JPS5912567A - Organic electrolyte battery - Google Patents

Abstract

PURPOSE:To prevent bulging of a battery by using iron sulfide or a mixture of iron sulfide and cupric oxide as a positive active mass and adding acetylene black having specified bulk density as a conductive material. CONSTITUTION:A positive electrode 1 comprising a positive active mass prepared by adding as a conductive material acetylene black having a bulk density of 0.03-0.09g/ml to iron sulfide or a mixture of iron sulfide and cupric oxide, a negative electrode 7 using lithium as an active mass, and a separator 4 are accommodated into a positive can 3 and a negative can 5. They are sealed with a gasket 8 interposed to form an organic electrolyte battery. Since porosity of the positive electrode 1 makes as large as 45-60vol% by adding acetylene black, discharge reaction products are absorbed in the boids. Therefore, bulging of a battery by discharging is prevented and discharge capacity is increased.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvement of an organic electrolyte battery using acetylene black as a conductive aid, and an object of the present invention is to provide an organic electrolyte with a large discharge current.

For example, organic electrolyte batteries that use lithium as the negative electrode active material and iron sulfide as the positive electrode active material have a higher electrical capacity per unit volume than organic electrolyte batteries that use manganese dioxide or carbon fluoride as the positive electrode active material. It has the advantage of being large and having a discharge voltage of approximately 1.5V, making it compatible with Lecrancier batteries and silver oxide batteries.However, during discharge, lithium ions move to the positive electrode side and react with the positive electrode active material. 2) Since Li2S with low bulk density is generated in the positive electrode, the volume of the positive electrode increases as the N release progresses, causing swelling in the battery, which may damage battery application equipment. There is a problem in that the electrolyte is occluded and a shortage of liquid occurs near the negative electrode, which immediately impedes normal discharge.

Therefore, by using acetylene black as a conductive additive, the porosity of the positive electrode can be increased to 45 to 60% by volume (if iron sulfide is used alone in the positive electrode active material and 17), the porosity is 50 to 60% by volume, and iron When a mixture of sulfide of We have succeeded in preventing the swelling of the battery due to discharge by absorbing it into the storage space and improving the amount of discharged electricity, and we have already filed a patent application for this.

The present inventors (・Ma, - Based on the above research results,
Furthermore, as a result of various studies on the effect that the bulk density of the acetylene black used has on the performance of electrolyte oil, it was found that the bulk density of the acetylene black is 0.03 to 0.099 parts ml, especially O, Oa.
~0,06 f/+y+7! It was discovered that when using acetylene black, an organic electrolyte battery with a large amount of discharged electricity can be obtained, and the present invention was completed.

In the present invention, the bulk density is 0.03 to 0.09 fl
The reason why the amount of discharged electricity can be improved by using acetylene black of /ml is considered to be that the acetylene black has good dispersibility and is mixed uniformly when mixing the positive electrode mixture. If the bulk density is greater than 0.0997111t, the dispersion will be poor, resulting in a decrease in the amount of discharged electricity, which is undesirable.If the bulk density is less than 0A13fl/me, it will become too fluffy and difficult to handle, resulting in poor workability. It becomes impractical in some respects. In the present invention, all bulk densities are measured by the bulk density measuring method specified in JIS K 1469.

Next, the present invention will be explained with reference to Examples.

Figure 1 is a partial sectional view showing a button-shaped organic electrolyte battery. In the drawing, (1) is a positive electrode can, (2) is a stainless steel annular pedestal, (3) is a positive electrode can, and (4) is a positive electrode can. This is a seven-layer filter made of polypropylene nonwoven fabric. (5) is a negative electrode mill; (6) is a stainless steel mesh spot welded to the inner surface of the negative electrode mill (5);
The negative electrode is crimped onto the net (6). (8
) is an annular gasket made of polypropylene.

Examples 1 to 3 and Comparative Examples 1 to 2 Using acetylene black having the bulk density shown in Table 1, 15 parts (parts by weight, same hereinafter) of the acetylene black, 21 parts
A positive electrode mixture consisting of 41.5 parts of flC iron oxide, 41.5 parts of cupric oxide, and 2 parts of polytetrafluoroethylene was prepared, and the mixture powder was placed in a mold in which an annular pedestal (2) was placed. Filled with a diameter of 111ffN at a pressure of 500 kflα2,
Pressure molded into a disk shape with a thickness of 0.9 mm, and this was made into a positive electrode (1).
shall be.

The negative electrode (7) has a diameter of 8 mm and a thickness of 1 mm. (Using a lithium plate of Iff in which lithium oxide was dissolved at a ratio of 0.5 mol/β, the diameter was 11.6 r* with the configuration shown in Figure 1.
.

An organic ft electrolyte battery having a thickness of B and Omm was manufactured.

These batteries were placed at 20°C with a load of 15Ω and a final voltage of 1.
The amount of electricity discharged when continuously discharging up to 2■ is the 17th
""・ As shown in Table 1, the bulk density of acetylene black is in the range of 0.03 to 0.09 II/me, especially O, Oa
The amount of discharged electricity is large in the range of ~0.06 f/lnl.

In addition, the bulk density is 0. (In the case of 129 parts ml, the amount of discharged electricity is large, but the acetylene black is too fluffy and difficult to handle, and is not suitable for practical use from the viewpoint of workability.

In the examples, lithium was used as the negative electrode active material, and a mixture of iron disulfide and cupric oxide was used as the positive electrode active material, but the invention is not limited to this, and lithium could be used instead of lithium as the negative electrode active material. For example, sodium, calcium, aluminum, etc. can be used, and as the positive electrode active material, for example, ferrous sulfide, ferric sulfide,
Use alone or in combination of two or more of iron sulfides such as iron disulfide, sulfides of copper and nickel, oxides of manganese, copper, bismuth, lead, and carbon fluoride as appropriate. I can do it.

Similarly, the electrolytic solution is not limited to those exemplified in the examples, but can be made using perchlorine in a single or mixed solvent of two or more of globylene carbonate, γ-butyrolactone, tetrahydrofuran, 1,2-dimethoxyethane, dioxolane, etc. An electrolyte solution such as lithium oxide or lithium fluoride can be appropriately selected and used.

[Brief explanation of the drawing]

FIG. 1 is a partial sectional view showing an embodiment of the organic electrolyte battery of the present invention. (1)...Seitsubaki, (7)...Negative electrode patent applicant
Hitachi Maxell, Ltd.: Figure 1 34 l 333

Claims (1)

[Claims] 1. Bulk density 0. +13~0.09
An organic electrolyte battery characterized by using acetylene black of 9/ml. 2. The bulk density of acetylene black is 0.08~0,
06 f/ml. The organic electrolyte battery according to claim 1. 8. The organic electrolyte battery according to claim 1 or 2, wherein the negative electrode active material is lithium and the positive electrode active material is iron sulfide. 4. The organic electrolyte battery according to claim 1 or 2, wherein the negative electrode active material is lithium and the positive electrode active material is a mixture of iron sulfide and cupric oxide.