WO1999016143A1

WO1999016143A1 - Sodium-sulfur battery

Info

Publication number: WO1999016143A1
Application number: PCT/JP1997/003336
Authority: WO
Inventors: Yoshimi Sato; Saburo Usami; Tadahiko Miyoshi; Hisamitsu Hato; Ryujiro Udo
Original assignee: Hitachi, Ltd.
Priority date: 1997-09-19
Filing date: 1997-09-19
Publication date: 1999-04-01

Abstract

In a sodium-sulfur battery in which a positive or negative electrode container flange formed by plastic molding, such as the press working, etc., is joined to an insulator ring, the occurence of a defective junction is prevented. The peripheral waviness of container flanges (3 and 4) caused by plastic molding is reduced by providing highly rigid bodies (7 and 7) formed by plastic molding which is performed simultaneously with, before, or after the plastic molding performed on the flanges (3 and 4) at the end sections of the flanges (3 and 4). Alternatively, the peripheral waviness of an aluminum or aluminum alloy ring member put on the joint surface of each container flange with the insulator ring having peripheral waviness caused by plastic molding is reduced by press-fitting and sticking aluminum or an aluminum alloy in and to the recessed section of the flange caused by the waviness while the joint surface of the flange is inserted into a planar rigid jig together with the aluminum or aluminum alloy ring member put on the surface and the jig is pressed against the flange.

Description

Specification

Technical field of sodium-sulfur battery

The present invention relates to a sulfur sulfur battery having a positive and negative electrode container flange structure suitable for plastic working such as pressing. Background art

The structure of a conventional sulfur battery is disclosed in, for example, JP-A-2-278671 and JP-A-7-94209. The structure is such that a cylinder is installed at the end of the negative electrode container flange ゃ positive electrode container flange to increase the joining distance by joining the cylindrical part by positioning during welding and welding, and to apply compressive stress to the joint part It is devised to do so. However, they are targeted at machined flanges. The positive and negative electrode container flanges are formed by plastic working such as pressing to reduce the circumferential undulation of the joint surface between the container flange and the insulating ring, which is a bottleneck for mass production, and to prevent poor joints at the joints by thermal pressure welding. No consideration was given to prevent it. Disclosure of the invention

In order to promote cost reduction and mass production of sodium sulfur batteries, it is effective to replace mechanical machining with plastic working such as pressing. It is an object of the present invention to provide a sodium-sulfur battery in which, in a plastically processed positive or negative electrode container flange, a circumferential undulation of a container flange serving as a joining surface with an insulating ring is reduced to prevent poor joining.

To achieve the above object, the first invention of the present application is to A high-rigidity battery is installed by plastic working at the end of the processing vessel flange, and the circumferential undulation of the joint surface with the insulating ring material is reduced to prevent poor joints. It is.

A second invention is a sodium-sulfur battery characterized in that the same cylinder or a tapered cylinder is provided as a highly rigid body.

A third invention is a sodium sulfur battery, wherein the flange end is wound or corrugated as a highly rigid body.

A fourth invention is a sodium-sulfur battery, characterized in that the rigid plate has a thickness that is twice or more the thickness of the press-formed plate of the container flange.

A fifth invention is a sodium sulfur battery characterized in that the high-rigidity body is installed by plastic working simultaneously with the formation of the negative electrode or positive electrode container flange. The sixth invention is a sodium sulfur battery _c characterized in that the high-rigidity body is installed either before or after the molding of the negative or positive electrode container flange. In addition, since the circumferential undulation is reduced, it is possible to prevent the bonding failure and to improve the Na resistance.

Also, in the seventh invention, at the stage of the raw material before the positive or negative electrode container flange is subjected to plastic working, the container flange material and the aluminum or aluminum alloy clad material are subjected to plastic working to form an insulating ring. This is a sodium-sulfur battery characterized by minimizing circumferential waviness at the joint surface to prevent poor joints.

Further, the eighth invention is characterized in that the aluminum or aluminum alloy is rubbed by rotating or reversely rotating it while pressing aluminum or an aluminum alloy on a joint surface of the positive electrode having a circumferential undulation and a flange of a single electrode and the insulating ring material, which is plastically worked. Ridge It was noted that the joint failure was prevented by filling the recess of the container flange having the aluminum or aluminum alloy with the aluminum or aluminum alloy and reducing the undulation of the aluminum or aluminum alloy to be the joining surface with the insulating ring. This is a sodium-sulfur battery.

