JPH0654667B2 - Non-aqueous electrolyte battery - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a non-aqueous electrolyte battery containing cupric oxide as a positive electrode active material.

(B) Conventional technology A non-aqueous electrolyte battery using cupric oxide as a positive electrode active material and lithium or a lithium alloy as a negative electrode active material is disclosed in, for example, Japanese Patent Publication No.
No. 9-33935, the battery voltage is about 1.4 V although it is slightly lower than 1.5 V, and therefore, such as existing silver oxide batteries and mercury batteries commonly used for power supplies of electronic devices. There is an advantage that it can be used interchangeably with a 5V system battery.

(C) Problems to be Solved by the Invention The present invention improves the battery voltage and the battery performance of a non-aqueous electrolyte battery using cupric oxide as a positive electrode active material and lithium or a lithium alloy as a negative electrode active material. Is to measure.

(D) Means for Solving the Problems The present invention provides a non-aqueous electrolytic solution comprising a negative electrode using lithium or a lithium alloy as an active material, a non-aqueous electrolytic solution, and a positive electrode using cupric oxide as an active material. A battery is characterized in that a two-component additive comprising iron disulfide and cuprous oxide is added to the positive electrode in an amount of 5 to 40% by weight with respect to cupric oxide.

(E) Operation When iron disulfide is added to the positive electrode whose active material is cupric oxide, the battery voltage rises slightly compared to the case of using cupric oxide alone.

Further, cuprous oxide added at the same time reacts with the residual water inside the battery or the invading water from the outside of the battery, so that it is possible to suppress the reaction of these water with the lithium negative electrode.

(F) Example 85% by weight of a positive electrode mixture in which 15% by weight of iron disulfide and 15% by weight of cuprous oxide were mixed with commercial grade cupric oxide.
In addition, acetylene black and graphite as a conductive agent
% And 5% by weight of fluorocarbon resin powder as a binder were added and mixed well, and this mixture was pressure-molded at a pressure of about 2 ton / cm ² to give a diameter of 15.0 mm and a thickness of 1.1 mm. A molded body is obtained, and this molded body is heat-treated at a temperature of 200 to 300 ° C. to obtain a positive electrode.

The negative electrode is obtained by rolling a lithium plate to a thickness of about 0.6 mm and punching this rolled lithium plate to a diameter of 15.0 mm.

The electrolytic solution is a mixed solvent of propylene carbonate and 1.2 dimethoxyethane in which 1 mol / mol of lithium perchlorate is dissolved, which is used by impregnating a separator with a diameter of 2
A battery (A) having a thickness of 0.0 mm and a thickness of 2.5 mm was prepared.

FIG. 1 shows a vertical cross-sectional view of the battery of the present invention. (1) is a positive electrode containing cupric oxide as an active material and iron disulfide and cuprous oxide are added, (2) is a lithium negative electrode, and (3) is It is a separator impregnated with an electrolytic solution. Also, (4) is the positive electrode ring, (5) is the positive electrode current collector,
(6) is a negative electrode current collector, (7) and (8) are positive and negative electrode outer cans, and (9) is an insulating packing.

Then, in order to examine the superiority of the battery of the present invention, a comparative battery (B) similar to the battery of the present invention was prepared except that iron disulfide and cuprous oxide were not added to the cupric oxide positive electrode.

FIG. 2 shows changes with time in internal resistance when these batteries were stored under conditions of a temperature of 60 ° C. and a humidity of 90%.

Further, FIG. 3 shows the discharge characteristics of these batteries at 20 ° C. and 5.6 KΩ constant load discharge, the solid line shows the initial characteristics, and the broken line shows the battery assembled and stored at a temperature of 60 ° C. and humidity of 90% for 20 days. The discharge characteristics after the operation are shown.

2 and 3 show that the battery (A) of the present invention has a higher battery voltage than the comparative battery (B) and has improved storage characteristics especially under high temperature and high humidity. .

To consider the reason for this, if iron disulfide is added first,
Since iron disulfide has a higher intrinsic potential than cupric oxide, it is considered that the battery voltage is higher than that of cupric oxide alone.

Further, since cuprous oxide added at the same time reacts with the residual water inside the battery or the invading water from outside the battery, it is possible to suppress the reaction of these water with the lithium negative electrode and improve the storage characteristics. Since the reaction product of cuprous oxide and water is cupric oxide and has the same composition as the active material, there is an advantage that the battery capacity can be increased.

(G) Effect of the Invention As described above, in the non-aqueous electrolyte battery provided with the positive electrode using cupric oxide as the active material, the two-component additive consisting of iron disulfide and cuprous oxide was added to the positive electrode. 5-4 for dicopper
The addition of 0% by weight makes it possible to obtain a 1.5 V non-aqueous electrolyte battery having an increased voltage and excellent storage characteristics, and its industrial value is extremely large.

[Brief description of drawings]

FIG. 1 is a vertical cross-sectional view of the battery of the present invention, FIG. 2 is a diagram showing the relationship between internal resistance and storage period, and FIG. 3 is a discharge characteristic of the battery. (1) …… Positive electrode, (2) …… Negative electrode, (3) …… Separator, (4)…
… Positive electrode ring, (5) …… Positive electrode current collector, (6) …… Negative electrode current collector, (7) (8) …… Positive and negative electrode outer can, (9) …… Insulation packing, (A) …… Inventive battery, (B) ... Comparative battery.

Claims (1)

[Claims] 1. A negative electrode using lithium or a lithium alloy as an active material, a non-aqueous electrolytic solution, and a positive electrode using cupric oxide as an active material, wherein the positive electrode contains iron disulfide and an oxide first oxide. A non-aqueous electrolyte battery, wherein a two-component additive made of one copper is added to the cupric oxide in an amount of 5 to 40% by weight.