, CVD method, thermal spraying, etc. is not required and the cost is low.

[Brief explanation of the drawing]

FIG. 1 is an external view showing a configuration example of a solid oxide fuel cell according to the present invention, FIG. 2 is a cross-sectional view of the solid oxide fuel cell shown in FIG. 1, and FIG. FIG. 2 is a top view and a bottom view of a solid oxide fuel cell top cover, an insulating plate green sheet, and an electrolyte green sheet. 1: Top lid, 2.4, 6.8: Green sheet for insulation board, 3.5, 7
: Green sheet for electrolyte, 92 lower lid, 23.63: Hollow part that becomes oxygen chamber, 43.83: Hollow part that becomes fuel chamber, 33.53, 73: Oxygen electrode, 34.54.74 + fuel electrode, 101-107: Interconnectors serving as negative electrodes of batteries; 111-117; Interconnectors serving as positive electrodes of batteries.

Claims (3)

[Claims] (1) A multilayer cell structure is created in which thin zirconia plates with a fuel electrode formed on one side and an oxygen electrode formed on the other side and hollow ceramic plates are alternately laminated to alternately have sealed fuel chambers and oxygen chambers. A solid oxide fuel cell comprising: a through hole for introducing fuel gas into the fuel chamber; a through hole for discharging unconsumed fuel gas and reaction-produced gas from the fuel chamber; and an oxygen chamber. A solid oxide fuel cell characterized in that a through hole for introducing oxygen into the oxygen chamber and a through hole for discharging unconsumed oxygen from the oxygen chamber are formed in the thin plate and the ceramic plate. (2) The solid oxide fuel cell according to claim 1, wherein the through hole is formed by hole processing in the green sheet stage. (3) The claim includes a gas supply and discharge nozzle that is sealed by inserting a ceramic tube into a through hole for introducing gas from the outside and a through hole for discharging gas to the outside during the green sheet stage, and firing and sealing the tube. 1
The solid oxide fuel cell described in Section 1.