JPS5931183B2 - Manufacturing method of non-aqueous electrolyte battery - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvement of a nonaqueous electrolyte battery using manganese dioxide as an anode active material, and aims to improve discharge performance.

In nonaqueous electrolyte batteries, the cathode active material is lithium, sodium, aluminum, magnesium, etc., and the electrolyte is an organic liquid in which chloride, perchlorate, fluoroborate, etc. are dissolved in various organic solvents.゛Manganese dioxide with a type crystal structure and manganese dioxide obtained by heat treatment of this type manganese dioxide are commonly used as active materials because they have little dissolution during storage, have a high monopolar potential, and are inexpensive. Sufficient discharge performance cannot be obtained because the discharge utilization rate of the material is low.

The present invention eliminates these drawbacks, and examples thereof will be described below.

About 0,1 mol of an aqueous solution of potassium permanganate is heated to boiling, and a hydrochloric acid solution prepared by diluting concentrated hydrochloric acid with an equal amount of water is gradually added dropwise thereto to form a brown precipitate.

The solution containing this precipitate is left in the air for about one month, and then the solution is filtered and the precipitate is washed with water to obtain α-type manganese dioxide containing potassium in its crystal structure. 1st
The figure shows a non-aqueous electrolyte battery using modified manganese dioxide produced in the same way.
0 parts by weight, 15 parts by weight of a conductive aid made of phosphorous graphite, and 10 parts by weight of a binder made of a suspension of polyfluoroethylene are uniformly mixed and pressure-molded to form an anode 1D. After drying, this is inserted into the bottom of the anode can 2.

Next, a separator 3 and absorbent paper 4 were sequentially placed on the anode, a gasket 5 having an L-shaped cross section was fitted into the opening of the anode can 2, and equal amounts of propylene carbonate and dimethoxyethane were mixed. A predetermined amount of an electrolytic solution in which 1 mol/l of lithium perchlorate is dissolved is injected onto the liquid-absorbing paper 4. Next, the cathode terminal plate 7 containing the cathode 6 made of lithium is fitted into the gasket 5, and the opening edge of the anode can 2 is bent inward to form a button-type battery. Battery A obtained in Example, conventional battery B using electrolytic manganese dioxide (γ-MnO2) as the anode active material, and type 5 manganese dioxide at 400°C.
Figure 2 shows the discharge characteristics of a conventional battery C using a heat-treated anode active material connected to a load resistance of 5KΩ and continuously discharged at 20°C. It can be seen that battery A using modified manganese dioxide has a higher discharge capacity than the conventional battery B due to the high discharge utilization rate of the active material, and has stable discharge characteristics.
As described in the examples, when hydrochloric acid is added dropwise to the potassium permanganate solution, it is necessary to keep the potassium permanganate fermentation solution in a boiling state at all times.

When potassium permanganate and hydrochloric acid are reacted without heating, some unreacted hydrochloric acid remains in the solution. If hydrochloric acid is added to the boiling water, the hydrochloric acid that does not participate in the reaction becomes vapor and is removed from the reaction system, making it possible to efficiently produce manganese dioxide. Further, if the precipitate produced by the reaction of potassium permanganate and hydrochloric acid is immediately subjected to F separation, manganese dioxide having a δ-type crystal structure is obtained, but this is unsuitable because the discharge utilization rate is low.

In order to obtain α-type manganese dioxide containing potassium in the crystal structure as in the present invention, approximately 2
If left for more than a week, the desired manganese dioxide can be obtained. As mentioned above, the present invention involves adding hydrochloric acid dropwise to a boiling potassium permanganate solution to form a precipitate, and then leaving it at room temperature for two weeks or more to form a potassium-containing carbon dioxide having an α-type crystal structure. Manganese is produced and used as an anode active material, and the above-mentioned modified manganese dioxide has a high discharge utilization rate, especially in a non-aqueous electrolyte.
The discharge capacity of the battery can be increased.

[Brief explanation of drawings]

FIG. 1 is a sectional view of a non-aqueous electrolyte battery according to the present invention, and FIG. 2 is a diagram showing the discharge characteristics of the battery.

Claims (1)

[Claims] 1 Add hydrochloric acid dropwise to a boiling potassium permanganate solution to form a precipitate, then leave it at room temperature for two weeks or more to produce α-type manganese dioxide containing potassium. A method for producing a non-aqueous electrolyte battery characterized by using as an anode active material.