JPS60249252A - Nonaqueous solvent battery - Google Patents

Abstract

PURPOSE:To provide a nonaqueous solvent battery having low voltage drop in the initial stage of high rate discharge by using a solution prepared by adding methacrolein to a solution containing oxyhalide of sulfur as a positive active material and electrolyte. CONSTITUTION:Methacrolein is added to a solution mainly comprising oxyhalide of sulfur which serves as a positive active material and electrolyte. The amount of methacrolein is spacified to 1-25g per liter of electrolyte when monomer of methacrolein is added, but to 0.2-10g per liter when polymer of mechacrolein is added. The electrolyte, a negative electrode such as Li, Na, or Al, and a positive electrode mainly comprising carbon are used to assemble a nonaqueous solvent battery. By this battery, voltage drop in the initial stage of high rate discharge is suppressed and voltage recovery time is shortened.

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.

[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 high energy density, excellent storage characteristics, and a wide operating temperature range, making them useful as backups for calculators, watches, and memory. It is widely used as a battery. Among them, lithium is used as the negative electrode.
using thionyl chloride (SOCT2) as the positive electrode active material.
Batteries using oxynochlorinated sulfur compounds such as sulfuryl chloride (SO□Ct2) are attracting attention because of their particularly high energy density. It has a positive electrode made of such a battery-like carbon and metal current collector, and is generally made by dissolving a Lewis acid such as aluminum chloride (AtCt) or aluminum bromide (MujBrs) and a Lewis base such as lithium chloride or lithium bromide. A liquid oxinol-10 compound of sulfur is used as the electrolyte. Therefore, the liquid oxyhalodanide serves both as a positive electrode active material and as an electrolyte, and by using a positive electrode with a suitable shape, a battery with excellent high rate discharge characteristics can be expected.

By the way, in the above-mentioned battery, since the sulfur oxyhalodide, which is the positive electrode active material, is in direct contact with the lithium, which is the negative electrode, a LICt film, which is a reaction product, is generated on the surface of the negative electrode lithium. This LIC1 film has the function of preventing direct contact between the negative electrode lithium and the oxyhalodide, 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 it cannot be ignored when the discharge current is large, and especially when stored at high temperatures for long periods of time, considerable growth of the LiCj film occurs. After discharge or during discharge at low temperatures, there is a problem in that a significant voltage drop occurs at the start of discharge, and it takes a long time to recover to a predetermined voltage.

[Purpose of the invention]

The present invention aims to provide a non-aqueous solvent battery that exhibits a small voltage drop even in the early stages of large 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 electrolytic solution that also serves as a positive electrode active material and mainly made of sulfur oxyhalodanide. The above-mentioned oxygen as an electrolyte
・The main idea is to use a solution containing rhodanide with methacrolein added. By using such an electrolyte solution containing methacrolein, there is no significant voltage drop even when a large current is discharged after storage.
Moreover, a nonaqueous solvent battery with excellent initial discharge characteristics and short voltage recovery time can be obtained.

The above methacrolein may be either a monomer or a polymer. When such methacrolein is a monomer, it is 1 to 2
5 cc, and in the case of polymers, it is desirable to add in the range of 0.2 to 10 I. The reason for this is that if the amount of methacrolein added is less than the lower limit above, the addition effect will be insufficient), but if it exceeds the upper limit, the effect will not increase or the discharge capacity of the battery will decrease. Decrease.

[Embodiments of the invention]

Hereinafter, embodiments of the present invention will be described in detail with reference to FIG.

Embodiment 1 Reference numeral 1 in the figure denotes a stainless steel can which doubles as a negative electrode terminal and has 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 is a positive electrode 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! A cylindrical separator 6 made of glass fiber nonwoven fabric
It is provided via 1r6m. The positive electrode is made by mixing commercially available acetylene f-lac and polytetrachloroethylene, and forming the mixture into a cylindrical shape together with a metal current collector 3 made of a stainless steel mesh so that the current collector 3 is on the inside. After molding, the porous carbon layer 4 is produced by drying the kneaded material under vacuum at 150°C.

