JPS58194257A - Organic electrolytic battery - Google Patents

Abstract

PURPOSE:To reduce the voltage drop of an organic electrolytic battery at the beginning of discharge and increase discharge capacity by using a mixture of cubric oxide and nickel sulfide as the positive electrode active material. CONSTITUTION:Cupric oxide and nickel sulfide are mixed together at a proper ratio and a conductive material such as acetylene black and a bonding agent are mixed therewith. A sheet-type electrode is manufactured by pressurizing and supplying this mixture into an expanded net such as Ni and a positive electrode is obtained by punching the electrode in specified dimensions. The button-type organic electrolytic battery assembled by using this positive electrode has the voltage drop reduced at the beginning of discharge and the discharge capacity increased.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to organic electrolyte batteries, and particularly to improvements in positive electrode active materials thereof.

An organic electrolyte battery using cupric oxide (Cub) as a positive electrode active material has a theoretical electric capacity per unit volume of cupric oxide of 4.
It has a very high discharge voltage of 26Ah/cc, and when combined with a lithium negative electrode, the discharge voltage is 1.3 to 1.6V, making it compatible with conventional silver oxide batteries. Therefore, it is attracting attention as a power source for electronic watches.

However, this type of battery has problems with its discharge characteristics, particularly its voltage characteristics at the initial stage of discharge. That is, as shown in FIG. 1, a voltage drop phenomenon is observed from when discharge starts until the voltage stabilizes from -C.

Therefore, as a power source for an electronic watch where battery voltage is important, there is a risk that the accuracy of the electronic watch may be adversely affected, especially under severe conditions such as -10'C.

The present invention eliminates the above-mentioned drawbacks by using a mixture of cupric oxide and nickel sulfide as the positive electrode active material.

Next, the present invention will be explained by examples.

As shown in the table below, cupric oxide and nickel sulfide are mixed in various proportions, an acetylene blank as a conductive material and polyethylene tetrafluoride as a binder are mixed, and this mixture is made into an expanded material made of nickel. Continuously pressurizes the net,
Fill it and make a sheet electrode with a thickness of 0.35m+n.
This is punched out to a diameter of 68 mm to form a positive electrode.

Margin below (Unit double placement part) Using these positive electrodes, a button-shaped battery as shown in Figure 2 was assembled. In Figure 2, 1 is a polypropylene gasket attached to the edge of nickel-plated stainless steel with a thickness of 0.16 mm, and 3 is a 6.5 mm diameter gasket attached to the roughened inner surface of the sealing plate. .

This is a negative electrode made of metallic lithium with a thickness of 0.25 mm.

3 is a separator made of polypropylene nonwoven fabric, which is impregnated with an electrolytic solution in which 1 mole/2 of lithium perchlorate is dissolved in a solvent that is a mixture of propylene carbonate and 1,2-dimethoxyethane at a volume ratio of 1:1. are doing. Reference numeral 6 denotes the above-mentioned positive electrode, and one side thereof is provided with the above-mentioned net 6 as a current collector. 7 is a case made of 0.16 mm thick nickel-plated stainless steel with an outer diameter of 9.5 fins and a height of 1.2 mm.

Figure 3 shows the discharge curves when batteries made using the various positive electrodes described above were subjected to a constant discharge of 30 Ω at 20°C, and the lowest voltage value of the voltage drop in the early stage of discharge and the discharge capacity are shown in Figure 3. Shown in Figure 4.

As is clear from these figures, it can be seen that in the battery using a mixture of cupric oxide and nickel sulfide as the positive electrode active material, the drop in voltage at the early stage of discharge is suppressed. In particular, a cathode active material with a mixing ratio of about 10 to 60% by weight of sulfurized Ni-Kel increases the discharge capacity and also reduces the drop in voltage at the initial stage of discharge.

Active materials that generally have a higher discharge voltage than copper oxide include bismuth oxide, lead oxide, and antimony oxide, and when these are mixed with cupric oxide, the discharge curve shown in Figure 5 is shown. There are many things. In other words, A in Figure 5
In the region, substances having a higher discharge voltage than cupric oxide, such as bismuth oxide, react first, and in the subsequent region B, the reaction of cupric oxide proceeds. Therefore, in the AB boundary region, a drop in voltage is observed at the initial stage of discharge of cupric oxide.

However, when nickel sulfide is mixed with cupric oxide, the drop in voltage as described above is suppressed.

This is thought to be because it reacts and operates efficiently as a hybrid electrode from the early stage of discharge.

Although Ni3S2 was used as the nickel sulfide in the above embodiment, NiS, NtS2, etc. may be used similarly.

As described above, according to the present invention, it is possible to suppress the drop in voltage at the initial stage of discharge, and it is possible to eliminate the adverse effects of the drop in voltage on devices such as electronic watches.

[Brief explanation of the drawing]

Fig. 1 is a diagram showing voltage changes in the early stage of discharge of a conventional battery, Fig. 2 is a half-sectional view of a battery according to an embodiment of the present invention, and Fig. 3 is a diagram showing various mixed samples of cupric oxide and nickel sulfide. Figure 4 shows the relationship between the mixing ratio of hexagonal cupric oxide and nickel sulfide and the minimum voltage value and discharge capacity at the initial stage of discharge. Figure 5 shows the discharge curve of the battery used. The discharge curve of a battery using a positive electrode is shown. 3...Φ...Negative electrode, 4...Separator, 60
...0 positive electrode. Name of agent: Patent attorney Toshio Nakao and 1 other person No. 4
Figure 5 Ferrous II Introduction (In-)

Claims (1)

[Claims] An organic electrolyte battery with a positive electrode whose active material is a mixture of cupric oxide and nickel sulfide.