FIG. 4 shows a state in which the negative electrode flange 3 is subjected to plastic working by press in claim 1. When forming the negative electrode container flange 3 from the disk using the die 13 and the punch 12, if no means is installed outside the negative electrode flange 3, large undulations in the circumferential direction will occur as shown in Fig. 4. As shown in FIG. 5, when the negative electrode flange 3 having the undulation is bonded to the insulating ring 2 by hot pressing through the aluminum alloy brazing 8 as shown in FIG. The α-alumina ring of the generated re-insulation ring 2 may crack. Also, Na resistance cannot be expected. On the other hand, as shown in FIGS. 2 and 3, by installing a cylinder of a highly rigid body 7 to increase rigidity at the end of the negative electrode container flange 3 or the positive electrode container flange 4, Alternatively, an effect of restraining the generation of circumferential undulation of the positive electrode flange 4 is produced, and it is possible to prevent poor connection of the heat-pressed portion and cracking of α-alumina of the insulating ring 2. Na resistance is also improved. Fig. 6 shows the measurement results of the circumferential waviness δ of the press-formed plastically processed negative electrode container flange. A comparison is made between the case where the rigid body 7 is installed at the end and the case where the rigid body 7 is not installed. When the high-rigidity body 7 is not installed, the maximum undulation force is 0.26. When the high-rigidity body 7 is installed, the maximum swelling is 0.08 mm, and the swelling can be reduced to about 1/3. I understand. In other words, by reducing the undulation of the container flange, it is possible to prevent poor connection of the heat-pressed portion and cracking of the insulating ring 2. Claims 2 to 6 have the same function and effect as claim 1. Claim 7 is more flexible than the material of the steel positive or negative flanges 3 and 4. The use of aluminum or aluminum alloy cladding material, which is a fragile material, utilizes the effect of reducing the undulation of the aluminum or aluminum alloy heat-welded joint surface.

Claim 8 aims at the same effect as claim 2, but claim 2 uses aluminum or aluminum alloy as the cladding material before plastic working, whereas claim 3 claims Although there is a difference in forming aluminum or aluminum alloy into a clad after plastic working of the container flange, the purpose of reducing the undulation of the joint surface and the effect of preventing a joint failure are the same. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows a sodium-sulfur battery according to the present invention. 2 and 3 show examples of application of the first invention of the present application. Fig. 4 shows the state of plastic working by press forming. Fig. 5 shows the undulation of the press-formed flange. FIG. 6 is a diagram comparing the undulations in the circumferential direction of the flange when the cylinder is installed as the highly rigid body of the second invention and when it is not installed. 7 to 9 show applied examples of the second invention, and FIGS. 10 to 14 show stress deformation examples of the first invention. No.

FIGS. 15 and 16 show an embodiment of the third invention. FIG. 17 shows an embodiment of the fourth invention. FIGS. 18 and 19 show an embodiment of the seventh invention.

FIG. 20 and FIG. 21 show an embodiment of the eighth invention. BEST MODE FOR CARRYING OUT THE INVENTION

One embodiment of the present invention is shown in FIG. 1, FIG. 2, and FIG. The sodium sulfur battery targeted by the present invention uses sodium as an edible electrode active material 5 and sulfur as a positive electrode active material 6 via a solid electrolyte tube 1 as shown in FIG. Α-aluminum separating the negative and positive electrodes from the upper opening of the bag tube 1 /

An insulating ring 2 made of metal is installed, and the negative electrode container flange 3 and the positive electrode container flange 4 manufactured by plastic working such as pressing on the insulating ring 2 are joined via an aluminum alloy of a brazing material 8. The structure is At the end of the flange 3 of the negative electrode container formed by plastic working such as pressing, a cylinder of a highly rigid body 7 is installed as shown in FIG. 2, and the flange 4 of the positive electrode container as shown in FIG. By installing the high-rigidity body 7 in which the cylinder of the rigidity body 7 is installed, it is possible to reduce circumferential waviness generated during plastic working of the negative electrode or the positive electrode container flanges 3 and 4. By reducing the undulations, it is possible to prevent the bonding failure of the thermal pressure welded joint, to prevent the α-alumina ring of the insulating ring 2 from cracking, and to improve the Na resistance.

Fig. 7 shows the case where the high rigid body 7 is a tapered cylinder, and Fig. 8 shows the case where the high rigid body 7 cylinder is installed at the end of the negative electrode container flange 3 in an upward direction different from that in Fig. 2. Similarly, in FIG. 9, a cylinder of a highly rigid body 7 facing downward from FIG. 3 is provided at the end of the flange 4 of the positive electrode container. In the high-rigidity member 7 shown in FIGS. 7 to 9, the effect of reducing the circumferential undulation of the flange is the same, but there is also a merit that the appearance of the joint can be easily inspected.

FIGS. 11 and 12 show modified examples of the first and second inventions. The negative electrode container flange 3 is formed into the shape shown in Fig. 10 by cutting it at the Α _ Α 'cross section after plastic working, and the undulation is the same as in Fig. 2 using the negative plastic container flange 3 as it is plastically processed. Can be reduced. Since the rigidity of the outer end is increased, the effect of suppressing the increase in circumferential undulation works, which has the effect of reducing undulation. In Fig. 13 and Fig. 14, even when cutting along the A-A cross section after plastic working, the rigidity inside increases, so the effect of suppressing the increase in circumferential undulations Since the undulation is further reduced, it is possible to prevent poor joining and to improve the Na resistance of the heat-welded portion. 10 to 14 can be similarly applied to the positive electrode container flange.

