JPS60200464A - Nonaqueous-solvent cell - Google Patents

Abstract

PURPOSE:To provide a nonaqueous-solvent cell whose voltage drop is small even at the initial stage of large-current discharge, by using an electrolyte subjected to an electrical current treatment by using a pair of an anode of a light metal and a cathode of carbon. CONSTITUTION:Before an electrolyte 13 comprising 1.5mol/l of aluminum chloride and 1.5mol/l of lithium chloride dissolved in thionyl chloride is injected into a can 1 through a tubular anode 10, the electrolyte is subjected to an electrical current treatment with an electrical current of 100mA per 10ml of the electrolyte for 10hr by using a pair of an anode of lithium and a cathode of a porous carbonaceous piece chiefly made of acetylene black. A cell A, which is an embodiment of the present invention and includes the electrolyte 13 subjected to the electrical current treatment before injected into the can 1, undergoes a smaller voltage drop at the initial stage of discharge than a conventional cell B including the electrolyte not subjected to the electrical current treatment, as shown in the drawing.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a non-aqueous solvent battery, and more particularly, to a non-aqueous solvent battery in which an electrolytic solution that also serves as a positive electrode active material is improved by %.

[Technical background of the invention and its problems]

Nonaqueous solvent batteries that use light metals such as lithium, sodium, and aluminum as negative electrode active materials have a high energy density, poor storage characteristics, and a wide operating temperature range, so they are used in calculators, watches, and memories. It is widely used as a backup battery. Among them, lithium is used for the negative electrode, and thionyl chloride (5ocz, ) is used as the positive electrode active material.
Batteries using sulfur oxyhalides, such as sulfuryl chloride (802Ct, ), are attracting attention because of their particularly high energy density. Such cells have a positive electrode that is also a carbon and metal current collector, typically aluminum chloride (ArCI!3), aluminum bromide (AI!Br
A liquid sulfur oxyhalide obtained by dissolving a Lewis acid such as 5) and a Lewis base such as lithium chloride or lithium bromide is used as the electrolyte. Therefore, the liquid oxyhalide serves both as a positive electrode active material and as an electrolyte, and by using a positive electrode with an appropriate shape, a battery with excellent high rate discharge characteristics can be expected.

By the way, in the above-mentioned battery, since the sulfur oxyhalide which is the positive electrode active material is in direct contact with the lithium of the negative electrode, a LiC/film which is a reaction product is generated on the surface of the negative electrode lithium. This LiC/film is a negative electrode lithium
It has the function of preventing direct contact with oxyhalides and serves to prevent battery capacity deterioration during storage. However, during discharge, it acts as a resistance component and causes a voltage drop in the early stage of discharge. The degree of this voltage drop is negligible when the discharge current is minute on the μA order, but
In the case of large current discharge, it cannot be ignored, especially when stored at high temperatures for a long time, LiCl! After considerable film growth has occurred or during discharge at low temperatures, a significant voltage drop occurs at the beginning of discharge.
There was a problem in that it took a considerable amount of time for the voltage to recover to a predetermined level.

[Purpose of the invention]

The present invention is intended to provide a non-aqueous solvent battery that exhibits a small voltage drop even in the early stages of high current discharge.

[Summary of the invention]

The present invention provides a non-aqueous solvent battery comprising a negative electrode made of a light metal such as lithium, a positive electrode mainly made of carbon, and an electrolyte that also serves as a positive electrode active material mainly composed of sulfur oxyhalide. The main idea is to use a pair of electrodes, the anode of which is made of a light metal anode and the cathode of which is made of a carbonaceous material, which are subjected to energization treatment as the self-electrolyte. By using an electrolytic solution that has undergone such a battery reaction in advance, it is possible to obtain a non-aqueous solvent battery with twisted initial discharge characteristics that does not cause a significant voltage drop even when discharged at a large current after storage.

It is desirable that the cathode used in the above H12 energization process be formed from a porous carbon body, especially from the viewpoint of improving the efficiency of the battery reaction.

The above energization treatment conditions are 100 r for 10 rM electrolyte.
It is preferable to use an amount of electricity of nAb to 2A11.[Embodiments of the Invention] Hereinafter, embodiments of the present invention will be described in detail with reference to FIG. 1.