Further, in the can body 1 above the positive electrode i, an insulating paper 7 supported by the separator 61 and having a hole in the center is disposed. The top opening of the can body 1 has a metal track 7°8.
was crowned by Rede Welder. A hole 9 is opened in the center of this metal tiger f8.
Inno wipe upper terminal, 10 is metal-glass sealing material 1
It is electrically insulated and fixed to the metal TOZZO 8 via 1. The lower end of the positive electrode terminal 10 is connected to the lead wire 1
2 to the metal current collector 8 of the positive electrode i. In the can body 1, there is the A? An electrolytic solution 13 injected from the pig-shaped positive electrode terminal 0 is accommodated therein. This electrolyte 13 contains aluminum chloride (HTCT) and lithium chloride (LiCj) in thionyl chloride (SOCl2).
1.5 mol/! 2 ca/# of methacrolein (monomer liquid) was added to the dissolved solution.

Further, a needle body 14 made of stainless steel, for example, is inserted into the positive electrode terminal 1o, and when the tip of the terminal 1° and the inserted needle body 14 are laser welded, the hole of the positive electrode terminal 10 is sealed. has been done.

Comparative Example 1 A battery having the same structure as in Example 1 was assembled, except that an electrolytic solution containing 1.5 mol/J of htct and LICt dissolved in 5oct2 without the addition of methacrolein was used.

After assembly, the batteries of Example 1 and Comparative Example 1 were stored at 25°C for 3 months, and a constant resistance discharge of 30Ω was performed to examine the characteristics at the initial stage of discharge. I got the diagram. In addition, in FIG. 2, A shows the discharge curve of the battery of Example 1, and B shows the discharge curve of the battery of Comparative Example. As is clear from Figure 2, the battery of Example 1, which uses an electrolyte with methacrolein (monomer liquid) added, has a lower initial voltage drop than the battery of Comparative Example 1, which uses an electrolyte without methacrolein. It can be seen that the voltage is small and the voltage recovery time is short.

Example 2 2 g of polymethacrolein produced by polymerizing in dimethylformamide using azobisisobutyronitrile as a polymerization initiator was added to 1.2 mol of IJ/J AICt3/Li
Comparative Example 2 A battery with the same structure as Example 1 was assembled except that an electrolyte added to CtIC3/LiCt was used. 1.2 mol/! of htct3 and LICt each in 5OC42 as an electrolyte! A battery having the same structure as in Example 1 was assembled, except that a battery without the addition of dissolved polymethacrolein was used.

Therefore, the batteries of Example 2 and Comparative Example 2 were stored at 45°C for 20 days after assembly, and a constant resistance discharge of 30Ω was performed, and the lowest voltage at the start of discharge was 2.5V.
We investigated the time it took to recover. The results are shown in the table below.

Table As is clear from the above table, the battery of Example 2 using the electrolyte containing polymethacrolein has a higher initial voltage even after high temperature storage than the battery of Comparative Example 2 using the electrolyte without polymethacrolein. It can be seen that the drop is small and the voltage recovery time is short.

〔Effect of the invention〕

As described in detail above, according to the present invention, it is possible to provide a non-aqueous solvent battery with excellent initial discharge characteristics, such as suppressing voltage drop and shortening voltage recovery time even in the initial stage of large current discharge.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of a non-aqueous solvent battery showing an example of the present invention, and FIG. 2 is a diagram showing the discharge characteristics of the battery of Example 1 and the battery of Comparative Example 1 at the initial stage of large current discharge. be. 1... Can body, 2... Negative electrode, 3... Metal current collector, 4
...Porous carbon layer! . . . Positive electrode, 61Ω 6g/shaft cell unit, 8 . . . Metal top, 1o . . . Pipe-shaped positive terminal, 13 . . . Figure 1 L

Claims (1)

[Claims] In a non-aqueous solvent battery comprising a negative electrode made of light metals such as lithium, sodium, and aluminum, a positive electrode mainly made of carbon, and an electrolytic solution serving as a positive electrode active material mainly composed of sulfur oxyhalodanide, the above-mentioned 1. A non-aqueous solvent battery, characterized in that an electrolyte containing a solution containing the oxyhalodanide to which methaqutetralein is added is used.