FIGS. 15 and 16 show an embodiment of the third invention. The case where the end portion of the flange is formed into a wound shape and a corrugated shape as the high rigid body 7 is shown.

FIG. 17 shows an embodiment of the fourth invention. A sodium-sulfur battery characterized by being formed as a highly rigid body 7 with a thickness that is at least twice the thickness of a press-formed plate of a container flange. The function and effect are the same as those of the first and second inventions.

FIGS. 18 and 19 show an embodiment of the seventh invention. In the state of the plate material shown in Fig. 18 before the plastic deformation of the negative electrode container flange 3, the container flange material 3 and aluminum or aluminum alloy 14 are used as a clad, and then formed into a plastic press Fig. 19 by plastic pressing. . Since aluminum or an aluminum alloy is soft, swelling of the bonding surface can be reduced by using the aluminum or aluminum alloy for the heat-bonding bonding surface, so that there is an effect that poor bonding can be prevented. The same can be applied to the positive electrode container flange.

FIG. 20 and FIG. 21 show an embodiment of claim 8. An aluminum or aluminum alloy ring 15 is sandwiched between a flat rigid jig 17 at the lower part of the negative electrode container flange 3 corresponding to the joint surface of the negative electrode flange 3 having undulations produced by plastic working with the insulating ring 2. By rotating or reversely rotating the flat rigid jig while pressing aluminum or aluminum alloy against the negative electrode container flange 3, the concave portion of the circumferential undulation of the negative electrode container flange 3 押し Pressing and filling aluminum or aluminum alloy 15 Aluminum or aluminum alloy to be joined to insulating ring 2 It has the effect of reducing the undulation on the lower surface of 15 and preventing the occurrence of poor joints at the heat-welded joint. 20 and 21 can be similarly applied to the positive electrode container flange. Industrial applicability

According to the present invention, since it can be manufactured by mechanical working and plastic working by pressing etc., it is possible to reduce circumferential undulation of the positive or negative electrode container flange, prevent poor joining with the insulator ring, and improve battery strength reliability. Can be improved.

Claims

Range of request

1. Using a solid electrolyte bag tube, sodium is used as the negative electrode active material and sulfur is used as the positive electrode active material. An insulator ring for separating the negative electrode and the positive electrode is installed at the upper opening of the solid electrolyte bag tube. In a blue sulfur battery having a negative electrode container flange and a positive electrode container flange joined to a body ring, at least one of the negative electrode container flange and the positive electrode container flange is formed by plastic working such as pressing. 2. A sulfur battery according to claim 1, wherein a high-rigidity body is provided at the end of the flange by plastic working to reduce circumferential waviness generated in the container flange.

2. In the sodium-sulfur battery according to claim 1, the negative electrode container flange or the positive electrode container flange formed by plastic working such as pressing is installed at least at one end of the battery by plastic working. A sodium-sulfur battery characterized in that it is a highly rigid body, cylinder or tapered cylinder.

3. The sodium-sulfur battery according to claim 1, wherein the negative electrode container flange or the positive electrode container flange formed by plastic working such as pressing is mounted on at least one end of the battery by plastic working. A sulfur battery as claimed in claim 1, wherein the end of the flange is wound or corrugated as a rigid body.

4. The sodium-sulfur battery according to claim 1, wherein the negative electrode container flange or the positive electrode container flange formed by plastic working such as pressing is mounted on at least one end of the battery by plastic working. A sodium sulfur battery, wherein the rigid body is formed with a thickness that is at least twice as large as the thickness of the press-formed plate of the container flange.

5. The plastic working according to any one of claims 1 to 4, A nutrient sulfur battery wherein a highly rigid body is installed simultaneously with the plastic working of either the anode container flange or the cathode container flange.

6. The high rigid body installed by the plastic working according to any one of claims 1 to 4, before or after the plastic working of any one of the negative electrode container flange and the positive electrode container flange. A natural sulfur battery characterized by being installed.

7. A sulfur battery according to any one of claims 1 to 6, wherein the high-rigid body installed by the plastic working is partially installed.

8. By using a clad material of the container flange material and aluminum or aluminum alloy for the plastic processing container flange, the circumferential undulation on the aluminum or aluminum alloy side, which is the joining surface with the insulator ring, is reduced by plastic processing. A sodium-sulfur battery, characterized in that:

9. The aluminum or aluminum alloy ring material is sandwiched by a flat rigid jig on the joint surface of the flange of the positive or negative electrode container with undulations formed by plastic working with the insulator ring, and the flat rigid jig is pushed in with the flat jig. By rotating or reversely rotating the aluminum or aluminum alloy, the aluminum or aluminum alloy is pressed into the recess of the processing vessel flange, which has rigidity with circumferential waviness. A natural sulfur battery characterized by reduced directional waviness.