1 in the figure is a stainless steel can which also serves as a negative electrode terminal with an open top surface, and a cylindrical negative electrode 2 made of metallic lithium is crimped onto the inner surface of this can. Inside the can 1 inside the negative electrode 2, a positive electrode 5 having a structure in which a cylindrical porous carbon layer 4 is crimped onto the outside of a metal current collector 3 made of a cylindrical stainless steel mesh is housed in a cage made of glass fiber nonwoven fabric. shaped separator'
t, 6tt- provided through. Note that the positive electrode 5
For example, commercially available acetylene black and polytetrafluoroethylene are mixed, and this mixture is formed into a cylindrical shape together with a metal current collector 3 made of a stainless steel net so that the current collector 3 is on the inside. The porous carbon body 4 is produced by drying the kneaded material under vacuum at 150°C.

Further, in the can body 1 above the positive electrode 5, an insulating paper 7 supported by the separator 6 and having a hole in the center is disposed. A metal top 8 is sealed to the upper opening of the can body 1 by laser welding or the like. A hole 9 is opened in the center of the metal top 8, and a pipe-shaped positive electrode terminal 10 is electrically insulated from the metal dog 8 through a metal-glass sealing material 1. Fixed. The lower end of the positive electrode terminal 10 is connected to the metal current collector 3 of the positive electrode 5 via a lead wire 12. The can body 1 accommodates an electrolytic solution 13 injected from the pipe-shaped positive electrode terminal 10. This electrolyte 13
The composition is 1.5 mol/l of aluminum chloride (HTCLS) and lithium chloride (LiCI) dissolved in thionyl chloride (SOClw), and the anode is made of lithium and the cathode is made of acetylene black before injection. Using a pair of electrodes made of porous carbon, a lOmI! solution was energized with a current of 1QQrnA for 10 hours.A sealing body 14 made of stainless steel, for example, was inserted into the pipe-shaped positive terminal lO. The hole of the positive terminal IO is sealed by laser welding the tip of the terminal 10 and the inserted seal 14.

Comparative Example A battery having the same structure as the example was assembled, except that an electrolytic solution was used that was not energized before injection.

After assembling, the batteries of this example and comparative example were stored at 25°C for 3 months, and their initial characteristics were investigated with a constant resistance of 30Ω (i:
A characteristic diagram shown in the m2 diagram was obtained.

In FIG. 2, A indicates the discharge curve of the battery of the example, and B indicates the discharge curve of the battery of the comparative example. As is clear from Fig. 2, the battery of this example, which uses an electrolyte that has been subjected to energization treatment before injection, has a higher initial discharge time than a conventional battery that is not subjected to energization treatment and uses an FC electrolyte. It can be seen that the voltage drop is small.

〔Effect of the invention〕

As described in detail above, according to the present invention, it is possible to provide a non-aqueous solvent battery that completely suppresses the voltage drop even at the initial stage of large current discharge and has excellent initial discharge characteristics.

[Brief explanation of the drawing]

FIG. 1 is a sectional view of a non-aqueous solvent battery showing an embodiment of the present invention, and FIG. 2 is a diagram showing discharge characteristics at the initial stage of large current discharge in the battery of the present invention and a conventional battery. l... Can body, 2... Negative electrode, 3... Metal current collector, 4
... Porous carbon layer, 5... Positive electrode, 61.62...
Separator, 8... Metal top, 10... Pipe-shaped positive terminal, 13... Electrolyte. Applicant's representative Patent attorney Takehiko Suzue 1st session Figure 2 Discharge time (seconds)

Claims (2)

[Claims] (1) A non-aqueous solvent composed of a negative electrode made of light metals such as lithium, sodium, and aluminum, a positive electrode mainly made of carbon, and an electrolytic solution that also serves as a positive electrode active material and whose main component is sulfur oxyhalide. A non-aqueous solvent battery, characterized in that the electrolytic solution is a pair of electrodes in which the anode is made of a light metal as a negative electrode and the B electrode is made of a carbon material, and the electrolyte is treated with gold. (2) The non-aqueous solvent battery according to claim 1, wherein the cathode used in the current treatment is made of a porous carbon body.